JP6614642B2 - Composition for makeup cosmetics - Google Patents

Description

  The present invention relates to a makeup cosmetic composition containing a modified polysiloxane compound.

  Amphiphilic polymer compounds have a high molecular weight and therefore have low skin penetration, less irritation to the skin, and strong adhesion that adheres firmly to the particle surface and coats the particles. Aggregation can be suppressed, dispersion stability can be imparted to particles, and various higher-order structures and aggregates can be formed due to the hydrophilic / hydrophobic balance. Yes.

  Examples of amphiphilic polymer compounds used in cosmetics include sodium alginate, sodium pectinate, xanthan gum, chitosan, corn starch and various starches; carboxymethylcellulose, carboxy starch, (meta) Semi-synthetic amphiphilic polymer compounds such as acrylic acid grafted starch, cationic starch, methylcellulose, ethylcellulose, hydroxyethylcellulose; silicone surfactants, (meth) acrylic acid copolymers, vinylpyridine copolymers, polyvinylpyrrolidone, Polyethyleneimine, polyoxyethylene polyoxypropylene copolymer, polyvinyl alcohol, polyvinyl ether, polyacrylamide, ethylene oxide adduct of alkylphenol formaldehyde condensate Such as synthetic based amphiphilic polymer compounds are known.

  The silicone surfactant is widely used as an emulsifying / gelling agent for a cosmetic composition containing silicone oil.

JP 2001-058926 A JP 2005-194523 A JP 2004-169015 A

  However, the powder dispersibility of the silicone surfactant is still insufficient. Further, a cosmetic composition containing a silicone surfactant has a problem in that it is inferior in terms of skin adhesion.

  Accordingly, an object of the present invention is to provide a composition for makeup cosmetics that is excellent in dispersion stability of the contained powder and skin adhesion.

  As a result of intensive studies to solve the above problems, the present inventors have identified a modified polysiloxane compound obtained by grafting a saturated hydrocarbon group and a dihydroxypropylamide group to a polysiloxane compound, an oil phase component, and a powder. It was found that the cosmetic composition contained in this ratio was excellent in powder dispersion stability and skin adhesion. The present invention has been completed based on these findings.

［式中、Ｒ¹〜Ｒ⁹は、同一又は異なって、炭素数１〜２０の直鎖状アルキル基、炭素数３〜６の分岐鎖状アルキル基、及び炭素数３〜６の環状アルキル基から選択される炭化水素基を示す。ｐ、ｑは、それぞれ括弧内に示されるシロキサン単位の数の平均値を示し、ｐは１以上の数、ｑは２以上の数である。Ａは下記式（２）で表される基、下記式（３）で表される基、及び水素原子から選択される基を示す。但し、変性ポリシロキサン化合物（Ａ）は、Ａが下記式（２）で表される基であるシロキサン単位、及びＡが下記式（３）で表される基であるシロキサン単位を少なくとも有している］

（式（２）中、Ｒ¹⁰は単結合、又は炭素数１〜１７の直鎖状若しくは分岐鎖状アルキレン基を示す。式（３）中、Ｒ¹¹は単結合、又は炭素数１〜１７の直鎖状若しくは分岐鎖状アルキレン基を示し、Ｒ¹²は水素原子又は炭素数１〜６の直鎖状、分岐鎖状、若しくは環状アルキル基を示す。尚、式（２）、及び（３）の左端がケイ素原子に結合する） That is, the present invention provides a makeup cosmetic composition containing the modified polysiloxane compound (A) represented by the following formula (1), the oil phase component (B), and the powder (C) in the following range. provide.
(A): 0.1 to 20% by weight of the total amount of the composition
(B): 0.1 to 95% by weight of the total amount of the composition
(C): 0.01 to 99% by weight of the total amount of the composition

[Wherein, R ^{1 to} R ⁹ are the same or different and are each a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic alkyl group having 3 to 6 carbon atoms. The hydrocarbon group selected from these is shown. p and q each represent an average value of the number of siloxane units shown in parentheses, p is a number of 1 or more, and q is a number of 2 or more. A represents a group selected from a group represented by the following formula (2), a group represented by the following formula (3), and a hydrogen atom. However, the modified polysiloxane compound (A) has at least a siloxane unit in which A is a group represented by the following formula (2) and a siloxane unit in which A is a group represented by the following formula (3). Yes]

(In Formula (2), R ¹⁰ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms. In Formula (3), R ¹¹ represents a single bond or 1 to 17 carbon atoms. Wherein R ¹² represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, wherein formulas (2) and (3) The left end of) is bonded to the silicon atom)

  The present invention also provides at least one compound selected from the group consisting of silicone oil, high polarity oil, low polarity oil, higher fatty acid, fat-soluble vitamin, and oil-soluble thickener as oil phase component (B). And a makeup cosmetic composition as described above comprising a pigment and / or a UV protection agent as powder (C).

  The present invention also provides the makeup cosmetic composition as described above, wherein the powder (C) is a powder (excluding an organic surface-treated powder) (C).

  The present invention also provides the above makeup cosmetic composition, wherein the makeup cosmetic is lipstick, lip gloss, foundation, teak, mascara, eyeliner, or eye shadow.

  Since the composition for makeup cosmetics of this invention has the said structure, it is excellent in the dispersion stability of powder. Therefore, it has excellent coating properties, no color unevenness, good color development, and a beautiful finish. In addition, it has excellent skin adhesion and good makeup. Furthermore, there is little irritation | stimulation to skin and it is excellent in safety.

It is a figure which shows the preparation method of the sample attached | subjected to skin adhesion evaluation. It is a figure which shows a skin adhesive evaluation result.

[Modified polysiloxane compound (A)]
The modified polysiloxane compound in the present invention is represented by the following formula (1). In formula, R < ¹ > -R < ⁹ > is the same or different, and is from a C1-C20 linear alkyl group, a C3-C6 branched alkyl group, and a C3-C6 cyclic alkyl group. Indicates the hydrocarbon group selected. p and q each represent an average value of the number of siloxane units shown in parentheses, p is a number of 1 or more, and q is a number of 2 or more. When p is 2 or more, two or more of R ⁷ and R ⁸ may be the same or different. Further, two or more R ⁹ may be the same or different.

The modified polysiloxane compound represented by the formula (1) is a random or block copolymer composed of a siloxane unit represented by the following formula (a) and a siloxane unit represented by the following formula (b). In the following formulae, R ⁷ , R ⁸ , R ⁹ and A are the same as described above.

In the above formula, A represents a group selected from a group represented by the following formula (2), a group represented by the following formula (3), and a hydrogen atom. In the formula (2), R ¹⁰ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms. In the formula (3), R ¹¹ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms, and R ¹² represents a hydrogen atom or a linear or branched chain having 1 to 6 carbon atoms. Or a cyclic alkyl group. In addition, the left end of Formula (2) and (3) couple | bonds with a silicon atom.

That is, the siloxane unit represented by the above formula (a) is any of the siloxane units represented by the following formulas (a1), (a2), and (a3). In the following formula, R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are the same as described above.

  However, in the modified polysiloxane compound in the present invention, A is a siloxane unit in which A is a group represented by the above formula (2) (that is, a siloxane unit represented by the above formula (a1)), and A is the above formula (3). ) At least a siloxane unit (that is, a siloxane unit represented by the above formula (a2)).

Examples of the linear alkyl group having 1 to 20 carbon atoms in R ^{1 to} R ⁹ include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl group and the like. Can do. Examples of the branched alkyl group having 3 to 6 carbon atoms include isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl group and the like. Examples of the cyclic alkyl group having 3 to 6 carbon atoms include cyclopentyl and cyclohexyl. In the present invention, a linear alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.

The linear or branched alkylene group having 1 to 17 carbon atoms in R ¹⁰ is preferably a linear alkylene group having 1 to 17 carbon atoms or a branched alkylene group having 2 to 17 carbon atoms. Linear alkylene groups such as methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene group; methylmethylene, methylethylene, etc. And a branched alkylene group in which an alkyl group having about 1 to 3 carbon atoms is graft-bonded to the linear alkylene group. R ¹⁰ in the present invention is preferably a linear or branched alkylene group having 2 to 13 carbon atoms (particularly a linear alkylene group).

The linear or branched alkylene group having 1 to 17 carbon atoms in R ¹¹ is preferably a linear alkylene group having 1 to 17 carbon atoms or a branched alkylene group having 2 to 17 carbon atoms. Examples similar to the examples of the linear or branched alkylene group having 1 to 17 carbon atoms in ¹⁰ can be given. R ¹¹ in the present invention is preferably a linear or branched alkylene group having 2 to 13 carbon atoms (particularly a linear alkylene group).

As the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms in R ^12, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 2 to 6 carbon atoms, or carbon A cyclic alkyl group of 3 to 6 is preferable, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, sec-butyl, tert-butyl, neopentyl, 1-ethylpropyl, cyclopentyl, cyclohexyl group and the like. Can do. R ¹² in the present invention is preferably a hydrogen atom or a methyl group.

  p and q each represent an average value of the number of siloxane units shown in parentheses, and p is a number of 1 or more, preferably 2 to 2000, more preferably 4 to 500, and most preferably 10 to 30. q is a number of 2 or more, preferably 2 to 2000, more preferably 4 to 500, and most preferably 10 to 30.

  (P + q) is, for example, about 4 to 5000, preferably 8 to 1000, more preferably 10 to 50, and most preferably 10 to 40.

  As a ratio of the siloxane unit represented by the formula (a) to the entire siloxane unit represented by the formula (a) and the siloxane unit represented by the formula (b) (100 mol%), for example, 5 to 90 mol% It is about 10 to 90 mol%, more preferably 10 to 70 mol%, still more preferably 30 to 60 mol%, particularly preferably 35 to 50 mol%, and most preferably 40 to 50 mol%. That is, q / (p + q) is about 0.05 to 0.9, preferably 0.1 to 0.9, more preferably 0.1 to 0.7, still more preferably 0.3 to 0.6, Especially preferably, it is 0.35-0.5, Most preferably, it is 0.4-0.5.

  Moreover, as a ratio of the siloxane unit represented by Formula (b) with respect to the whole (100 mol%) of the siloxane unit represented by Formula (a) and the siloxane unit represented by Formula (b), it is 5-90, for example. It is about mol%, preferably 10 to 90 mol%, more preferably 10 to 70 mol%, particularly preferably 30 to 60 mol%, and most preferably 50 to 60 mol%. That is, p / (p + q) is about 0.05 to 0.9, preferably 0.1 to 0.9, more preferably 0.1 to 0.7, particularly preferably 0.3 to 0.6, Most preferably, it is 0.5-0.6.

  Furthermore, siloxane units in which A in the formula (a) is a group represented by the formula (2) with respect to the entire siloxane units (100 mol%) represented by the formula (a) (that is, in the above formula (a1)) The proportion of the siloxane unit represented is preferably about 75 to 99 mol%, and in particular, 80 to 98 mol%, particularly 80 to 95 mol%, is miscible with other compounding raw materials. It is preferable at the point which is excellent in property. When the ratio of the siloxane unit represented by the above formula (a1) is less than the above range, the miscibility with hydrocarbon wax or oil tends to decrease. On the other hand, when the proportion of the siloxane unit represented by the above formula (a1) exceeds the above range, the miscibility with a silicone-based component or the like tends to decrease.

  Furthermore, the siloxane unit in which A in the formula (a) is a group represented by the formula (3) with respect to the entire siloxane unit (100 mol%) represented by the formula (a) (that is, the above formula (a2) The ratio of the siloxane unit represented by the formula (1) is preferably 1 mol% or more, and more preferably 2 to 25 mol%, and particularly preferably 5 to 20 mol%. When the ratio of the siloxane unit represented by the above formula (a2) is below the above range, the film-forming property and the skin adhesion tend to be lowered. On the other hand, even if the proportion of the siloxane unit represented by the above formula (a2) is too large, the viscosity becomes too high, the solubility in the oil phase component (B) decreases, and the handling properties in the production process. There is a tendency for usability to decrease.

  Further, the siloxane unit in which A in the formula (a) is a hydrogen atom (that is, the siloxane unit represented by the above formula (a3)) with respect to the entire siloxane unit (100 mol%) represented by the formula (a). The ratio is preferably about 10 mol% or less (in particular, 5 mol% or less, particularly 2 mol% or less), and the siloxane unit represented by the above formula (a3) may not be substantially contained. . When the ratio of the siloxane unit represented by the above formula (a3) exceeds the above range, the water repellency, oil repellency, emulsion stability, dispersibility, compoundability, and storage stability tend to decrease. Further, when the Si—H group of the siloxane unit represented by (a3) remains in the makeup cosmetic composition without being consumed by the reaction with the powder (C), the makeup cosmetic is stored during storage. Moisture contained in the composition for use and the Si—H group may react gradually to generate hydrogen gas, which may cause problems such as swelling of the container and ejection of the contents when opened.

The number of siloxane units represented by formula (b) constituting the modified polysiloxane compound represented by formula (1) is p, the number of siloxane units represented by formula (a1) is (q-1), ( When the number of siloxane units represented by a2) is represented as (q-2)
The ratio of p to the total of p, (q-1), and (q-2) is, for example, 10 to 90 mol%, more preferably 30 to 60 mol%, and still more preferably 45 to 55 mol%.
The ratio of (q-1) to the total of p, (q-1), and (q-2) is, for example, 10 to 90 mol%, more preferably 20 to 50 mol%, and still more preferably 35 to 45 mol%.
The ratio of (q-2) to the total of p, (q-1), and (q-2) is, for example, 1 to 20 mol%, more preferably 5 to 15 mol%, and still more preferably 5 to 10 mol%.

  The modified polysiloxane compound represented by the formula (1) has a siloxane unit having a lipophilic group represented by the formula (2) and a siloxane unit having a hydrophilic group represented by the formula (3). In addition, it can be mixed with the oil phase component (B) at a relatively low temperature without requiring a high-temperature dissolution step, and the production cost and environmental burden can be reduced.

  In addition, the modified polysiloxane compound represented by the formula (1) is excellent in emulsion stability and gelling ability, and not only has excellent ability to disperse powders such as pigments (dispersibility), but also water and oil repellency. Excellent. Therefore, the makeup cosmetic composition of the present invention containing the modified polysiloxane compound represented by the formula (1) can form a film excellent in water repellency and oil repellency, and has a finish and a feeling of use. Good, particularly good adhesion to the skin (that is, long-lasting makeup).

The modified polysiloxane compound represented by the above formula (1) is, for example, a polysiloxane compound represented by the following formula (4), a compound represented by the following formula (5), and a table represented by the following formula (6): Is produced through a step of grafting the compound to be produced by a hydrosilylation reaction.

In formula (4), R ^{1 to} R ⁹ are the same or different and are a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic group having 3 to 6 carbon atoms. A hydrocarbon group selected from alkyl groups is shown. p and q each represent an average value of the number of siloxane units shown in parentheses, p is a number of 1 or more, and q is a number of 2 or more. R ^{1 to} R ⁹ and p and q correspond to R ^{1 to} R ⁹ and p and q in the modified polysiloxane compound represented by the formula (1), respectively.

In the formula (5), R ¹⁰ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms. R ¹⁰ corresponds to R ¹⁰ in the group represented by the formula (2) in the modified polysiloxane compound represented by the formula (1).

In Formula (6), R ¹¹ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms, and R ¹² represents a hydrogen atom or a linear or branched chain having 1 to 6 carbon atoms. Or a cyclic alkyl group. R ¹¹ and R ¹² correspond to R ¹¹ and R ¹² in the group represented by the formula (3) in the modified polysiloxane compound represented by the formula (1), respectively.

  The hydrosilylation reaction is preferably performed in the presence of a catalyst. The catalyst is not particularly limited as long as it is a catalyst generally used for hydrosilylation reaction. In the present invention, chloroplatinic acid, Karstedt catalyst, dichloro (cycloocta-1,5-diene) Platinum group metal compounds such as platinum, palladium chloride, chlorotris (triphenylphosphine) rhodium (I), dichlorotris (triphenylphosphine) ruthenium (II); platinum supported on solids such as platinum / carbon, palladium / carbon, platinum / alumina A platinum group metal protective colloid prepared by reducing various platinum group metal compounds in the presence of a surfactant; a platinum group metal oxide solid catalyst such as platinum oxide or the like can be suitably used.

The amount of the catalyst used is not particularly limited. For example, it is 10 ⁻⁷ to 10 ^{− with} respect to the total amount (1 mol) of the compound represented by formula (5) and the compound represented by formula (6). ^{A range of 2} mol (preferably 10 ⁻⁶ to 10 ⁻³ mol, particularly preferably 10 ⁻⁵ to 10 ⁻⁴ mol) is preferable. When the amount of the catalyst used is too small, a long reaction time is required, and there is a concern that the quality may be adversely affected by coloring due to thermal history or mixing of by-products into the product. On the other hand, if the amount of the catalyst used is excessive, the above-mentioned catalyst used for the hydrosilylation reaction is generally expensive, and this is not preferable because it increases the production cost.

  The hydrosilylation reaction is performed in the presence or absence of a solvent. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, hydrocarbon solvents such as pentane, hexane, and cyclohexane; aromatic solvents such as benzene, toluene, and xylene; cyclopentyl methyl ether, diethyl ether, Ether solvents such as diisopropyl ether; alcohol solvents such as methanol, ethanol, isopropanol and butanol; cyclic silicone solvents such as octamethyltetracyclosiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; ethyl acetate and isopropyl acetate And ester solvents such as butyl acetate; and mixtures thereof. When the alcohol solvent is used, a pH adjuster such as potassium acetate (see JP-A-57-149290) may be used in order to prevent or suppress the reaction between the Si—H group and the hydroxyl group. desirable.

  The hydrosilylation reaction temperature is, for example, 0 ° C. to 200 ° C., and it is preferably performed at 0 ° C. to 100 ° C. in consideration of the reaction rate, coloring, and the like. The reaction time is not particularly limited, but is preferably 0.5 to 72 hours from the viewpoint of productivity.

  The reaction may be performed under normal pressure, or may be performed under reduced pressure or increased pressure. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  When impurities (for example, a compound represented by the above formula (5) and its isomer, and / or a compound represented by the above formula (6) and its isomer) are mixed into the reaction product, emulsification / gelation The quality may be deteriorated due to deterioration of characteristics or generation of odor or harmful substances due to oxidative deterioration over time. In that case, after completion of the hydrosilylation reaction, dehydroboiling treatment under high vacuum conditions, decomposition by acid treatment (see JP-A-2-302438), or saturated hydrocarbonation by hydrogenation treatment ( It is desirable to remove the impurities by adding a post-treatment process such as extraction and removal with a solvent, as disclosed in JP-A-9-165318).

  According to the said manufacturing method, the modified polysiloxane compound represented by Formula (1) can be manufactured efficiently.

  The content of the modified polysiloxane compound (A) (when two or more types are contained, the total amount) is 0.1 to 20% by weight, preferably 0.3 to 15% by weight of the total amount of the makeup cosmetic composition. %, Particularly preferably 0.5 to 10% by weight, most preferably 0.7 to 7% by weight.

  The content of the modified polysiloxane compound (A) (when two or more types are contained, the total amount thereof) is, for example, 0.1 with respect to 100 parts by weight of the oil phase component (B) contained in the makeup cosmetic composition. -30 parts by weight, particularly preferably 0.5-20 parts by weight, most preferably 1-10 parts by weight.

  The content of the modified polysiloxane compound (A) (when two or more types are contained, the total amount) is, for example, 0.01 to 1 part by weight of the powder (C) contained in the makeup cosmetic composition. 3 parts by weight, particularly preferably 0.05 to 2 parts by weight, most preferably 0.1 to 1 part by weight.

  Since the composition for makeup cosmetics of the present invention contains the modified polysiloxane compound (A) in the above range, the powder (C) is prevented from agglomerating and stably maintained in a highly dispersed state. Can do. Moreover, the outstanding skin adhesiveness can be exhibited.

[Oil phase component (B)]
As the oil phase component (B), those having a high affinity for the polydialkylsiloxane main chain and / or side chain alkyl group of the modified polysiloxane (A) are preferably used. Silicone oil, highly polar oil, low Examples include polar oils, higher fatty acids, fat-soluble vitamins, and oil-soluble thickeners. These can be used alone or in combination of two or more.

  Examples of the silicone oil include higher alkoxy-modified silicones such as dimethylpolysiloxane (less than 50000 cs), methylphenylpolysiloxane, cyclic dimethicone, stearoxysilicone, alkyl-modified silicones, and higher fatty acid ester-modified silicones.

  Examples of the highly polar oil include neopentyl glycol dicaprate, tri (capryl / capric acid) glycerin, trimethylolpropane trioctanoate, cetyl octanoate, diisobutyl adipate, 2-hexyldecyl adipate, di-2 adipate -Heptylundecyl, isononyl isononanoate, isotridecyl isononanoate, isostearyl myristate, glyceryl trimyristate, glyceryl myristate / stearate, isocetyl stearate, butyl stearate, isostearyl isostearate, glyceryl diisostearate, triisostearic acid Trimethylolpropane, glyceryl triisostearate, cholesteryl 12-hydroxystearate, isopropyl 12-hydroxystearate Octyl 12-hydroxystearate, cetyl 2-ethylhexanoate, neopentyl glycol di-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, tetra-2-ethyl Pentaerythritol hexanoate, oleyl oleate, octyldodecyl oleate, decyl oleate, phytosteryl oleate, 2-ethylhexyl succinate, diisopropyl sebacate, cetyl lactate, myristyl lactate, octyl dodecyl lactate, isostearyl lactate, 2-palmitate Ethylhexyl, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, glyceryl triisopalmitate, diisostearyl malate, 2-ethylhexyl paramethoxycinnamate Diparamethoxycinnamic acid, glyceryl monoisooctylate, pentaerythritol tetrarosinate, dilauroyl glutamate (phytosteryl / octyldodecyl), dilauroglutamate (cholesteryl / phytosteryl / octyldodecyl), dilauroylglutamate (cholesteryl / octyldodecyl) , Dilauroylglutamate di (octyldodecyl / phytosteryl / benhenyl), lauroylsarcosine isopropyl, myristoylmethyl-β-alanine (phytosteryl / decyltetradecyl), glyceryl dioctyldodecanoate, lauryl alcohol, hexyldecanol, isostearyl alcohol, heptylun Examples include decanol, octyldodecanol, and decyltetradecanol.

  Examples of the low polar oil include olive oil, jojoba oil, avocado oil, sunflower oil, lavender oil, macadamia nut oil, liquid paraffin, liquid polyisobutylene, squalane, linseed oil, almond oil, beeswax, carnauba wax, candelilla wax, and beef fat. , Beef leg fat, beef bone fat, hardened beef fat, wheat germ oil, sesame oil, rice germ oil, rice bran oil, safflower oil, soybean oil, camellia oil, evening primrose oil, corn oil, rapeseed oil, horse fat, palm oil, palm Kernel oil, castor oil, hydrogenated castor oil, mink oil, cottonseed oil, palm oil, hydrogenated palm oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin fatty acid isopropyl, olive squalane, squalene, ceresin, paraffin wax, petrolatum, α -An olefin oligomer etc. can be mentioned.

  Examples of the higher fatty acid include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, and linolenic acid.

  Examples of the fat-soluble vitamins include various fat-soluble vitamins and derivatives thereof, such as tocopherol and derivatives thereof, retinol and derivatives thereof, and ascorbic acid derivatives.

  Examples of the oil-soluble thickener include long-chain hydroxy fatty acids such as 12-hydroxystearic acid; zinc stearate, aluminum stearate, magnesium stearate, zinc palmitate, aluminum palmitate, zinc myristate, myristic acid Fatty acid metal salts such as magnesium; hydrogenated (styrene / isoprene) copolymer, hydrogenated polyisobutene, dextrin palmitate, dextrin (palmitate / hexyldecanoate), dextrin (palmitate / ethylhexanoate), dextrin myristate, inulin stearate And polymer compounds such as dextrin isostearate; surface lipophilic fine particles such as silylated silica; and aggregates of various hydrophilic polymers and surfactants.

  The composition for make-up cosmetics of the present invention may further contain an oil-soluble binder as the oil phase component (B). By blending an oil-soluble binder in the makeup cosmetic composition, an effect of suppressing the occurrence of “smoothness” due to the powder (C) entering the wrinkles with time after application can be obtained.

  Examples of the oil-soluble binder include heavy fluid isoparaffin, high-viscosity dimethylpolysiloxane (50000 cs or more), metal soap, microcrystalline wax, and branched paraffin wax. These can be used alone or in combination of two or more.

  The blending amount of the oil-soluble binder (the total amount when containing two or more) is, for example, about 0.1 to 30% by weight, preferably 1 to 15% by weight, more preferably the total amount of the makeup cosmetic composition. Is 2 to 10% by weight. When the blending amount of the oil-soluble binder is less than the above range, the effect of suppressing “smoothness” tends to be hardly obtained. On the other hand, when the blending amount of the oil-soluble binder exceeds the above range, the coating feel becomes heavy and the usability tends to be lowered.

  The content of the oil phase component (B) (when 2 or more types are contained, the total amount thereof) is 0.1 to 95% by weight, preferably 3 to 90% by weight, and particularly 3 to 90% by weight, based on the total amount of the makeup cosmetic composition. Preferably it is 5-85 weight%.

[Powder (C)]
Examples of the powder (C) include pigments and UV protection agents. These can be used alone or in combination of two or more.

As said pigment, the well-known organic or inorganic pigment used for cosmetics can be used. Examples of inorganic pigments include titanium oxide-coated mica, colored titanium oxide-coated mica, titanium oxide / silica / titanium oxide-coated mica, titanium oxide-coated talc, iron oxide-coated silica powder, titanium oxide-coated silica powder, and titanium oxide-coated glass powder. Pearl pigments such as iron oxide / silica coated aluminum powder, titanium oxide coated alumina, iron oxide / silica coated iron oxide, titanium oxide coated synthetic mica, iron oxide / titanium oxide coated synthetic mica, iron oxide (Bengara), yellow iron oxide , Black iron oxide, carbon black, titanium oxide, ultramarine, bitumen, talc, sericite, kaolin, mica, silica, zinc white, bentonite, barium sulfate, hydroxyapatite, boron nitride and the like. Examples of organic pigments include red 104, red 201, red 202, red 226, red 230, yellow 4, yellow 5, yellow 401, blue 1, blue 404, nylon , Polyester, polymethyl methacrylate, polyethylene, polyethylene terephthalate, polyurethane, silicone resin, silk, cellulose laminated film powder, N ^ε -lauroyl-L-lysine, natural pigments, and the like.

  As the ultraviolet protective agent, known organic or inorganic ultraviolet protective agents used in cosmetics can be used. For example, surface aqueous aluminated titanium oxide, surface aqueous alumina silica-treated titanium oxide, stearic acid-coated surface Aqueous aluminized titanium oxide, silicone-coated surface aqueous alumina silica-treated titanium oxide, various surface-treated zinc oxides of silicone, triazine compounds (for example, methylenebisbenzotriazolyltetramethylbutylphenol, bisethylhexyloxyphenol methoxyphenyltriazine, trisbiphenyltriazine) Etc.).

  The shape of the powder (C) is not particularly limited, and examples thereof include a spherical shape, a plate shape, a scale shape, and a needle shape. Moreover, the structure of powder (C) is not specifically limited, The structure of a single layer may be sufficient and the structure of a multilayer (multilayer) may be sufficient. Further, the powder (C) may be any of solid particles, hollow particles, porous particles and the like. The average primary particle diameter (by dynamic light scattering (DLS) method) of the powder (C) is, for example, about 0.1 to 1000 nm, preferably 1 to 800 nm, particularly preferably 10 to 500 nm.

  As the powder (C) (particularly inorganic pigment) used in combination with the modified polysiloxane compound (A), it is particularly preferable to use a powder that has not been subjected to organic surface treatment. That is, the powder (C) of the present invention is preferably “powder (excluding organic surface-treated powder) (C)”.

  The organic surface treatment of the powder is performed for the purpose of increasing the hydrophobicity of the powder surface, and by using a powder subjected to the organic surface treatment (hereinafter referred to as “organic surface-treated powder”), An effect of repelling sweat and water can be imparted to cosmetics. However, when an organic surface-treated powder is blended with the makeup cosmetic composition of the present invention, the effect of improving the skin adhesion by the modified polysiloxane compound (A) and the effect of improving the dispersion stability of the powder are obtained. This is not preferable because it is difficult to be formed. In addition, since the composition for makeup cosmetics of the present invention has an effect of repelling sweat and water by the modified polysiloxane compound (A), it is a powder not imparted with an effect of repelling sweat or water, that is, an organic surface Even when untreated powder is used, the powder can be well adhered and held on the skin, and the makeup feeling is good.

  The makeup cosmetic composition of the present invention may contain an organic surface-treated powder, but the content thereof is 30% by weight or less of the total amount of the powder contained in the makeup cosmetic composition (0 -30% by weight), preferably 10% by weight or less, 30% by weight or less (0-30% by weight), preferably 10% by weight or less of the total amount of the makeup cosmetic composition, and organic surface-treated powder Most preferably, it does not contain.

  The organic surface-treated powder includes dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, and silicones such as copolymers thereof; silane coupling agents; carbon such as stearic acid and magnesium stearate. It includes powders surface-treated with organic compounds such as higher fatty acids of several tens or more and metal salts thereof (in particular, polyvalent metal salts such as calcium, magnesium and zinc).

  The content of the powder (C) (the total amount when containing two or more) is 0.01 to 99% by weight, preferably 0.05 to 95% by weight, based on the total amount of the makeup cosmetic composition. Particularly preferred is 0.1 to 90% by weight, most preferred is 0.2 to 85% by weight, and particularly preferred is 0.5 to 70% by weight.

[Composition for makeup cosmetics]
The composition for makeup cosmetics of the present invention contains the modified polysiloxane compound (A), the oil phase component (B), and the powder (C).

  The composition for make-up cosmetics of the present invention includes water, a moisturizer (for example, glycerin, 1,3-butylene glycol, 1 , 3-propanediol, etc.), water-soluble thickeners, plant extract extracts, fermented extract extracts, water phase components such as pigments (other than the above component (C)); surfactants (modified polysiloxane compounds ( 1) or more of astringents, preservatives, antibacterial agents, antioxidants, chelating agents, pH adjusters, pearl agents, scrub agents, whitening active ingredients, blood circulation promoting agents, hair nourishing agents, perfumes, etc. Can be blended.

  The water is not particularly limited as long as it can be generally used for cosmetics, but purified water is preferably used.

  Examples of the water-soluble thickener include water-soluble polymer compounds and polysaccharide derivatives (for example, gum arabic, arginine carbomer, sodium alginate, propylene glycol alginate, carboxymethyl cellulose, xanthan gum, synthetic sodium silicate, dimethyl stearyl ammonium hectorite. , Cyclodextrin, sodium polyacrylate, hyaluronic acid derivatives, etc.). The water-soluble thickener may be used in the form of an aqueous solution.

  There is no restriction | limiting in particular in content of the water phase component in the composition for makeup cosmetics of this invention, According to the dosage form of the target cosmetics, it can adjust suitably.

  The composition for makeup cosmetics of this invention can be manufactured by performing the said component according to a conventional method, such as a heating, mixing, stirring.

  The makeup cosmetic composition of the present invention includes, for example, lipstick, lip gloss, oily foundation, cake type foundation, emulsified type foundation, teak, mascara, eyeliner, eye shadow and the like.

  Since the composition for makeup cosmetics of the present invention contains a specific amount of the modified polysiloxane compound (A), the dispersion stability of the powder (C) is excellent. Therefore, it has excellent coating properties, no color unevenness, good color development, and a beautiful finish. In addition, it has excellent skin adhesion and good makeup. Furthermore, there is little irritation | stimulation to skin and it is excellent in safety.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Preparation Example 1
(Synthesis of 3- [N-methyl (10-undecenoylamide)] propane-1,2-diol)
317.29 g (1.60 mol) of methyl 10-undecenoate in a 1 L 5-neck flask equipped with a reflux tube, a nitrogen inlet with a three-way cock, a vent with a three-way cock, a stirring blade with a vacuum seal, and a thermometer, 173.27 g (1.65 mol) of 3-aminopropane-1,2-diol and 3.78 g (16.0 mmol) of 24% sodium methoxide methanol solution were added, and the pressure was reduced from 500 hPa to 50 hPa, and the temperature was reduced from 108 ° C to 117 ° C. The mixture is heated and stirred for 24.5 hours while distilling off the methanol produced, cooled to room temperature, added with 290 g of ethanol, stirred and diluted, and then mixed with an inorganic synthetic adsorbent (trade name “KYOWARD 700”, 50 g of Kyowa Chemical Industry Co., Ltd.) was added, heated and stirred at 75 ° C. for 2 hours, and filtered. The obtained filtrate was concentrated with a rotary evaporator and dried to a constant weight in a vacuum desiccator to give 3.8.80 g of 3- [N-methyl (10-undecenoylamide)] propane-1,2-diol as a white paste. (Yield: 77.5%) was obtained. The structure of the obtained reaction product was confirmed by ¹ H-NMR spectrum and IR spectrum.

(Synthesis of modified polysiloxane compounds)
A 1-liter five-necked flask equipped with a reflux pipe with a hydrogen inlet with a three-way cock, a nitrogen inlet with a three-way cock, a thermometer, and a stirring rotor was added to a dimethylsiloxane-methylhydrosiloxane copolymer (trade name “ KF-9901 ", manufactured by Shin-Etsu Chemical Co., Ltd.) 176.03 g, 1-decene 134.66 g (0.96 mol), butyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) 310.68 g were added, and the inside was replaced with nitrogen did. Put 0.2432 g (4.8 μmol of chloroplatinic acid hexahydrate) in 0.2% chloroplatinic acid hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and gradually raise the temperature to 70 ° C. And stirred for 3 hours.
Next, 64.90 g (0.24 mol) of 3- [N-methyl (10-undecenoylamide)] propane-1,2-diol obtained above and 0.2% chloroplatinic acid hexahydrate were obtained. 4.9718 g (19.2 μmol of chloroplatinic acid hexahydrate) of butyl acetate solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added, the temperature was gradually raised to 70 ° C., and 16 hours later, 1-decene 67.32 g (0.48 mol), and further 10 hours later, 33.66 g (0.24 mol) of 1-decene was added and stirred for 10 hours.
The reaction solution was sampled and cooled after confirming that the signal derived from Si-H protons of methylhydrosiloxane units observed at δ4.65 ppm to δ4.70 ppm disappeared by ¹ H-NMR (deuterated chloroform solution). .
The obtained reaction mixture was concentrated and dried with a rotary evaporator, transferred to a separatory funnel, and subjected to liquid separation washing operation with acetone until 1-decene contained in the upper layer liquid was 10 ppm or less. It was concentrated and dried to a constant value with an evaporator to obtain 286.72 g of a modified polysiloxane compound (1) in the form of a light yellowish brown transparent oil having a siloxane unit represented by the following formula. ^From the integrated value of the ¹ H-NMR signal, the introduction ratio [pmol%: (q-1) mol%: (q-2) mol%] of each siloxane unit was 52.1: 40.5: 7.4. Something was calculated.

Preparation Example 2
(Synthesis of modified polysiloxane compounds)
Instead of 3- [N-methyl (10-undecenoylamide)] propane-1,2-diol, 1- (10-unde) obtained by synthesis according to the method described in JP-A-7-53431. A modified polysiloxane compound (2) having a siloxane unit represented by the following formula was obtained in the same manner as in Preparation Example 1, except that senyloxy) propane-2,3-diol was used. ^From the integrated value of the ¹ H-NMR signal, the introduction ratio [pmol%: (q-1) mol%: (q-2) mol%] of each siloxane unit was 52.0: 41.1: 6.9. Something was calculated.

Examples 1-12, Comparative Examples 1-12
Each component was weighed on a tile according to the formulations (units: parts by weight) shown in Tables 1 to 3 below, and kneaded well with a spatula to obtain a composition. About the obtained composition, the dispersibility of powder was evaluated by the following method.

Dispersibility evaluation method:
An observation sample prepared by placing the composition on a slide glass and placing a cover glass on the slide glass was observed using a microscope (Nikon optical microscope “Nikon ECLIPSE 50i”, magnification 20 × or 40 ×). The dispersibility was evaluated according to the following criteria.
Evaluation Criteria A: No agglomerates are observed. O: Agglomerates having a diameter of 5 μm or less are present, but most particles are primary particles. Δ: Agglomerates having a diameter of 5 μm or more are present, and there are few primary particles. Mostly agglomerates with a diameter of 5 μm or more

Iron oxide: Bengala-silica mixture, average primary particle size 100 nm, trade name “Unipure Red LC 381”, manufactured by Sensitive Cosmetic Technologies titanium oxide: aqueous alumina surface-treated titanium oxide, average primary particle size 250 nm, trade name “CR-50” Red 202 No. manufactured by Ishihara Sangyo Co., Ltd .: average primary particle diameter 50 nm, trade name “Unipure Red LC 3079”, manufactured by Sensitive Cosmetic Technologies triethylhexanoin: trade name “TIO”, Nisshin Oillio Group ( Co., Ltd. dicapric acid neopentyl glycol: trade name “Esthemol N-01”, Nisshin Oillio Group Co., Ltd. α-olefin oligomer: trade name “NOMCOAT HP-30”, Nisshin Oilio Group Co., Ltd.) polydimethylsiloxane: trade name "SH-200 Fluid 1.5cs", manufactured by Dow Corning Toray Co., Ltd.

Reference Examples 1-3
As the amphiphilic polymer compound, the modified polysiloxane compound (1) obtained in Preparation Example 1 (referred to as (1)), the modified polysiloxane compound obtained in Preparation Example 2 (2) referred to as (2) ), Glyceryl ether-modified silicone (trade name “Penetor SI-U”, manufactured by Kao Corporation: GE), or polyether-modified silicone (trade name “KF-6015”, manufactured by Shin-Etsu Chemical Co., Ltd .: PE) And amphiphilic polymer compound and pure water in a ratio of 90:10 (amphiphilic polymer compound: pure water (weight ratio)) to a total amount of 1.0 g, Samples were prepared.
More specifically, first, each amphiphilic polymer compound is weighed in a 2.0 mL microtube, and stirred with a spatula until uniform while adding pure water little by little to a predetermined blending amount. A sample was obtained. The stirring time was 30 minutes in all steps.

About the obtained sample, skin adhesiveness was evaluated by the following method.
Using a skin model made of wet hand-pig leather, weighed 0.05 g of each sample and applied it to the surface of one hand-craft pork leather sample. The pig leather for handicrafts was piled up, and a 2 kg weight was put on it for 1 minute, followed by a peel test (see FIG. 1).
The attachment surface portions of two pieces of pig skin leather for handicrafts were clamped and fixed with a digital force gauge clip, and the peeling stress was measured at a peeling speed of 50 mm / min. The results are shown in FIG.
In the peel test, referring to [6] T-peel peel of Japanese Industrial Standard (JIS), the peeling stress when peeling the adhesive layer in the 180 ° direction was measured with a digital force gauge (trade name “ZP-5N”). ”, Manufactured by Imada Co., Ltd.).

Pig skin is similar in chemical composition to human skin, and the absorption mechanism by pig skin is considered to be close to that of human skin ("Cosmetic Handbook" Shigeru Sekine, Chuo Printing Co., Ltd., 2006 ) Adhesion to wet pork leather surface for handicraft can be an indicator of adhesion to human skin.
From FIG. 2, the peel strength when the modified polysiloxane compound (1) is used as the amphiphilic polymer compound is the highest, and the modified polysiloxane compound (2), glyceryl ether modified silicone (GE), polyether modified silicone ( It is clear that the composition for makeup cosmetics of the present invention containing the modified polysiloxane compound (A) is excellent in skin adhesion from the fact that it exceeds the peel strength when using PE). .

Example 13, Comparative Examples 13-14
The quality of the dispersion of the powder such as pigment is an important factor that affects the appearance of the solid formulation for makeup cosmetics. Therefore, using the modified polysiloxane compound (1) obtained in Preparation Example 1, lipstick Were prepared and solid appearance compositions (1) to (3) were prepared to evaluate the appearance.
First, 70% by weight of the modified polysiloxane compound (1) obtained in Preparation Example 1 and dilauroyl glutamate (phytosteryl / octyldodecyl) (trade name “El Deu PS-203”, manufactured by Ajinomoto Healthy Supply Co., Ltd.) 30% by weight A mixture (referred to as “MDU-P30”) was prepared.
Each component was weighed in accordance with the formulation shown in Table 4 below (unit: parts by weight), heated and mixed at 100 ° C., mixed with a spatula for 10 minutes, further heated and mixed at 100 ° C. for 5 minutes, and poured into a mold. It was cooled to 0 ° C. and sufficiently solidified to obtain a solid blend composition. The appearance of the obtained solid blend composition was evaluated according to the following criteria.
Evaluation criteria A: There is no aggregation of the pigment and the color development is good (bright).
◯: Pigment aggregation is not visually observed, but color development is slightly poor.
(Triangle | delta): Although the pigment is disperse | distributing mostly, aggregation is recognized partially and color development is unsatisfactory.
X: Aggregation of the pigment is recognized as a whole.

PEG-12 dimethicone: trade name “SH3775”, manufactured by Toray Dow Corning Co., Ltd. Iron oxide: Bengala-silica mixture, average primary particle size 100 nm, trade name “Unipure Red LC 381”, manufactured by Sensitive Cosmetic Technologies titanium oxide: aqueous Alumina surface-treated titanium oxide, average primary particle size 250 nm, trade name “CR-50”, manufactured by Ishihara Sangyo Co., Ltd. Red No. 202: average primary particle size 50 nm, trade name “Unipure Red LC 3079”, branch made by Sensitive Cosmetic Technologies Paraffin wax: Trade name “Paraffin Wax MW”, manufactured by Nippon Seiki Co., Ltd. Linear Paraffin Wax: Trade name “Paraffin Wax HNP-9”, manufactured by Nihon Seiki Co., Ltd. Decyl: Trade name “Saracos 913”, Nisshin Oilio Group Co., Ltd. Dicapric acid neopentyl glycol: Trade name “Esthemol N-01”, Nisshin Oilio Group Co., Ltd. α-olefin oligomer: Trade name “Nom Coat HP-30 ", manufactured by Nisshin Oillio Group Co., Ltd. Petrolatum: Product name" Nom Coat W ", manufactured by Nisshin Oilio Group Co., Ltd.

  From Table 4, the solid compounding composition (1) using the modified polysiloxane compound (1) obtained in Preparation Example 1 is a solid compounding composition (2) that does not contain the modified polysiloxane compound (1), ( It is clear that the appearance is superior to 3).

Example 14 (Teak)
The ingredients shown in Table 5 were mixed at 50 ° C. and then pressed to obtain teak (blusher). All the inorganic powder components were not treated with an organic surface, but the resulting cheek had good color development, and the cosmetic film adhered to the skin remained for a long time without peeling off, giving good color development. Lasted.

Example 15 (Eyeshadow)
The components shown in Table 6 were mixed at 50 ° C. and then pressed to obtain an eye shadow. All inorganic powder components were used which had not been subjected to organic surface treatment. However, the obtained eye shadow had good color development and light coating feel.

Example 16 (mascara)
Mascara was obtained by stirring and mixing the components shown in Table 7. The inorganic powder component (pigment) was not subjected to any organic surface treatment, but the obtained mascara had good dispersibility of the powder component and was difficult to become lumpy.

Example 17 (foundation)
A foundation was obtained by mixing the components shown in Table 8 using a hammer mill. All inorganic powder components were used which had not been subjected to organic surface treatment, but the obtained foundation had good color development and was difficult to cause dust scattering.

  As shown in the above examples, the composition of the present invention containing the modified polysiloxane compound (A) is excellent in powder dispersibility and skin adhesion. Therefore, it is apparent that these performances can be suitably used for make-up cosmetics, which is an important factor affecting the feeling of use of the product.

1 Sample application surface 2 Attachment surface 3 Wet pig leather for handicraft

Claims (4)

The modified polysiloxane compound (A) represented by the following formula (1), the oil phase component (B), and the powder (C) are contained in the following range , and the content of (A) is the above (C ) A composition for makeup cosmetics in the range of 0.01 to 3 parts by weight per 1 part by weight .
(A): 0.1 to 20% by weight of the total amount of the composition
(B): 0.1 to 95% by weight of the total amount of the composition
(C): 0.01 to 99% by weight of the total amount of the composition

[Wherein, R ^{1 to} R ⁹ are the same or different and are each a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 6 carbon atoms, and a cyclic alkyl group having 3 to 6 carbon atoms. The hydrocarbon group selected from these is shown. p and q each represent an average value of the number of siloxane units shown in parentheses, p is a number of 1 or more, and q is a number of 2 or more. A represents a group selected from a group represented by the following formula (2), a group represented by the following formula (3), and a hydrogen atom. However, the modified polysiloxane compound (A) has at least a siloxane unit in which A is a group represented by the following formula (2) and a siloxane unit in which A is a group represented by the following formula (3). Yes]

(In Formula (2), R ¹⁰ represents a single bond or a linear or branched alkylene group having 1 to 17 carbon atoms. In Formula (3), R ¹¹ represents a single bond or 1 to 17 carbon atoms. Wherein R ¹² represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, wherein formulas (2) and (3) The left end of) is bonded to the silicon atom)   The oil phase component (B) contains at least one compound selected from the group consisting of silicone oil, high polarity oil, low polarity oil, higher fatty acid, fat-soluble vitamin, and oil-soluble thickener, The composition for makeup cosmetics according to claim 1, comprising a pigment and / or a UV protection agent as C).   The composition for makeup cosmetics according to claim 1 or 2, wherein the powder (C) is a powder (excluding powder subjected to organic surface treatment) (C).   The makeup cosmetic composition according to any one of claims 1 to 3, wherein the makeup cosmetic is lipstick, lip gloss, foundation, teak, mascara, eyeliner, or eye shadow.

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