JP4567585B2 - Cosmetics - Google Patents

Description

  The present invention relates to a cosmetic containing both-end silicone-modified glycerin having a specific structure.

  Silicone oil is blended in many cosmetics as a refreshing oil. For example, alkyl-modified silicone (Patent Document 1), fluorine-modified silicone (Patent Document 2), cholesterol-modified silicone (Patent Document 3), acylalkylimine-modified silicone (Patent Document 4), glyceryl-modified silicone (Patent Document 5), alkyl Glyceryl ether-modified silicone (Patent Document 6) and alkyl monoglyceryl ether / fluorine co-modified silicone (Patent Document 7) are blended in cosmetics.

  However, since the silicone oil has a refreshing feeling and a feeling of squeaky skin, a silicone oil having a feel that is more familiar to the skin has been strongly desired.

  On the other hand, water-in-oil type emulsion compositions having an oil phase as an outer phase and an aqueous phase as an inner phase are used in various cosmetics. Such a water-in-oil emulsion composition is superior to the oil-in-water type in terms of protecting the skin, imparting flexibility, and suppressing skin moisture evaporation, and is suitable as an external preparation for skin. It is considered that the dosage form.

  As an emulsifier for a water-in-oil emulsion composition, a conventional lipophilic surfactant of about HLB 1 to 12, for example, a polyhydric alcohol fatty acid ester surfactant such as glycerin fatty acid ester or sorbitan fatty acid ester, polyoxyalkylene-modified Organopolysiloxane surfactants have been used (Non-Patent Document 1).

However, water-in-oil emulsion compositions using these emulsifiers are poor in emulsion stability, resulting in separation of the water phase and oil phase under high temperature conditions or over time, making it extremely difficult to stabilize as a preparation. there were.
In addition, a method of stabilizing the dosage form by blending a wax in an oil phase that is an outer phase is also performed. However, since the wax melts or softens under high temperature conditions, there is a problem that the stability of the preparation is not sufficient. Furthermore, there are new usability problems such as heavy spread and stickiness during application.

  Also, since many cosmetics containing sunscreen and foundation powders are required to have water resistance and sweat resistance, in many cases, hydrophobized powders are added to W / O type preparations. ing.

  However, when a large amount of powder is added to the W / O type preparation, there is a problem that the viscosity of the preparation increases due to aggregation of the powder, and it is difficult to spread it during use, and further, the skin after application becomes white. Therefore, techniques for more stably dispersing powder in oil have been developed.

  The technology for primary dispersion of powders has progressed with miniaturization equipment such as roller mills, bead mills, and high-pressure homogenizers. It has become a challenge. Since many cosmetics contain silicone oil as an oil component, patents relating to powder dispersants using modified silicone have been filed. For example, Patent Document 8 discloses powder dispersion in oil using a dispersant obtained by copolymerizing (A) an organopolysiloxane monomer, (B) a monomer having a polylactone-containing group, a hydroxyl group or an anionic group. Things are being used. In Patent Document 9, ultraviolet blocking fine particles are dispersed by a silicone-based dispersant made of modified silicone or reactive silicone.

  Patent Document 10 discloses a dispersant in oil for inorganic powder comprising a fatty acid to which an alkylene oxide has been added. Examples thereof include POE (4.5) lauryl ether acetic acid, POE (4) stearyl ether. Dispersibility and stability of acetic acid, POE (10) lauryl ether acetic acid, POE (12) stearyl ether acetic acid, and POE (10) sodium lauryl ether acetate have been confirmed.

JP-A-5-262616 JP-A-5-247214 JP-A-5-25280 JP-A-5-112423 JP-A-6-157236 JP-A-5-112424 JP-A-9-249518 JP-A-11-263706 Republished patent WO97 / 45097 Japanese Patent Laid-Open No. 2000-262883 "Fourth Edition, Petrochemical Handbook-Lipids and Surfactants", edited by Japan Oil Chemists' Society, Maruzen Co., Ltd.

  As a result of diligent research in view of the above-mentioned viewpoints, the present inventors have formulated a two-end silicone-modified glycerin having a specific structure as an oil component. An emulsified cosmetic and an oil-in-water emulsion composition were obtained, and it was found that a cosmetic having excellent powder dispersibility was obtained, and the present invention was completed.

  An object of the present invention is to provide a cosmetic material that is particularly refreshing and has a feeling of familiarity with the skin.

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基であり、Ｒ２は炭素数２〜１１のアルキレン基であり、ｍは１０〜１２０、ｎは１〜１１である。 That is, this invention provides the cosmetics characterized by containing the both terminal silicone modified glycerol represented by the following general formula (a).
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkylene group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .

  The present invention also provides the cosmetic described above, wherein the cosmetic is an oily cosmetic.

  Furthermore, the present invention provides the cosmetic described above, wherein the cosmetic is a water-in-oil emulsified cosmetic.

  Moreover, this invention provides said cosmetics characterized by the said cosmetics being an oil-in-water emulsion composition.

  Furthermore, the present invention provides the cosmetic described above, wherein the cosmetic further contains a powder.

(1) Since the cosmetic of the present invention contains both ends of the silicone-modified glycerin having a specific structure as an oil component, the skin familiarity is extremely good while refreshing.
(2) The both-end silicone-modified glycerin used in the present invention exhibits an excellent emulsifying function with respect to the water-in-oil emulsion composition. As a result, it is possible to provide a water-in-oil emulsified cosmetic that is excellent in stability and excellent in feeling of use even when substantially no surfactant is blended.
(3) Moreover, in an oil-in-water type emulsion cosmetic, the emulsion composition excellent in stability and usability is obtained by using a known hydrophilic emulsifier together.
(4) The cosmetic of the present invention has extremely high powder dispersion stability, and can provide a stable powder-dispersed cosmetic. In particular, the stability of the powder is remarkably high in oil containing silicone oil. FIG. 1 shows a schematic diagram of powder dispersion stability. The above-mentioned both-end silicone-modified glycerin has a dispersion site consisting of silicone chains at both ends as a powder dispersion stabilizer, so that the powder is held at the adsorption site consisting of polyglycerin chains with very high adsorptivity, It is thought that the polymer spreads in the solvent of the dispersion medium and exhibits a very remarkable dispersion stability effect.
(5) The both-end silicone-modified glycerin used in the present invention can exhibit various HLB and viscosities in cosmetics by appropriately selecting the molecular weight of the dimethylpolysiloxane chain and the polyglycerin chain. As a result, a cosmetic having a desired feeling of use can be designed.

式中、Ｒ１はそれぞれ、炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基、ｍは１０〜１２０の数である。Ｒ１はそれぞれが同一であっても、異なっていても良い。 The basic structure of the both-end silicone-modified glycerin used in the present invention is a BAB type triblock copolymer, and for B, for example, one-end hydrogen residue silicone represented by the following structure (c) can be used. In general formula (a), each R1 may be the same or different. Also, each R2 may be the same or different.
A is a glycerin residue.
One-terminal hydrogen silicone having the following structure (c) is a known compound. A BAB type triblock copolymer having an arbitrary degree of polymerization can be produced by a known method.
(C)

In the formula, each R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, and m is a number of 10 to 120. R1 may be the same or different.

式中、ｎは１〜１１の数である。 The bond between A and B is not an essential structure for the present invention, but the both-end silicone-modified glycerin exemplified in the present invention is obtained by converting a compound (c) and a compound represented by the following structural formula (d) into platinum. A catalyst is used and bonded by an ether bond.


(D)

In formula, n is a number of 1-11.

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基であり、Ｒ２は炭素数２〜１１のアルキル基であり、ｍは１０〜１２０、ｎは１〜１１である。
（ｂ）

式中、Ｒ１は炭素数１〜１２の直鎖又は分岐アルキル基、もしくはフェニル基、ｍは１０〜１２０、ｎは１〜１１である。 The BAB type triblock copolymer can be synthesized by a known method. A synthesis scheme is shown in FIG.
In this manner, a double-end silicone-modified glycerin represented by the following structural formula (a) {preferably the structural formula (b)} is obtained.
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkyl group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .
(B)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, m is 10 to 120, and n is 1 to 11.

The polymerization degree m of the silicone chain is preferably 10 to 120. The side chain substituent is preferably a methyl group, but may be substituted with phenyl or other alkyl.
As for n of the polymerization degree of a glycerol chain, 1-11 are preferable.
As shown in FIG. 1, the solubility of the B block in a solvent and the high adsorbability of the A block chain on the powder surface are important for the functional expression of the both-end silicone-modified glycerin. That is, the hydrophilic / lipophilic balance (HLB) of both AB blocks is in an appropriate range, which is essential for function expression. The HLB can be obtained by a known method, and is calculated, for example, by the Griffin equation (HLB value = glycerin molecular weight × 20 / total molecular weight). In the present invention, the HLB is preferably 0.2 to 3.0.

  Further, the spread of the A block chain that prevents aggregation between powders depends on the molecular weight of the polymer, and the higher the molecular weight of the A block chain, the higher the aggregation preventing effect. On the other hand, the adsorption to the powder is considered to be due to a weak force such as van der Waals force of the B block chain and hydrogen bond. However, by using polyglycerin as the B block chain, a strong adsorption force can be obtained as compared with polyethylene glycol and the like, so that a sufficient adsorption force can be obtained with a relatively low molecular weight. Moreover, if the molecular weight of both AB blocks is too high, it may be difficult to spread the cosmetic, and the weight of the stretch may be felt. From the above, there is an appropriate range for the molecular weight, and the molecular weight is preferably 2000 to 20000.

The compounding quantity of the both terminal silicone modified glycerol used for this invention is determined suitably. Usually, it is 0.1-50 mass% with respect to cosmetics whole quantity, Preferably it is 0.1-30 mass%.
In the case of a cosmetic containing powder and silicone oil, about 0.1 to 30% by mass is usually blended with respect to the total amount of the powder, silicone oil and both-end silicone-modified glycerin.

In the cosmetic of the present invention, other oils can be blended in addition to the both-end silicone-modified glycerin blended as an oil. In the present invention, an oily cosmetic is preferred.
Linear polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, modified silicones such as polyether-modified silicone, alkyl-modified silicone and epoxy-modified silicone, trimethyl One or more oils such as silicone resins such as siloxysilicic acid and highly polymerized methylpolysiloxane are preferred.
Moreover, other oil-based components can be blended with the silicone-based dispersion medium as long as the effects of the present invention are not impaired. For example, liquid paraffin, solid paraffin, petrolatum, ceresin, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl stearate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyl octanoate , Cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, dicaprin Acid neopentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-ethylhexanoic acid Limethylolpropane, trimethylolpropane triisostearate, glyceryl trioctanoate, glycerin triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, tri-2- Glyceryl ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, oleic acid oleyl, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethyl sebacate Hexyl, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, avocado oil, camellia oil, macadamia nut oil, corn oil, olive oil Rapeseed oil, sesame oil, wheat germ oil, sasanqua oil, castor oil, flaxseed oil, safflower oil, cottonseed oil, soybean oil, peanut oil, grape seed oil, almond oil, tea seed oil, rice bran oil, jojoba oil, meadow foam Oils such as oil and germ oil can be added.

  Moreover, the said both terminal silicone modified glycerol functions as an emulsifier excellent with respect to the water-in-oil type emulsified cosmetics. Therefore, according to the present invention, it is possible to provide a water-in-oil emulsified cosmetic excellent in emulsification stability and usability. The blending amount of the both-end silicone-modified glycerin that functions as an emulsifier is not particularly limited. Usually, 0.1-10.0 mass% is mix | blended with respect to water-in-oil type emulsified cosmetics. A blending amount of 0.5 to 5.0% by mass is suitable. When the blending amount is less than 0.1% by mass, the emulsion stability may be inferior, and even when blending more than 10.0% by mass, the effect is not improved. In addition, in the water-in-oil emulsified cosmetic of the present invention, other emulsifiers can be used in combination, but a stable emulsified cosmetic can be obtained substantially by blending only with both terminal silicone-modified glycerin.

  On the other hand, the above-mentioned both-end silicone-modified glycerin can be used in combination with a known hydrophilic emulsifier for oil-in-water emulsified cosmetics, whereby an emulsion composition having excellent stability and usability can be obtained. The blending amount of the above-mentioned both-end silicone-modified glycerin is generally 0. 0 with respect to the total amount of the oil phase of the oil-in-water emulsion cosmetic (the total amount of the powder dispersed in the oil phase and the oil constituting the oil phase). 1-30 mass% is mix | blended. The blending amount of the hydrophilic emulsifier is not particularly limited. It is normally blended in an amount of 0.1 to 10.0% by mass with respect to the oil-in-water emulsified cosmetic.

  The present invention is to improve the powder dispersibility and the emulsion stability by blending the above-mentioned both-end silicone-modified glycerin into cosmetics. In the cosmetic of the present invention, components usually used in cosmetics and pharmaceuticals can be blended within a range that does not impair the effects of the present invention, and can be produced by a conventional method.

  The oil content blended in the water-in-oil emulsified cosmetic and the oil-in-water emulsified cosmetic is not limited. The blending amount of the oil is not limited and is appropriately determined. Usually, in the case of a water-in-oil emulsified cosmetic, it is 10 to 95% by mass, preferably 20 to 80% by mass, and in the case of an oil-in-water emulsified cosmetic, 5 to 70% by mass, preferably 10 to 30% by mass. Is preferred. The cosmetic of the present invention is produced by a conventional method by mixing essential components.

  Further, since the cosmetic of the present invention is excellent in powder dispersibility, it is preferably used as a powder-containing cosmetic. The powder to be dispersed is not particularly limited. Inorganic powders (particularly titanium oxide or zinc oxide) are preferred. It is a feature of the present invention that the dispersion stability of both the mixed powders is extremely high.

The average particle size of the powder is preferably 0.5 to 150 nm.
In this case, when blending titanium oxide or zinc oxide powder as an ultraviolet scattering agent, fine particles having an average particle diameter of 1 to 50 nm are preferable.

  The powder blended in the cosmetic of the present invention can improve the dispersion stability of the powder by subjecting the powder to a surface treatment.

The cosmetic of the present invention in which powder is blended can be produced by mechanically dispersing powder, both-end silicone-modified glycerin, and a silicone-based dispersion medium.
An appropriate dispersing machine may be used for pre-kneading and dispersion treatment while heating as necessary. Depending on the viscosity of the slurry to be adjusted, a dispersing machine such as a roller mill, a high-pressure homogenizer, or a bead mill is appropriately selected and used.

  In addition, an ultraviolet scattering agent can be suitably mix | blended as the powder disperse | distributed to the said cosmetics. Examples of the ultraviolet scattering agent include inorganic powders such as titanium oxide and zinc oxide, or the surface of this inorganic powder such as aluminum stearate and zinc palmitate fatty acid soap, stearic acid, myristic acid, palmitic acid and other fatty acids, palmitic acid. Examples thereof include surface-coated inorganic powders coated with fatty acid esters such as acid dextrin.

  One or more of the above ultraviolet scattering agents may be selected and blended. The blending amount of the ultraviolet scattering agent is preferably 0.1 to 50.0% by mass, more preferably 1.0 to 40.0% by mass in the cosmetic. If the blending amount of the UV scattering agent is too small, a sufficient UV protection effect may not be seen, and if it is too much, an emulsion may not be obtained. The cosmetic of the present invention has an excellent effect that the ultraviolet scattering powder is very well dispersed.

  The usage application of the cosmetic of the present invention is not particularly limited. For example, lotion, milky lotion, cream, foundation, lipstick, cleansing foam, shampoo, hair rinse, lip balm, hair spray, hair foam, sun cream, sun cream, eyeliner, mascara, nail cream, body makeup cosmetics, etc. It can be applied to various products.

  Next, the present invention will be described more specifically with reference to examples. The present invention is not limited by these examples. A compounding quantity is the mass% with respect to the whole quantity unless there is particular notice.

"Synthesis Example 1 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 3.5 g of triglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)

“Synthesis Example 2 Synthesis of Silicone Modified Glycerin at Both Ends”
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (e) (Mw≈4600), 4.3 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(E)

"Synthesis Example 3 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of one-terminal hydrogenated dimethylpolysiloxane of formula (f) (Mw≈7600), 2.6 g of tetraglyceryl diallyl ether, and 100 g of isopropyl alcohol, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.





(F)

式中、Ｐｈはフェニル基を表す。 "Synthesis Example 4 Synthesis of Silicone Modified Glycerin at Both Ends"
Charge 100 g of hydrogenated methylphenylpolysiloxane (Mw≈5600) of formula (g), 2.9 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl chloroplatinic acid isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(G)

In the formula, Ph represents a phenyl group.

“Synthesis Example 5 Synthesis of Silicone-Modified Glycerin at Both Ends”
Charge 100 g of hydrogenated methyldodecyl polysiloxane (Mw≈5900) of formula (h), 2.7 g of triglyceryl diallyl ether and 100 g of isopropyl alcohol into a reaction vessel, and add 0.05 g of 3% isopropyl platinate isopropyl alcohol solution. For 5 hours at 80 ° C. Subsequently, 1.5 g of a 0.01N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours, followed by neutralization by adding 0.2 g of 1% sodium bicarbonate water. The reaction solution is concentrated by evaporation to obtain the target compound as a fluid viscous liquid.
(H)

The synthesis scheme of the synthesis examples 1 to 5 is shown in FIG. FIG. 3 shows the IR spectrum of Example 1. Polydimethylsiloxane than peak around in 800,1000,1260,2960Cm ^-1 spectrum, and from the peak derived from a secondary alcohol in the polyglycerol around 1400 cm ^-1 is observed each synthesis proceeds Scheme Street It can be seen that the target compound is obtained.

"Evaluation of dispersion stability"
<Creation of dispersion>
The fine particle powder 38 g, the dispersant prepared by the method of Synthesis Example 1 and Synthesis Example 2 and the comparative sample 5 g were added to 57 g of the silicone-based dispersion medium, and the weight ratio with the fine particle powder was 1: 1. Add glass beads (1 mmΦ) and mix for 1 hour in a paint shaker to create a slurry dispersion. Further, instead of the dispersant produced in Synthesis Example 1, a dispersion using 5 g of the dispersant produced by the method of Comparative Example 1 is similarly prepared. As the powder to be dispersed, a mixed powder of P1 and P2 each in half is used.
Each component used is shown below.
(1) Fine particle powder (P1): Fatty acid soap-treated fine particle titanium dioxide Product name: 100TV (manufactured by Teika)
Particle size: major axis about 0.03 μm, minor axis about 0.005 μm
Aluminum myristate treatment amount: 10% by mass
(2) Fine particle powder (P2): Silicone-treated silica-coated zinc oxide Product name: SS-Activox C80 (manufactured by Showa Denko)
Particle size: about 0.03μm
Silica treatment amount: 20% by mass
(3) Comparative sample: polyether-modified silicone Product name: Silicone KF6017 (manufactured by Shin-Etsu Chemical)
Polyether modification rate: 20% Molecular weight: about 6000 HLB value: 4.0
(4) Dispersion medium: Decamethylcyclopentasiloxane Product name: KF-995 (manufactured by Shin-Etsu Chemical)

<Evaluation of dispersion characteristics>
The rheology of the dispersion is measured, and the dispersion stability of each terminally-modified silicone-modified glycerin powder is evaluated.
(Evaluation methods)
Evaluation device: Corn Instruments viscometer AR1000-N manufactured by TA Instruments
Measurement conditions: 4cm4 ° steel geometry
Shear rate 0.1 s ^{-1 to} 500 s ^-1 25 ° C
(result)
The evaluation result of the dispersion using the both-end silicone-modified glycerin of Synthesis Example 1 is shown in FIG.
The evaluation result of the dispersion using the both-end silicone-modified glycerin of Synthesis Example 2 is shown in FIG.
The evaluation result of the dispersion using the polyether-modified silicone as a comparative sample is shown in FIG.
If the dispersion stability of the powder in the dispersion is good, its flow characteristics will reflect the flow characteristics of silicone as a dispersion medium, and it will have a Newtonian behavior with almost constant viscosity at any shear rate. Show.
In FIG. 6 showing the behavior of the dispersion using the dispersant of the comparative sample, the dispersion obtained by mixing titanium oxide (P1) and zinc oxide (P2) was confirmed to have a significant increase in viscosity in the low shear rate region. It was suggested that the powder was agglomerated.
On the other hand, in FIG. 4 showing the behavior of the dispersion using the dispersant synthesized in Synthesis Example 1 and Synthesis Example 2, the dispersion in which titanium oxide (P1) and zinc oxide (P2) are mixed is almost the same. It showed Newtonian flow characteristics, suggesting very good dispersion stability. There have been few reports of dispersants in which the dispersion exhibits almost Newtonian behavior when using mixed powders (P1 and P2), indicating that the effect of improving dispersion stability is very high. Yes.
From said evaluation measurement, the compound of the synthesis examples 1-2 exhibits the outstanding dispersion stabilizer. The compound of Synthesis Example 3 also exhibits the same dispersion stability as in Synthesis Examples 1 and 2.

“Evaluation of dispersion stability: Relationship between HLB and molecular weight”
The following shows the results of rheological measurements of the powder dispersion characteristics of both terminal-modified silicone-modified glycerin and polyether-modified silicone synthesized in the same manner as in Synthesis Examples 1 to 3 and the comparative sample. From each table, it can be seen that the both-end silicone-modified glycerin used in the present invention has excellent dispersion characteristics.

分散特性
○：良好、△：ほぼ良好、×：不良

Dispersion characteristics ○: Good, Δ: Almost good, ×: Poor

分散特性
○：良好、△：ほぼ良好、×：不良

Dispersion characteristics ○: Good, Δ: Almost good, ×: Poor

  Next, an emulsification stability test was conducted on the water-in-oil cream formulated with the above-mentioned both-end silicone-modified glycerin as an emulsifier and the water-in-oil cream formulated with a conventional emulsifier. The composition of the water-in-oil cream and the results are shown in “Table 3” below. In addition, diglyceryl diisostearate was used in Comparative Example 1 and POE (3) hydrogenated castor oil was used in Comparative Example 2 as conventional representative water-in-oil emulsifiers. Moreover, 2-methoxyhexyl paramethoxycinnamate (IOB 0.28) and di-2-ethylhexyl succinate (IOB 0.32) were mix | blended as a polar oil-based component.

(1) Stability over time (after one month)
After holding the water-in-oil creams of Examples and Comparative Examples at room temperature for 1 month, the form of the emulsion was observed visually (or by an optical microscope).
<Evaluation criteria>
A: The particles were uniform and the emulsified state was good.
○: Some variation was observed in the particles, but the emulsified state was good.
(Triangle | delta): Particle | grains became coarse and isolation | separation of the water phase and the oil phase was seen.
X: The water phase and the oil phase were completely separated.

(2) Temperature stability (50 ° C)
After holding the water-in-oil creams of Examples and Comparative Examples at 50 ° C. for 1 month, the form of the emulsion was observed visually (or with an optical microscope). The evaluation criteria are as follows.
<Evaluation criteria>
A: The particles were uniform and the emulsified state was very good.
○: The particles were almost uniform and the emulsified state was good.
Δ: Some variation was observed in the particles, and slight separation of the water phase and the oil phase was observed.
X: The water phase and the oil phase were completely separated.

  From the results of the above “Table 3”, Example A of the present invention is extremely excellent in stability with time and temperature stability of the emulsion composition as compared with Comparative Examples 1 and 2 using a conventional water-in-oil emulsifier. I understand that

  The cosmetics containing both terminal silicone modified glycerin are shown below.

Example 1 <Mascara>
(Prescription) (mass%)
Light isoparaffin 7
Compound 2 of Synthesis Example 1
Decamethylcyclopentasiloxane 10
Trimethylsiloxysilicate 10
Methyl polysiloxane emulsion Appropriate amount 1,3-butylene glycol 4
Dioleic acid polyethylene glycol 2
Diglyceryl diisostearate 2
DL-α-tocopherol acetate 0.1
P-Hydroxybenzoate appropriate amount black iron oxide 7
Seaweed extract 0.1
Bentonite 1
Dimethyl distearyl ammonium hectorite 6
Polyvinyl acetate emulsion 30
Purified water remaining (evaluation)
The obtained mascara had good gloss and excellent color development.

Example 2 <Mascara>
(Prescription) (mass%)
Light isoparaffin Remaining decamethylcyclopentasiloxane 8
Compound 3 of Synthesis Example 2
Trimethylsiloxysilicate 8
Polyoxyethylene / methylpolysiloxane copolymer 2
1,3-butylene glycol 2
Macadamia nut oil 1
Polyoxyethylene hydrogenated castor oil triisostearate 2
Acrylic resin coated aluminum powder 4
Dimethyl distearyl ammonium hectorite 5
Dextrin palmitate 2
Purified water 2
(Evaluation)
The obtained mascara had good gloss and excellent color development.

Example 3 <Mascara>
(Prescription) (mass%)
Light isoparaffin remaining methyl hydrogen polysiloxane 1
Decamethylcyclopentasiloxane 10
Compound 1 of Synthesis Example 1
Castor oil 2
Candelilla Row 5
Isostearic acid 3
Oleic acid 1
Glyceryl tri-2-ethylhexanoate 2
Mukuroji extract 0.1
Oat extract 0.1
Dextrin palmitate 13
Trimethylsiloxysilicate 15
Tetradecene 0.1
Polyethylene 5
Microcrystalline wax 5
(Evaluation)
The obtained mascara had good gloss and excellent color development.

Example 4 <Mascara>
(Prescription) (mass%)
Light isoparaffin Compound 3 of residual synthesis example 3
Decamethylcyclopentasiloxane 5
Octyl palmitate 1
Isostearic acid 1
Microcrystalline wax 1
Carnauba wax 2
Crow 2
(Palmitic acid / octanoic acid) dextrin 15
Sucrose mixed fatty acid ester 20
("Cosmelike MX-10"; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Sucrose tetraisostearate 10
("Crodesta 4-IS"; manufactured by Coda Japan Co., Ltd.)
Trimethylsiloxysilicic acid 5
Aluminum stearate 1
Silicone-coated pigment (iron oxide) 0.5
Silicone-coated pigment (titanium oxide) 0.3
Silicone-coated pigment (Bengara) 0.2
Barium sulfate 0.1
Bengala-coated mica appropriate amount δ-tocopherol 0.1
(Evaluation)
The obtained mascara had good gloss and excellent color development.

Example 5 <Lipstick>
(Prescription) (mass%)
Methylphenylpolysiloxane 5
Non-aqueous polymer emulsion (*) 30
Fluorine-modified methylphenylpolysiloxane 25
Decamethylcyclopentasiloxane 5
Compound 5 of Synthesis Example 4
Dimethylpolysiloxane Residual polyoxyethylene-modified silicone 5
Glycerin 3
Pigment 5
Ceresin 10
Candelilla Row 2
Aerosil R972 (Degussa) 1
Spherical silica 0.5
δ-Tocopherol 0.05
Octyl methoxycinnamate 0.5
Laponite 0.3
(*) 15% methyl methacrylate monomer, 25% ethyl acrylate monomer, 0.1% polymerization initiator, 5% dispersion stabilizer dimethylpolysiloxane graft polymer (molecular weight about 150,000) 5% decamethylcyclopentasiloxane 54.9%, polymerized by stirring at 120 ° C. for 10 hours, and then de-monomerized by decompression, then cooled to 25 ° C., the appearance was milky white and the average particle size of the dispersed polymer particles A non-aqueous polymer dispersion using a volatile silicone having a diameter of 1 μm as a dispersion medium was obtained.
(Evaluation)
The obtained lipstick gave a moist feel and had a good feeling of use with little stickiness.

Example 6 <Lipstick>
(Prescription) (mass%)
Ceresin 6
Decamethylcyclopentasiloxane Residual Synthesis Example 5 Compound 5
Polyoxyethylene methylpolysiloxane copolymer (MW = 6000)
Five
"Non-aqueous dispersion of alkyl acrylate / tris (trimethylsiloxy) silylpropyl methacrylate dispersed in decamethylcyclopentasiloxane"
30
Dimethylsiloxane ・ Diphenylsiloxane ・ Methyl (perfluoroalkyl) siloxane 20
Methylphenylpolysiloxane 5
Stearoxymethylpolysiloxane 2
Candelilla Row 4
Silylated silica 1
Silicone coated pigment (Bengara, titanium oxide, etc.) 7
Bengala coated mica titanium 5
Mica 1
Dye Suitable amount Silicic anhydride 2
Titanium oxide 3
Poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer (MW = 50000) 2
Perfume appropriate amount (evaluation)
The obtained lipstick was glossy, gave a moist feel, had little stickiness, and had a good use feeling.

Example 7 <Lipstick>
(Prescription) (mass%)
α-Olefin oligomer 5
Methylphenylpolysiloxane 5
Compound 2 of Synthesis Example 1
Diisostearyl malate Residual heavy liquid isoparaffin 25
Pigment 7
Glycerin 1
1,3-butylene glycol 3
Calcium chloride 0.1
Acetylated sodium hyaluronate 0.02
2-Ethylhexyl paramethoxycinnamate 2
Synthetic sodium silicate / magnesium 1.5
Dextrin palmitate 2.5
Polyoxyethylene / methylpolysiloxane copolymer 0.5
Purified water 1
Perfume appropriate amount (evaluation)
The obtained lipstick gave a moist feel and had a good feeling of use with little stickiness.

Example 8 <Solid powdery foundation>
(Prescription) (mass%)
Dimethylpolysiloxane 5
Compound 2 of Synthesis Example 1
Isostearic acid 0.5
Diisostearyl malate 3
Tri-2-ethylhexane sangglyceryl 1
Sorbitan sesquiisostearate 1
Spherical PMMA-coated mica 6
Prism tone powder YR 1
Fine zinc oxide 0.5
Fine particle titanium oxide 2
Synthetic phlogopite 2
Metal soap treated talc 8
Spherical silica 5
Vitamin E acetate 0.1
δ-tocopherol 0.1
Ethyl paraben Appropriate amount of methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate
1
2-Ethylhexyl paramethoxycinnamate 3
Spherical polyalkyl acrylate powder 6
Methyl hydrogen polysiloxane coated talc Residual methyl hydrogen polysiloxane coated sericite 20
Methyl hydrogen polysiloxane coated titanium oxide 15
Methyl hydrogen polysiloxane coated pigment (colorant) 5
(Evaluation)
The obtained lipstick solid powdery foundation was excellent in coloring and very smooth to the touch.

Example 9 <solid powdery foundation>
(Prescription) (mass%)
Synthetic hydrocarbon wax particles 2
Dimethylpolysiloxane 6
Purified lanolin 5
Compound 5 of Synthesis Example 4
Glyceryl tri-2-ethylhexanoate 2
Sorbitan sesquiisostearate 0.5
Acicular fine particle titanium oxide 5
Fine zinc oxide 1
Silicone-coated iron oxide / titanium oxide sintered product 7
Barium sulfate 8
Calcined sericite residual titanium reduction treated mica titanium pearl pigment 2
Silicone-coated synthetic phlogopite 5
Silicone-coated talc 2
Spherical silica 3
Silicone-coated mica 15
Stearyl glycyrrhetinate 0.1
Ascorbyl dipalmitate 0.1
DL-α-tocopherol acetate 0.1
D-δ-tocopherol 0.1
P-Hydroxybenzoic acid ester 2-ethylhexyl paramethoxycinnamate 3
Silicone coated Bengala 1
Silicone coated yellow iron oxide 1
Silicone coated black iron oxide 1
Spherical polyalkyl acrylate 3
Perfume

Example 10 <Solid Powder Foundation>
(Prescription) (mass%)
Silicone-treated sericite 15
Silicone-treated mica 20
Silicone-treated synthetic mica 10
Silicone-treated talc Residual zinc oxide 2
Methylsiloxane network polymer spherical powder 4
Boron nitride 3
Zinc myristate 2
Mica titanium grinding liquid 3
Silicone-treated titanium oxide 10
Silicone-treated iron oxide 4
Silicone-treated zinc oxide 5
Dimethylpolysiloxane 4
Compound 2 of Synthesis Example 1
2-Ethylhexyl paramethoxycinnamate 3
Polyoxyethylene / alkyl co-modified silicone 1
Sorbitan sesquiisostearate 1
Paraben Appropriate amount δ-Tocopherol Appropriate perfume Appropriate amount (Manufacturing method and evaluation)
The powder component, oil component and mica titanium pulverized liquid in the formulation were dispersed and mixed in ethyl alcohol using a sand grinder mill containing zirconia beads having a diameter of 3 mm. After distilling ethyl alcohol, it was pulverized once with a pulverizer, filled into a container (resin-made middle dish), and dry molded by a known method to obtain a solid powdery foundation. The obtained solid powdery foundation was excellent in smoothness.

Example 11 <Solid powdery foundation>
(Prescription) (mass%)
Methyl (N-propyl-pyrrolidone carboxylic acid)
Siloxane / Methylpolysiloxane Copolymer 5
Compound 5 of Synthesis Example 1
Dimerlinoleic acid (phytosteryl / behenyl) 5
Tri-2-ethylhexanoic acid glycerin 3
Methyl polysiloxane 2
Sorbitan sesquiisostearate 1
Pearl pigment (trade name: Temilon MP-115) 40
Mica 10
Yellow iron oxide 2
Talc remaining amount (production method and evaluation)
After mixing the powder component with a Henschel mixer or the like, the oil component is added and mixed uniformly to prepare a cosmetic base. On the other hand, 60-70 mass% of ethanol is added and mixed uniformly to form a slurry. At this time, since a part of the oily component was lost due to the removal of ethanol, an increase in the amount of 120 to 160% was appropriately performed so that the blending amount in the final product was the prescribed amount. This is filled into an inner dish and compression molded using a molding head (molding pressure 20 kg), and ethanol is sucked from the back surface of the molding head at the same time. After suction, the molded product was dried at 50 ° C. for 2 hours. The slurry obtained in the production process has improved fluidity and productivity.

Example 12 <Foundation>
(Prescription) (mass%)
Dimethylpolysiloxane 3
Decamethylcyclopentasiloxane 10
Compound 1 of Synthesis Example 1
Polyoxyethylene / methylpolysiloxane copolymer 3
Dodecamethylcyclohexasiloxane 5
Glycerin 4
1,3-butylene glycol 5
Palmitic acid 0.5
Distearyldimethylammonium chloride 0.2
Metal soap treated talc 2
Cross-linked silicone powder (Trefil E-506) 0.1
Bengala-coated mica titanium 0.5
N-lauroyl-L-lysine 2
Tocopherol acetate 0.1
δ-tocopherol 0.1
P-Hydroxybenzoate Appropriate amount Phenoxyethanol 0.2
Spherical nylon powder 1
Spherical polyalkyl acrylate powder 3
Merrilot extract 2
Purified water Residual dextrin fatty acid-treated talc 3
Dextrin fatty acid-treated titanium dioxide 15
Dextrin fatty acid-treated yellow iron oxide 3
Dextrin fatty acid-treated black iron oxide 0.5
(Manufacturing method and evaluation)
Each of the oily component and aqueous component in the formulation is heated and completely dissolved. The aqueous phase is added to the oil phase and emulsified with an emulsifier. The obtained emulsion was cooled by a heat exchanger to obtain a foundation. The obtained foundation was excellent in smoothness and had a good feeling of use with no stickiness.

Example 13 <Foundation>
(Prescription) (mass%)
Dimethylpolysiloxane 15
Decamethylcyclopentasiloxane 20
Compound 5 of Synthesis Example 5
Polyoxyethylene / methylpolysiloxane copolymer 5
High molecular weight amino-modified silicone 0.1
Glycerin 5
1,3-butylene glycol 10
Palmitic acid 0.5
Macadamia nut oil fatty acid cholesteryl 0.1
Distearyldimethylammonium chloride 0.2
Alkyl-modified silicone resin coated yellow iron oxide 2
Alkyl modified silicone resin coated bengara 1
Alkyl-modified silicone resin coated black iron oxide 0.3
Alkyl modified silicone resin coated titanium oxide 10
Alkyl modified silicone resin coated talc oxide 1.5
Silicone coated spindle-shaped titanium oxide 3
DL-α-tocopherol acetate 0.1
P-Hydroxybenzoate Methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate
0.1
Dimethyl distearyl ammonium hectorite 1.5
Spherical nylon powder 1
Purified water Residual fragrance Appropriate amount (Production method and evaluation)
Each of the oily component and aqueous component in the formulation is heated and completely dissolved. The aqueous phase is added to the oil phase and emulsified with an emulsifier. The obtained emulsion was cooled by a heat exchanger to obtain a foundation. The obtained foundation was excellent in smoothness and had a good feeling of use with no stickiness.

Example 14 <Rinse>
(Prescription) (mass%)
Dimethylpolysiloxane 2
Compound 2 of Synthesis Example 2
Stearyl alcohol 2
Behenyl alcohol 1
Glycerin 1.5
Octyl palmitate 1
Polyoxyethylene stearyl ether 0.2
Citric acid 0.05
Paraoxybenzoic acid ester Appropriate amount Phenoxyethanol Appropriate amount Hydroxyethylcellulose 0.1
Stearyltrimethylammonium chloride 1
Highly polymerized methylpolysiloxane 1.5
Purified water Residual fragrance Appropriate amount (Production and evaluation)
The said component was mixed by the conventional method and the hair rinse was obtained. The obtained rinse was not sticky, had no squeaky feeling, and improved the smoothness of the hair.

Example 15 <Rinse>
(Prescription) (mass%)
Dimethylpolysiloxane 15
Compound 5 of Synthesis Example 4
Highly polymerized dimethylpolysiloxane 1
Cetanol 4.5
Glycerin 10
Cetyl 2-ethylhexanoate 2
Alkyltrimethylammonium chloride 1.5
Distearyldimethylammonium chloride 0.3
Citric acid 0.01
Tocopherol acetate 0.05
P-hydroxybenzoate appropriate amount phenoxyethanol appropriate amount hydroxyethylcellulose 0.05
Purified water Residual fragrance Appropriate amount (Production method and evaluation)
The said component was mixed by the conventional method and the hair rinse was obtained. The obtained rinse was not sticky, had no squeaky feeling, and improved the smoothness of the hair.

Example 16 <Rinse>
(Prescription) (mass%)
Dimethylpolysiloxane 0.5
Compound of Synthesis Example 5 0.5
Benzyl alcohol 5
Cetostearyl alcohol 7
Behenyl alcohol 3
Self-emulsifying glyceryl monostearate 1
N-stearoyl-N-methyltaurine sodium 1
Citric acid 0.2
Phenoxyethanol Appropriate amount of purified water Residual fragrance Appropriate amount (Production method and evaluation)
The said component was mixed by the conventional method and the hair rinse was obtained. The resulting rinse had a good feel and improved the smoothness of the hair.

Example 17 <Hair Shampoo>
(Prescription) (mass%)
Dimethylpolysiloxane 1.5
Compound of Synthesis Example 3 0.5
Dipropylene glycol 3
Ethylene glycol distearate 2
Palm oil fatty acid monoethanolamide 2
Lauroylmethyl taurine sodium 0.1
Sodium polyoxyethylene lauryl ether sulfate 7.5
Polyoxyethylene lauryl ether sulfate triethanolamine
3.5
Palm oil fatty acid amidopropyl betaine 3.5
Marcote 550 (Calgon) 7.5
Citric acid 0.01
L-glutamic acid 0.2
Sodium chloride 1
Sodium benzoate proper amount disodium edetate proper amount sodium hydroxide 0.01
Purified water Residual fragrance Appropriate amount <Production method and evaluation>
The above components were mixed by a conventional method to obtain a hair shampoo. The hair washed with the obtained hair shampoo was excellent in the feel of the hair during use.

Example 18 <Hair Shampoo>
(Prescription) (mass%)
Dimethylpolysiloxane 0.1
Compound of Synthesis Example 1 0.1
Highly polymerized dimethylpolysiloxane 0.15
Ethylene glycol distearate 2.5
Palm oil fatty acid diethanolamide 6
Sodium dodecane-1,2-diol acetate ether 1.5
Palm oil fatty acid methyl taurine sodium 7.5
Palm oil fatty acid amidopropyl betaine 5
Polymer JR-400 (Union Carbide) 0.1
Dimethyldiallylammonium chloride acrylamide copolymer
1
Citric acid 0.7
Sodium chloride 0.7
Phenoxyethanol Appropriate amount Sodium benzoate Appropriate amount Disodium edetate Appropriate amount Purified water Residual perfume Appropriate amount <Production method and evaluation>
The above components were mixed by a conventional method to obtain a hair shampoo. The hair washed with the obtained hair shampoo was excellent in the feel of the hair at the time of use, and further gave gloss to the hair after drying.

Example 19 <Rinse In Shampoo>
(Prescription) (mass%)
Dimethylpolysiloxane 2
Compound 1 of Synthesis Example 2
Polyoxyethylene / methylpolysiloxane copolymer 2
Cetanol 0.5
Polyoxyethylene hydrogenated castor oil 4
Ethylene glycol distearate 2
Palm oil fatty acid diethanolamide 7
Sodium polyoxyethylene lauryl ether sulfate 5
Polyoxyethylene lauryl ether sulfate triethanolamine
2.5
Lauroylmethyl-β-alanine sodium 1
Coconut oil fatty acid methyl taurine sodium 4
Lauryldimethylaminoacetic acid betaine 5
Polymer JR-400 (Union Carbide) 0.4
Stearyltrimethylammonium chloride (25%) 0.1
Citric acid 0.4
Sodium benzoate Appropriate amount Disodium edetate Appropriate amount Purified water Residual perfume Appropriate amount <Production and evaluation>
The above components were mixed by a conventional method to obtain a rinse-in shampoo. The hair washed with the rinse-in shampoo thus obtained was excellent in the feel of the hair during use, particularly smooth, and the hair after drying was also smooth.

Example 20 <Cleansing Oil>
(Prescription) (mass%)
Ion exchange water 4
Glycerin 1
PEG (8) glyceryl isostearate 35
Liquid paraffin Residual glyceryl triisooctanoate 5
Isoparaffin 5
Dimethylpolysiloxane (6mPa.s) 3
Compound 1 of Synthesis Example 4
Pentaerythrityl tetraoctanoate 3
Squalane 3
Methylphenylpolysiloxane 3
Ascorbic acid glucoside 0.1
(Manufacturing method and evaluation)
Cleansing oil was obtained by mixing and dissolving. The obtained cleansing oil was smooth and non-sticky, and had a good feeling of use with no squeaky feeling after washing.

Example 21 <Cleansing Oil>
(Prescription) (mass%)
Liquid paraffin 73
Dimethylpolysiloxane 2
Compound 1 of Synthesis Example 2
Ethanol 0.3
Isostearic acid 0.5
Lauric acid 0.1
Cetyl 2-ethylhexanoate 10
Diisostearic acid PEG-12 4
PEG-8 1 diisostearate
PEG-10 3 isostearate
Vitamin E 0.1
Purified water residue (Production method and evaluation)
Cleansing oil was obtained by mixing and melting. The obtained cleansing oil was smooth and non-sticky, and had a good feeling of use with no squeaky feeling after washing.

Example 22 <Hair Spray>
(Prescription) (mass%)
Volatile isoparaffin 14
Dimethylpolysiloxane 3
Compound 1 of Synthesis Example 1
Ethanol appropriate amount purified water 2
Highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer
Four
Poly (oxyethylene / oxypropylene) / methylpolysiloxane copolymer
Four
Perfume

Stock solution / propellant = 40/60 (LPG 0.115 MPa)
(Manufacturing method and evaluation)
After mixing and melting, an aerosol spray was formed at the above composition ratio. The hair sprayed with the obtained hair spray was less sticky after application and showed a smooth and good feel.

Example 23 <Hair Cream>
(Prescription) (mass%)
Dimethylpolysiloxane 5
Compound of Synthesis Example 5 10
Polyoxyethylene methyl polysiloxane copolymer 0.2
Ethanol 10
Propylene glycol 5
2-amino-2-methyl-1-propanol appropriate amount trisodium edetate appropriate amount xanthan gum 0.1
Vinyl acetate / vinyl pyrrolidone copolymer 0.5
Acrylic acid / alkyl methacrylate copolymer 0.2
Carboxyvinyl polymer 0.4
Highly polymerized dimethylsiloxane / methyl (aminopropyl) siloxane copolymer
0.5
Highly polymerized dimethylpolysiloxane 1
Purified water Residual fragrance Appropriate amount (evaluation)
This hair cream showed an excellent effect of giving hair suppleness.

Example 24 <Hair Cream>
(Prescription) (mass%)
Volatile isoparaffin 10
Dimethylpolysiloxane 1
Compound 1 of Synthesis Example 2
Ethanol 10
1,3-butylene glycol 5
Isostearic acid 0.5
Polyoxyethylene hydrogenated castor oil 0.1
2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine
1
Sodium hydroxide 0.3
Highly polymerized methylpolysiloxane 2
Carboxyvinyl polymer 0.8
P-Hydroxybenzoate appropriate amount edetate trisodium appropriate amount purified water residual fragrance appropriate amount

Example 25 <Hair Cream>
(Prescription) (mass%)
Liquid paraffin 5
Vaseline 2
Dimethylpolysiloxane 3
Compound 3 of Synthesis Example 4
Cetanol 4
Stearyl alcohol 1
1,3-butylene glycol 10
Polyoxypropylene glyceryl ether 2
Polyoxyethylene glyceryl isostearate 2
Lipophilic glyceryl monostearate 2
Polymer JR-400 0.5
P-Hydroxybenzoate Equal amount Purified water Residual perfume Appropriate amount (Evaluation)
This hair cream has an excellent effect of giving hair suppleness.

Example 26 <Hair Mousse>
(Prescription) (mass%)
Ethanol 10
Propylene glycol 5
Lauric acid diethanolamide 0.2
Alkyltrimethylammonium chloride (77%) 0.1
Yuka Femer SM 10
Polyoxyethylene / methylpolysiloxane copolymer 1
Volatile isoparaffin 5
Highly polymerized dimethylpolysiloxane 1
Compound 1 of Synthesis Example 4
Purified water Residual fragrance

Stock solution / propellant = 40/60 (LPG 0.43 MPa)
(Manufacturing method and evaluation)
The aqueous component and the oil component are mixed and dissolved, and the oil phase portion is added to the aqueous phase portion and emulsified using a homogenizer. The obtained emulsion was made into an aerosol formulation with the above composition. The obtained hair mousse showed smooth and non-sticky usability.

Example 27 <Wax Mousse>
(Prescription) (mass%)
Liquid paraffin 6
Dimethylpolysiloxane 5
Compound 3 of Synthesis Example 3
Glycerin 8
Propylene glycol 8
Butylethylpropanediol 0.5
Jojoba oil 1
Carnauba wax 5
Isostearic acid 0.5
Polyoxyethylene hydrogenated castor oil 0.5
Polyoxyethylene behenyl ether 5
2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine
8
Phenoxyethanol 0.5
Highly polymerized dimethylpolysiloxane 0.5
Purified water Residual fragrance

Stock solution / propellant = 90/10 (LPG 0.43 MPa)
(Evaluation)
This wax mousse showed a good feel when used without any stickiness, smoothness and gloss.

Example 28 <Wax>
(Prescription) (mass%)
Liquid paraffin 10
Vaseline 5
Microcrystalline wax 5
Stearyl alcohol 2
Propylene glycol 10
Carnauba wax 3
Isostearic acid 1
Stearic acid 2
Compound 1 of Synthesis Example 5
Tetra-2-ethylhexanoic acid pentaerythrit 3
Polyoxyethylene glyceryl isostearate 1
Self-emulsifying glyceryl monostearate 2
Kaolin 5
Silicic anhydride 2
Triethanolamine 0.3
Sodium metaphosphate appropriate amount paraoxybenzoate appropriate amount xanthan gum 0.1
Bentonite 1
Purified water Residual fragrance
This hair wax had no stickiness and showed a good feeling of use.

Example 29 <Hair Oil>
(Prescription) (mass%)
Hydrogenated polyisobutene Residual ethanol 10
Oxybenzone appropriate amount highly polymerized methylpolysiloxane 10
Compound 2 of Synthesis Example 4
(Manufacturing method and evaluation)
Hair oil was obtained by mixing and melting. The obtained hair oil was not sticky and gave good gloss to the hair.

Example 30 <Emulsion>
(Prescription) (mass%)
Dimethylpolysiloxane 2
Compound 1 of Synthesis Example 1
Behenyl alcohol 1
Batyl alcohol 0.5
Glycerin 5
1,3-butylene glycol 7
Erythritol 2
Hardened oil 3
Squalane 6
Tetra-2-ethylhexanoic acid pentaerythlit 2
Polyoxyethylene glyceryl isostearate 1
Polyoxyethylene glycerol monostearate 1
Potassium hydroxide Appropriate amount Sodium hexametaphosphate 0.05
Phenoxyethanol appropriate amount carboxyvinyl polymer 0.1
Purified water residue (Production method and evaluation)
An emulsion was prepared using conventional methods. The obtained emulsion gave a smooth and good feel while refreshing.

Example 31 <Emulsion>
(Prescription) (mass%)
Liquid paraffin 7
Vaseline 3
Decamethylcyclopentasiloxane 1
Compound 1 of Synthesis Example 5
Behenyl alcohol 1
Glycerin 5
Dipropylene glycol 7
Polyethylene glycol 1500 2
Jojoba oil 1
Isostearic acid 0.5
Stearic acid 0.5
Behenic acid 0.5
Tetra-2-ethylhexanoic acid pentaerythrit 3
Cetyl 2-ethylhexanoate 3
Glycerol monostearate 1
Polyoxyethylene glycerol monostearate 1
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.05
Stearyl glycyrrhetinate 0.05
L-Arginine 0.1
Royal Jelly Extract 0.1
Yeast extract 0.1
Tocopherol acetate 0.1
Acetylated sodium hyaluronate 0.1
Edetate trisodium 0.05
4-t-butyl-4'-methoxydibenzoylmethane 0.1
2-Ethylhexyl paramethoxycinnamate 0.1
Carboxyvinyl polymer 0.15
Paraben Appropriate amount of purified water Residual fragrance Appropriate amount (Production method and evaluation)
An emulsion was prepared using conventional methods. The obtained emulsion gave a smooth and good feel while refreshing.

Example 32 <Protector>
(Prescription) (mass%)
Dimethylpolysiloxane 2
Decamethylcyclopentasiloxane 20
Compound 5 of Synthesis Example 4
Dodecamethylcyclohexasiloxane 10
Polyoxyethylene / methylpolysiloxane copolymer 1.5
Trimethylsiloxysilicate 1
1,3-butylene glycol 5
Squalane 0.5
Talc 5
Dipotassium glycyrrhizinate 0.1
Tocopherol acetate 0.1
Edetate trisodium 0.05
4-t-butyl-4'-methoxydibenzoylmethane 1
2-methoxyhexyl paramethoxycinnamate 5
Diparamethoxycinnamic acid mono-2-ethylhexanoic acid glyceryl
1
Silicone coated fine particle titanium oxide (40nm) 4
Dimethyl distearyl ammonium hectorite 0.5
Spherical polyethylene powder 3
Phenoxyethanol Appropriate amount of purified water Residual fragrance Appropriate amount (Production method and evaluation)
The oil phase part and the water phase part are mixed and dissolved. In the oil phase part, the powder is sufficiently dispersed, and the water phase part is added and emulsified using a homogenizer. The obtained protector was highly transparent and excellent in refreshing.

Example 33 <Protector>
(Prescription) (mass%)
Dimethylpolysiloxane 2
Compound 2 of Synthesis Example 2
Methylphenylpolysiloxane 2
Ethanol 5
Glycerin 4
Dipropylene glycol 5
1,3-butylene glycol 5
Di-2-ethylhexyl succinate 3.5
Potassium hydroxide 0.1
Sodium hexametaphosphate 0.1
Thiotaurine 0.1
Edetate trisodium 0.1
4-t-butyl-4'-methoxydibenzoylmethane 3
2-methoxyhexyl paramethoxycinnamate 3
Iron oxide 0.01
Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)
0.1
Carboxyvinyl polymer 0.2
Paraben Appropriate amount of purified water Residual perfume Appropriate amount (Production method and evaluation)
The oil phase part and the water phase part are mixed and dissolved. Add the oil phase to the water phase and emulsify using a homogenizer. The obtained protector was highly transparent and excellent in refreshing.

Example 34 <Lotion>
(Prescription) (mass%)
Dimethylpolysiloxane 0.5
Compound of Synthesis Example 3 0.5
Ethanol 3
Behenyl alcohol 0.3
Glycerin 5
Dipropylene glycol 5
Erythritol 1
Polyethylene glycol 4000 1
Squalane 0.4
Cetyl 2-ethylhexanoate 0.1
N-stearoyl-sodium L-glutamate 0.2
Magnesium chloride 0.1
Arginine chloride 0.1
Hipotaurine 0.1
Edetate trisodium 0.1
Paraben Appropriate amount of purified water Residual perfume Appropriate amount (evaluation)
This lotion showed a smooth and good feel.

Example 35 <Cream>
(Prescription) (mass%)
Dimethylpolysiloxane 3
Compound 1 of Synthesis Example 1
Decamethylcyclopentasiloxane 15
Trimethylsiloxysilicate 1
Polyoxyethylene / methylpolysiloxane copolymer 2
Glycerin 1
1,3-butylene glycol 5
Squalane 1
Titanium oxide 1
Talc 2
Aluminum stearate 0.5
Oil-soluble licorice extract 0.5
Edetic acid 3Na appropriate amount paraben appropriate amount phenoxyethanol appropriate amount dimethyl distearyl ammonium hectorite 0.8
Spherical nylon powder 1
Purified water residue (production method and evaluation)
The oil phase part and the water phase part are mixed and dissolved. Add the water phase to the oil phase and emulsify using a homogenizer. The resulting cream showed a smooth and good feel.

Example 36 <Cream>
(Prescription) (mass%)
Stearic acid 10
Compound 1 of Synthesis Example 5
Stearyl alcohol 4
Butyl stearate 8
Stearic acid monoglycerin ester 2
Vitamin E acetate 0.5
Vitamin A palmitate 0.1
Macadamia nut oil 1
Fragrance Appropriate Glycerin 4
1,2 pentanediol 3
Sodium hyaluronate 1
Potassium hydroxide 2
Magnesium ascorbate phosphate 0.1
L-arginine hydrochloride 0.01
Edetate trisodium 0.05
Purified water residue (Production method and evaluation)
The oil phase part and the water phase part are each heated to 70 ° C. and completely dissolved. Oil is added to the aqueous phase and emulsified with an emulsifier. The emulsion was cooled by a heat exchanger to obtain a cream. The obtained cream was excellent in smoothness and showed a good feeling of use with no stickiness.

Example 37 <Sunscreen>
(Prescription) (mass%)
Decamethylcyclopentasiloxane 15
Compound 2 of Synthesis Example 2
Trimethylsiloxysilicate 1
Polyoxyethylene / methylpolysiloxane copolymer 2
Dipropylene glycol 4
Squalane 5
Silicone coated fine particle titanium oxide (20nm) 10
Talc (hydrophobized product) 6
Paraben appropriate amount phenoxyethanol appropriate amount 4-t-butyl-4'-methoxydibenzoylmethane 0.1
2-Ethylhexyl paramethoxycinnamate 7
Diparamethoxycinnamic acid mono-2-ethylhexanoic acid glyceryl
0.5
Spherical polyethylene powder 5
Dimethyl distearyl ammonium hectorite 1
Purified water Residual fragrance Appropriate amount (Production method and evaluation)
The oil phase part and the water phase part are mixed and dissolved. In the oil phase part, the powder is sufficiently dispersed, and the water phase part is added and emulsified using a homogenizer. The obtained sunscreen was highly transparent and excellent in refreshing.

Example 38 <Gel>
(Prescription) (mass%)
Dimethylpolysiloxane 3
Compound 2 of Synthesis Example 3
Glycerin 2
1,3-butylene glycol 5
Polyethylene glycol 1500 3
Polyethylene glycol 20000 3
Cetyl octanoate 3
Citric acid 0.01
Sodium citrate 0.1
Sodium hexametaphosphate 0.1
Dipotassium glycyrrhizinate 0.1
Ascorbic acid glucoside 2
Tocopherol acetate 0.1
Ogon Extract 0.1
Yukinoshita Extract 0.1
Edetate trisodium 0.1
Xanthan gum 0.3
Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-2)
0.05
Agar powder 1.5
Phenoxyethanol Appropriate amount Dibutylhydroxytoluene Appropriate amount of purified water Residue (Production and evaluation)
In accordance with a conventional method, after producing a translucent emulsion composition, it is cooled to 30 ° C. or less to be gelled, and when sufficiently hardened, the gel is crushed using a disper to obtain a microgel (average particle size 70 μm), and then removed. A gel product was obtained. The obtained gel was refreshing, smooth and free from squeaky, and showed good usability.

Example 39 <Sunscreen Latex>
(Prescription) (mass%)
Dimethylpolysiloxane 5
Decamethylcyclopentasiloxane 25
Compound 2 of Synthesis Example 4
Trimethylsiloxysilicate 5
Polyoxyethylene / methylpolysiloxane copolymer 2
Ethyl hexanoate 5
Dipropylene glycol 5
Dextrin palmitate coated fine zinc oxide (60nm) 15
Glutathione 1
Thiotaurine 0.05
Clara extract 1
Paraben appropriate amount phenoxyethanol appropriate amount 2-methoxyhexyl paramethoxycinnamate 7.5
Dimethyl distearyl ammonium hectorite 0.5
Spherical polyalkyl acrylate powder 5
Butylethylpropanediol 0.5
Purified water Residual fragrance Appropriate amount (Production and evaluation)
The oil phase part and the water phase part are mixed and dissolved. In the oil phase part, the powder is sufficiently dispersed, and the water phase part is added and emulsified using a homogenizer. The obtained sunscreen formulation was excellent in refreshing.

Example 40 <Sunscreen Latex>
(Prescription) (mass%)
Dimethylpolysiloxane 5
Decamethylcyclopentasiloxane 25
Trimethylsiloxysilicate 5
Compound 2 of Synthesis Example 2
Polyoxyethylene / methylpolysiloxane copolymer 2
Squalane 5
Dipropylene glycol 5
Fine zinc oxide (hydrophobized 60nm) 15
Paraben appropriate amount phenoxyethanol appropriate amount 2-methoxyhexyl paramethoxycinnamate 7.5
Dimethyl distearyl ammonium hectorite 0.5
Spherical polyalkyl acrylate powder 5
Purified water Residual fragrance Appropriate amount (Production and evaluation)
The oil phase part and the water phase part are mixed and dissolved. In the oil phase part, the powder is sufficiently dispersed, and the water phase part is added and emulsified using a homogenizer. The obtained sunscreen formulation had a low viscosity and was excellent in refreshing.

Example 41 W / O type foundation (1) Sericite 5 mass%
(2) Kaolin 4
(3) Titanium dioxide 6
(4) Bengala 0.36
(5) Yellow iron oxide 0.8
(6) Black iron oxide 0.16
(7) Aluminum stearate-treated titanium dioxide 4
(8) Zinc oxide treated with dextrin fatty acid 4
(9) Compound 3 of Synthesis Example 3
(10) Liquid paraffin 5
(11) Decamethylcyclopentasiloxane 29
(12) POE-modified dimethylpolysiloxane 4
(13) Ion exchange water 36
(14) 1,3-butylene glycol 5
(15) Preservative 0.1
(16) Perfume 0.08
(Manufacturing method)
(7), (8) and (9) were dispersed and crushed with a bead mill, and then (1) to (6), (10) and (11) were added and mixed to obtain an oil phase. (12) to (15) were heated and dissolved at 70 ° C. and added to the oil phase to emulsify. Further, add (16), mix and fill the container.

Example 42 Oily foundation (1) Talc 14.3 mass%
(2) Kaolin 10
(3) Bengala 1
(4) Dextrin fatty acid-treated yellow iron oxide 3
(5) Dextrin fatty acid-treated black iron oxide 0.2
(6) Dextrin fatty acid-treated titanium dioxide 5
(7) Dextrin fatty acid-treated zinc oxide 5
(8) Liquid paraffin 20
(9) Dimethylpolysiloxane 15
(10) Octyl methoxycinnamate 1
(11) Sorbitan sesquiisostearate 2
(12) Isohexadecyl alcohol 10
(13) Ceresin 4
(14) Carnavalou 1
(15) Compound 1 of Synthesis Example 1
(16) Perfume appropriate amount (production method)
(8) and (10) to (14) were heated and mixed at 90 ° C. to obtain an oil phase. Separately, (6), (7), (9) and (15) were mixed and dispersed and crushed with a bead mill, and then this kneaded product and (1) to (5) were added to the oil phase and mixed with a disper. . Further, (16) is mixed, filled into a container and cooled.

Example 43 Two-layer Type W / O Sunscreen (1) Talc 6% by mass
(2) Aluminum stearate-treated fine particle titanium dioxide 6
(3) Aluminum stearate-treated fine particle zinc oxide 10
(4) Compound 3 of Synthesis Example 3
(5) Liquid paraffin 1
(6) Decamethylcyclopentasiloxane 30
(7) Dimethylpolysiloxane 20
(8) POE-modified dimethylpolysiloxane 2
(9) Ion exchange water 15
(10) 1,3-butylene glycol 8
(11) Preservative 0.1
(12) Fragrance 0.1
(Manufacturing method)
(5), (6) and (8) are heated and mixed at 70 ° C. to obtain an oil phase. Separately, (2) to (4) and (7) were mixed and kneaded with three rollers. This kneaded product and (1) are added to the oil phase and mixed with a disper. A solution obtained by heating and dissolving (9) to (11) at 70 ° C. is added thereto to emulsify, and (12) is further mixed and filled into a container.

Example 44 Stick-type sunscreen (oil-based cosmetic)
(1) Talc 3% by mass
(2) Kaolin 10
(3) Mica 3
(4) Aluminum palmitate-treated fine particle titanium dioxide 25
(5) Dimethylpolysiloxane 20
(6) Isopropyl palmitate 13.9
(7) Solid paraffin 2
(8) Microcrystalline wax 3
(9) Vaseline 10
(10) Ceresin 8
(11) Carnavalou 1
(12) Compound 2 of Synthesis Example 2
(13) Fragrance 0.1
(Manufacturing method)
(6) to (11) are heated and mixed at 90 ° C. to obtain an oil phase. Separately, (4), (5) and (12) were mixed and kneaded with three rollers. This kneaded product and (1) to (3) are added to the oil phase and mixed with a disper. Further, (13) is mixed, filled into a container and cooled.

Example 45: Suncut oil-in-water emulsion (1) Aluminum stearate-treated titanium dioxide 5% by mass
(2) Dextrin stearate-treated zinc oxide 5
(3) Compound 3 of Synthesis Example 1
(4) Decamethylpentacyclosiloxane 13
(5) Octyl paramethoxycinnamate 5
(6) PEG-60 hydrogenated castor oil 2
(7) Dynamite glycerin 6
(8) Succinoglycan 0.3
(9) Carboxymethylcellulose 0.3
(10) Ethanol 5
(11) Ion exchange water residue (Production method and evaluation)
(1) to (5) are mixed and dispersed and crushed by a bead mill, and then added to a water phase in which (6) to (11) are dissolved while applying a homomixer. The obtained sun-cut oil-in-water emulsion was refreshed and showed a good feeling of use with good skin familiarity.

Example 46: Oil-in-water emulsion foundation (1) Aluminum palmitate-treated titanium dioxide 5% by mass
(2) Zinc oxide treated with aluminum palmitate 5
(3) Metal soap treated talc 3
(4) Alkyl-modified silicone resin coated yellow iron oxide 0.8
(5) Alkyl modified silicone resin coated black iron oxide 0.16
(6) Alkyl modified silicone resin coated Bengala 0.36
(7) Compound 3 of Synthesis Example 3
(8) POE-modified methylpolysiloxane 1
(9) Decamethylpentacyclosiloxane 15
(10) Octyl paramethoxycinnamate 5
(11) PEG-60 hydrogenated castor oil 2
(12) Dynamite glycerin 6
(13) Xanthan gum 0.3
(14) Carboxymethylcellulose 0.3
(15) Ethanol 5
(16) Ion exchange water residue (Production method and evaluation)
(1) to (10) are mixed, dispersed and crushed by a bead mill, and then added to a water phase in which (11) to (16) are dissolved while applying a homomixer. The obtained foundation did not have uneven color, showed a good feeling of use that was easy to spread and was not sticky.

Example 47: UV protection whitening serum (oil-in-water emulsified cosmetic)
(1) Aluminum stearate-treated titanium dioxide 5% by mass
(2) Zinc oxide treated with aluminum stearate 5
(3) Compound 3 of Synthesis Example 2
(4) Decamethylpentacyclosiloxane 15
(5) Octyl paramethoxycinnamate 5
(6) PEG-60 hydrogenated castor oil 2
(7) Dynamite glycerin 6
(8) Succinoglycan 0.3
(9) Carboxymethylcellulose 0.3
(10) Ethanol 6
(11) Citric acid appropriate amount (12) Sodium citrate appropriate amount (13) Ascorbic acid glycoside 2
(14) Caustic potash appropriate amount (15) Ion-exchanged water residue (Production method and evaluation)
(1) to (5) are mixed, dispersed and crushed by a bead mill, and then added to a water phase in which (6) to (15) are dissolved while applying a homomixer. The obtained essence was smooth and smooth and showed a good feeling of use without stickiness.

  ADVANTAGE OF THE INVENTION According to this invention, cosmetics with a very favorable skin familiarity can be provided, refreshing. In addition, oily cosmetics, water-in-oil emulsified cosmetics and oil-in-water emulsified compositions having excellent usability and stability can be provided. Furthermore, powder dispersion cosmetics with extremely high powder dispersion stability and excellent stability can be provided.

It is a schematic diagram which shows the powder dispersion stability of the both terminal silicone modified glycerol used for this invention. It is the figure explaining the synthetic scheme of the both terminal silicone modified glycerol obtained by an ether bond. 2 is an IR spectrum of both-end silicone-modified glycerin of Synthesis Example 1. It is the rheology measurement result which changed the shear rate of the powder dispersion composition using the both-ends silicone modified glycerin of the synthesis example 1. It is the rheology measurement result which changed the shear rate of the powder dispersion composition using the both-ends silicone modified glycerin of the synthesis example 2. It is the rheology measurement result which changed the shear rate of the powder dispersion composition using the polyether modified silicone of the comparative example sample.

Claims (5)

Cosmetics characterized by containing the both-ends silicone modified glycerin represented by the following general formula (a).
(A)

In the formula, R1 is a linear or branched alkyl group having 1 to 12 carbon atoms or a phenyl group, R2 is an alkylene group having 2 to 11 carbon atoms, m is 10 to 120, and n is 1 to 11. .   The cosmetic according to claim 1, wherein the cosmetic is an oily cosmetic.   The cosmetic according to claim 1, wherein the cosmetic is a water-in-oil emulsified cosmetic.   The cosmetic according to claim 1, wherein the cosmetic is an oil-in-water emulsion composition. The cosmetic according to claim 1, 2, 3, or 4, wherein the cosmetic further contains a powder.

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