JP3380376B2 - Manufacturing method of cosmetics - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cosmetic composition which has a long-lasting cosmetic effect and is resistant to twisting and collapse. More specifically, the present invention relates to a fluorine-modified silicone having a silanol group in the molecule. The present invention relates to a method for producing a cosmetic having excellent durability of cosmetic effect by blending a resin dispersion .

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION In the previous application, the present inventor has made a fluorine-modified silicone resin having a silanol group in the molecule (hereinafter referred to as FQ resin).
It has been proposed that various characteristics can be obtained by blending ss with cosmetics.

However, since this FQ resin is originally solid and has the purpose of water and oil repellency, it is dissolved in a solvent such as cyclic silicone or coated on powder when it is blended in a cosmetic composition. There is no compounding method other than the method of using, and there is a problem that it is difficult to compound with powder foundations and eye shadows that do not use a solvent.

Then, as a result of intensive studies to solve this problem, the present inventor obtained a dispersion of the FQ resin by finely pulverizing the FQ resin in an oil agent, and by adding this to a cosmetic, We have found that it is possible to easily mix FQ resin into cosmetics.

[0005]

That is, the present invention relates to a fluorine-modified silicone resin having a silanol group in the molecule, wherein a compound having the following structure is added to an oil agent (however,
Cyclic silicone and / or light liquid paraffin
Does not include. ) Is mixed with a dispersion liquid previously dispersed.
The present invention relates to a method for producing a featured cosmetic . Average formula R ¹ _n SiO _{(4-n) / 2} (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf, wherein the hydroxyl group and the general formula are -R ² is selected -Rf from the functional groups essentially containing optionally, ^{R 2} is a divalent alkylene group having 2 to 6 carbon atoms, Rf is a perfluoroalkyl group having 1 to 8 carbon atoms, n represents an average The number is 1.0 ≦ n ≦ 1.8.)

The FQ resin of the present invention preferably has an OH group in the silanol group in the molecule thereof in the range of 0.1 to 5% by weight based on the weight of the resin. That is, within this range, the adhesiveness to the skin and powders is necessary and sufficient.

Further, the FQ resin of the present invention preferably does not dissolve in squalane containing water in order to prevent the FQ resin from dissolving in sebum components. When dissolved in squalane,
There is also a problem that makeup durability is reduced.

The compounding amount of the FQ resin of the present invention in cosmetics is preferably 0.001 to 30 parts by weight, more preferably 0 to 100 parts by weight of the cosmetics in order to obtain the effects of the present invention. 1 to 10 parts by weight.

The FQ resin of the present invention is a cyclic silicone and
And / or dispersed in an oil agent other than light liquid paraffin in advance . As the type of oil agent, the oil agent conventionally used in cosmetics can be used. Examples of oil agents include stearyl alcohol, cetyl alcohol,
Higher alcohols such as isostearyl alcohol, lauryl alcohol, hexadecyl alcohol, octyldodecanol, glycerin, polyethylene glycol, 1,
Polyhydric alcohols such as 3-butanediol, propylene glycol and malbitol, fatty acids such as isostearic acid, stearic acid, undecylenic acid and oleic acid, myristyl myristate, hexyl laurate, decyl oleate, isopropyl myristate, isopropyl palmitate, Hexyldecyl dimethyloctanoate, glycerin monostearate, diethyl phthalate, ethylene glycol monostearate, esters such as octyl oxystearate, liquid paraffin, hydrocarbons such as vaseline and squalane, waxes such as lanolin, reduced lanolin and carnauba wax , mink oil, cacao butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, oils such as olive, ethylene-alpha-olefin co-oligomer, liquid isoparaffin, Pas rough Emissions, and the like.

Examples of other types of oil agents include, for example, dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, polyether-modified organopolysiloxane, perfluoroalkyl / polyoxyalkylene co-modified silicone, alkyl. Silicone compounds other than cyclic silicones such as modified organopolysiloxanes, modified organopolysiloxanes (substituents may be located at side chains or at terminals), fluorine-modified organopolysiloxanes, amodimethicone, amino-modified organopolysiloxanes, silicone gels, etc. And fluorine compounds such as perfluoropolyether, fluorinated pitch, fluorocarbon and fluoroalcohol.

It is also possible to use a solvent as an example of the oil agent. For example, ethanol, methanol,
Examples include isopropyl alcohol, LPG, ether, hexane, N -methylpyrrolidone, and isoprene glycol.

[0012] Among these oil agents, in the case of an oil agent in which the FQ resin does not match the polarity and the FQ resin is separated and aggregated, it is necessary to disperse the FQ resin in combination with a surface-active component.
As examples of the surface active component, polyether-modified silicone, alkyl / polyether co-modified silicone, and perfluoroalkyl / polyoxyalkylene co-modified silicone are preferable.

In general, it is preferable to use the above-mentioned silicone type oil agent. When the dispersion liquid is obtained, the FQ resin may be partially dissolved in the oil agent.

The method for producing the dispersion of the present invention includes:
For example, after adding an oil agent to an FQ resin solution dissolved in a solvent, distilling off the solvent, and then finely pulverizing with a wet pulverizer to obtain a dispersion liquid, or a device such as a paint shaker, the FQ resin is used. And a method of physically pulverizing the syrup with a pulverizing medium to obtain a dispersion.

In the cosmetic of the present invention, in addition to the above-mentioned components, powders, oils, resins, surfactants, ultraviolet absorbers, fragrances, preservatives, bactericides, moisturizers, which are usually used in cosmetics, A viscous agent, a physiologically active ingredient, a solvent, salts, water and the like can be added at the same time.

Examples of powders are Red No. 104 and Red 2.
No. 01, yellow No. 4, blue No. 1, black No. 401, etc.
Rake pigments such as yellow No. 4 Al lake and yellow No. 203 Ba lake, polymers such as nylon powder, silk powder, urethane powder, Teflon powder, silicone powder, cellulose powder, yellow iron oxide, red iron oxide,
Colored pigments such as black iron oxide, chromium oxide, carbon black, ultramarine blue and dark blue, white pigments such as zinc oxide, titanium oxide and cerium oxide, body pigments such as talc, mica, sericite and kaolin, and pearl pigments such as titanium mica. , Barium sulfate, calcium carbonate, magnesium carbonate, aluminum silicate, magnesium silicate and other metal salts, silica, alumina and other inorganic powders, fine particles of titanium oxide, fine particles of zinc oxide, fine particles of iron oxide, alumina treated particles of titanium oxide, silica treated particles Examples thereof include titanium oxide, bentonite, and smectite. There is no particular limitation on the shape of these powders.

These powders are conventionally known surface treatments, for example, fluorine compound treatment, silicone treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, oil agent treatment, N-acylated lysine treatment, polyacryl. It may or may not be surface-treated in advance by acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment and the like.

Examples of the fluorine compound treatment include surface treatment using perfluoroalkyl phosphoric acid ester and its salt, perfluoroalkylsilane, Teflon, perfluoroalkylcarboxylic acid, metal soap treatment, surface fluorination treatment by plasma, Examples include mechanochemical composite treatment with Teflon.

Examples of the oil agent include the oil agents exemplified above.

As the surface active agent, for example, an anionic surface active agent, a cationic surface active agent, a nonionic surface active agent or an amphoteric surface active agent can be used.

Examples of the organic ultraviolet absorber include 2-ethylhexyl paramethoxycinnamate (eg, Parasol M).
CX, manufactured by Givaudan), paradimethylaminobenzoic acid 2
-Ethylhexyl, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, p-methoxyhydrocinnamic acid diethanolamine salt, para-aminobenzoic acid (Hereinafter PA
Abbreviated as BA), ethyldihydroxypropyl PABA,
Glyceryl PABA, homomenthyl salicylate, methyl-O-aminobenzoate, 2-ethylhexyl-2-
Cyano-3,3-diphenyl acrylate, octyl dimethyl PABA, octyl methoxycinnamate, octyl salicylate, 2-phenyl-benzimidazole-5
Sulfuric acid, triethanolamine salicylate, 3- (4-methylbenzylidene) camphor, 2,4-dihydroxybenzophenine, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4 '-
Dimethoxybenzophenone, 2-hydroxy-4-N-
Octoxybenzophenone, 4-isopropyldibenzoylmethane, butylmethoxydibenzoylmethane, 4
-(3,4-dimethoxyphenylmethylene) -2,5-
Examples thereof include 2-ethylhexyl dioxo-1-imidazolidinepropionate.

Examples of the sticking agent include polycarboxylic acid, polyacrylic acid, polyvinyl alcohol, agar, gellan gum, gum arabic, tragacanth gum, karaya gum, xanthan gum, tamarind gum, guar gum, alginic acid and carboxyvinyl polymer.

Examples of physiologically active ingredients are anti-inflammatory agents, tyrosinase activity inhibitors, plant extracts, vitamins,
Examples include sulfur and urea.

Examples of salts include sodium chloride, potassium chloride, calcium chloride, calcium lactate, aluminum chloride, various phosphates and the like.

Examples of the cosmetics of the present invention include oily foundations, emulsified foundations, foundations using water, foundations for both purposes, white powder, blusher, pressed powder, cheek color, undercover, lipstick, lip coat, eye shadow, eye liner. , Nail color, makeup base, emulsion, lotion, cream, sunscreen, hand lotion, conditioner, shampoo, dry shampoo, conditioner, hair liquid, hair treatment, setting agent, perfume, deodorant, cleansing agent, soap, etc. To be

[0026]

EXAMPLES The present invention will be described in detail below with reference to production examples, examples and comparative examples.

The evaluation of the collapse of the cosmetics used in the examples and comparative examples was carried out by using the cosmetics prepared in the examples and comparative examples for 10 male panelists aged 24 to 34. We asked them to answer the questions in a questionnaire. The evaluation is +10 points when responding that each panel has an effect, -10 points when responding that there is no effect, and 0 point when no panel is said to be effective. Was used as the evaluation result. Therefore, the higher the score, the higher the evaluation. In this evaluation, the level of sebum resistance and durability was evaluated as the collapse and drop of the cosmetic.

Production Example 1 147 parts by weight of 16% by weight hydrochloric acid water was placed in a reactor, and a mixture of 154 parts by weight of sodium J silicate No. 3 (manufactured by Nippon Kagaku Kogyo) and 220 parts by weight of water and isopropyl alcohol 158 were placed in the reactor. After adding 1 part by weight with stirring, CF ₃ CH
₂ CH ₂ (CH ₃ ) ₂ SiCl: 22 parts by weight, trimethylchlorosilane: 51.2 parts by weight and IP Solvent 1620 (manufactured by Idemitsu Petrochemical): 70 parts by weight A rate at which the internal temperature is maintained at 20 to 30 ° C. It was dripped at. Subsequently, after reacting at 80 to 90 ° C. for 5 hours, the reaction solution was washed with water until the aqueous layer became neutral. The reaction product was heated under reduced pressure, the reaction product obtained by distilling off the solvent, infrared absorption spectrum analysis,
As a result of nuclear magnetic resonance spectrum analysis, a fluorine-modified silicone resin having a structure represented by the following average composition formula was obtained.

(CF ₃ CH ₂ CH ₂ (CH ₃ ) ₂ SiO
_1/2 ) _0.088 ((CH ₃ ) ₃ SiO _1/2 ) _0.57 (SiO
_4/2 ) _0.78 (HOSiO _3/2 ) _0.22

The amount of hydroxyl groups was separately confirmed by the Karl Fischer method. As a result, the amount of hydroxyl groups was 3.
It was 0% by weight.

Production Example 2 147 parts by weight of 16% by weight hydrochloric acid water was placed in a reactor, and a mixture of 154 parts by weight of sodium J silicate No. 3 and 220 parts by weight of water and 158 parts by weight of isopropyl alcohol were stirred in the reactor. After the addition, C ₄ F ₉ CH ₂ CH ₂ (C
H ₃ ) ₂ SiCl: 80.7 parts by weight, trimethylchlorosilane: 38.4 parts by weight and IP solvent 162
0:70 parts by weight of the mixture was added dropwise at such a rate that the internal temperature was maintained at 20 to 30 ° C. Subsequently, after reacting at 80 to 90 ° C. for 5 hours, the reaction solution was washed with water until the aqueous layer became neutral. The reaction product obtained by heating the reaction product under reduced pressure and distilling off the solvent was subjected to infrared absorption spectrum analysis and nuclear magnetic resonance spectrum analysis, and as a result, fluorine-modified having a structure represented by the following average composition formula. A silicone resin was obtained.

(C ₄ F ₉ CH ₂ CH ₂ (CH ₃ ) ₂ Si
O _1/2 ) _0.19 ((CH ₃ ) ₃ SiO _1/2 ) _0.44 (SiO
_4/2 ) _0.82 (HOSiO _3/2 ) _0.18

The amount of hydroxyl groups was confirmed by the Karl Fischer method as described above. As a result, the amount of hydroxyl groups was 2.0% by weight.

Production Example 3 100 parts by weight of the FQ resin obtained in Production Example 1 was dissolved in 300 parts by weight of octamethylcyclotetrasiloxane (hereinafter referred to as D4) to obtain a solution. To this, 100 parts by weight of dimethylpolysiloxane (10 cSt, 25 ° C.) was added, and D4 was distilled off by heating with stirring. Then, fine pulverization was performed with a wet fine pulverizer (Micros, manufactured by Nara Machinery Co., Ltd.) to obtain a target dispersion liquid.

Production Example 4 100 parts by weight of the FQ resin obtained in Production Example 2 was added to 100 parts by weight of perfluoropolyether, and the mixture was pulverized by using a paint shaker together with a pulverizing medium, and then a wet pulverizer (micros). Fine pulverization was performed to obtain a target dispersion liquid.

Example 1 Foundation Using the FQ resin dispersion liquid of Production Example 3, a foundation was prepared according to the formulation shown in Table 1. As the modified powder, 5% of perfluoroalkyl phosphate ester salt manufactured by Daito Kasei
The treated powder was used.

[0037]

[Table 1]

After mixing the powder components with a Henschel mixer, the liquid components were added and further stirred and mixed. Then, after pulverizing with an atomizer, it was punched with a die to obtain a product.

Example 2 Sunscreen Agent Using the FQ resin dispersion obtained in Production Example 4, a sunscreen agent was obtained according to the formulation shown in Table 2.

[0040]

[Table 2] ^* Note) D5: Decamethylcyclopentasiloxane

The mixture of each component was crushed using a paint shaker and then filled in a bottle together with a stainless ball to obtain a product.

Comparative Example 1 Foundation A foundation was obtained in the same manner except that dimethylpolysiloxane (10 cSt) was used in place of the FQ resin dispersion liquid of Example 1.

Comparative Example 2 Sunscreen Agent A sunscreen agent was obtained in the same manner as in Example 1 except that perfluoropolyether was used instead of the FQ resin dispersion liquid.

Table 3 shows the results of the evaluation of the difficulty of falling and the difficulty of falling of the cosmetics using the examples and comparative examples.

[0045]

[Table 3]

From the comparison between the example and the comparative example, it can be seen that the example is more resistant to collapse of the cosmetic material than the comparative example and is excellent in durability and sebum resistance.

[0047]

From the above, it is clear that the present invention provides a method for producing a cosmetic composition which is less likely to lose makeup and has excellent durability of the cosmetic effect.

Claims (2)

(57) [Claims] 1. A fluorine-modified silicone resin having a silanol group in the molecule, wherein a compound having the following structure is added to an oil agent (provided that cyclic silicone and / or light
Does not contain liquid paraffin. ) To a dispersion previously dispersed in
A method for producing a cosmetic, comprising blending . Average formula R ¹ _n SiO _{(4-n) / 2} (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, a phenyl group, a hydroxyl group, or a general formula —R ² —Rf, wherein the hydroxyl group and the general formula are -R ² is selected -Rf from the functional groups essentially containing optionally, ^{R 2} is a divalent alkylene group having 2 to 6 carbon atoms, Rf is a perfluoroalkyl group having 1 to 8 carbon atoms, n represents an average The number is 1.0 ≦ n ≦ 1.8.) 2. An oil agent is a silicone compound (provided that a cyclic compound is used).
Does not contain recone. Cosmetic method according to claim 1, characterized in that) it is.