JP4566135B2 - Water-in-oil type skin external composition - Google Patents

Description

  The present invention relates to a water-in-oil type external composition for skin. In particular, the present invention relates to a water-in-oil type skin external composition having improved emulsification stability when a polar oil component and an ultraviolet absorber are blended.

  Conventionally, water-in-oil emulsion compositions having an oil phase as an outer phase and an aqueous phase as an inner phase have been 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.

  Conventional emulsifiers for water-in-oil emulsions include lipophilic surfactants of about HLB 1-12, for example, polyhydric alcohol fatty acid ester surfactants such as glycerin fatty acid esters and sorbitan fatty acid esters, polyoxyalkylene-modified organo Polysiloxane surfactants have been used (Non-Patent Document 1).

  However, water-in-oil emulsions using these emulsifiers have poor emulsification stability, resulting in separation of the water phase and the oil phase under high temperature conditions or over time, making it extremely difficult to stabilize as a preparation. It was.

  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.

  On the other hand, by using a polar oil such as a fatty acid ester as the oil phase of the water-in-oil emulsion, a non-polar oil or a component that is difficult to dissolve in silicone oil (for example, a specific ultraviolet absorber) is stably blended in the preparation. It becomes possible.

  However, when preparing a water-in-oil emulsion containing a polar oil component, the lipophilic part of a general emulsifier (for example, a long-chain alkyl group) has a low affinity for the polar oil component. It was easy to cause separation, and a stable preparation could not be obtained.

  On the other hand, in order to increase the affinity with the polar oil component, when trying to obtain a stable formulation by increasing the polarity of the lipophilic part of the emulsifier, the HLB (hydrophilic-lipophilic balance of the emulsifier as a whole. ) Is inclined to the hydrophilic side, so that the emulsion is likely to be in an oil-in-water type, and on the contrary, there is a problem that the stability of the water-in-oil emulsion system cannot be maintained.

"Fourth Edition, Petrochemical Handbook-Lipids and Surfactants", edited by Japan Oil Chemists' Society, Maruzen Co., Ltd.

  As a result of intensive studies in view of the above-mentioned problems, the present inventors have used a both-end silicone-modified glycerin having a specific structure as an emulsifier, compared with an emulsifier used in a conventional water-in-oil emulsion composition. In particular, it has been found that the emulsion stability is extremely excellent when a polar oil component and a specific ultraviolet absorber are blended, and the present invention has been completed.

  An object of this invention is to provide the water-in-oil type skin external composition excellent in the emulsion stability at the time of mix | blending a polar oil-based component and a ultraviolet absorber.

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, the present invention
(A) a double-end silicone-modified glycerin represented by the following general formula (a);
(B) a polar oil component;
(C) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and / or 2,4 , 6-Trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine is provided, and a water-in-oil type skin external composition is provided. is there.
(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. .

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 present invention also provides:
(A) Both-ends silicone-modified glycerin represented by the following general formula (b);
(B) a polar oil component;
(C) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and / or 2,4 , 6-Trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine is provided, and a water-in-oil type skin external composition is provided. is there.
(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.

  Further, in the present invention, the polar oil component is one or more selected from polar oils having an IOB of 0.05 to 0.80. It provides things.

  Further, in the present invention, the polar oil component is selected from the group consisting of 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, tripropylene glycol dipivalate, cetyl octanoate, tri-2-ethyl Hexanoic acid trimethylol propane, tetra 2-ethyl hexanoic acid pentane erythritol, tri 2-ethyl hexanoic acid glyceryl, naphthalene dicarboxylate diethyl hexyl, benzoic acid (carbon number 12-15) alkyl, tri (capryl capric acid) glycerin What is provided is a water-in-oil type skin external composition as described above, which is one or more selected from the group consisting of di (capryl / capric acid) propylene glycol and di-2-ethylhexyl succinate It is.

  The present invention also provides the water-in-oil type skin external composition described above, which further contains silicone oil.

  Furthermore, the present invention provides the above-described water-in-oil type composition for external skin, further comprising an ultraviolet scattering agent.

  The water-in-oil type skin external composition of the present invention using both ends of the silicone-modified glycerin having a specific structure as a novel emulsifier has excellent emulsification stability, particularly when a polar oil component is blended. It has been improved.

Hereinafter, preferred embodiments of the present invention will be described in detail.

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。 The basic structure of the both-end silicone-modified glycerin used as an emulsifier 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.
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.

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 binds the compound (c) and the compound represented by the following structural formula (d). It is a thing.
(D)

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

  The BAB type triblock copolymer can be synthesized by a known method. The synthesis scheme is shown in FIG.

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。 Thus, the both-ends silicone modified glycerin represented by following structural formula (a), (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. Moreover, in the outstanding function expression as an emulsifier, it is preferable that HLB is 0.2-3.0. (HLB can be determined by a known method, but is calculated by, for example, the Griffin equation (HLB value = glycerin molecular weight × 20 / total molecular weight).)
On the other hand, if the molecular weight of both AB blocks is too high, it may be difficult to spread the emulsion composition, and the weight of the elongation may be felt. Accordingly, there is an appropriate range for the molecular weight, and the molecular weight is preferably 2000 to 20000 in the both-end silicone-modified glycerin of the present invention.

  The compounding quantity of the both-ends silicone modified glycerin mix | blended as an emulsifier in this invention is not restrict | limited in particular. Usually, 0.1-10.0 mass% is mix | blended with respect to the water-in-oil type emulsion composition whole quantity. 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. On the other hand, when the blending amount is more than 10.0% by mass, the effect is not improved.

  This invention improves the emulsification stability of the said water-in-oil type external composition for skin by mix | blending said both terminal silicone modified glycerin in the water-in-oil type external composition for skin. Moreover, the water-in-oil type skin external composition of this invention can mix | blend the component normally used for cosmetics and a pharmaceutical in the range which does not impair the effect of this invention. The emulsifier may be used in combination with other emulsifiers, but a stable water-in-oil type composition for external skin can be obtained by blending substantially only both-end silicone-modified glycerin as the emulsifier.

  A polar oil-based component can be suitably blended in the water-in-oil type skin external composition of the present invention. Conventionally, when trying to prepare a water-in-oil external preparation containing a polar oil component using a general emulsifier, the emulsion phase is poor and the water phase and the oil phase are separated, resulting in an appearance. There was a case where it deteriorated remarkably. In contrast, the water-in-oil type composition for external skin of the present invention can improve the emulsion stability when a polar oily component is used by blending both terminal silicone-modified glycerin. And since a polar oil-based component can be stably emulsified, it becomes possible to mix | blend stably the component (component which is easy to melt | dissolve in a polar oil-based component) which is hard to melt | dissolve in oil components, such as a nonpolar oil component and silicone oil.

The polar oily component used in the present invention is not particularly limited, but the IOB value is preferably 0.05 to 0.80, and the IOB value is further 0.10 to 0.60. preferable.
The IOB value is an abbreviation of Inorganic / Organic Balance (inorganic / organic ratio), and is a value representing the ratio of the inorganic value to the organic value, and is an index indicating the degree of polarity of the organic compound. It will be. The IOB value is specifically expressed as “IOB value = inorganic value / organic value”. Here, for each of the “inorganic value” and “organic value”, for example, “organic value” is 20 for one carbon atom in the molecule, and “inorganic value” is 100 for one hydroxyl group. As described above, “inorganic value” and “organic value” corresponding to various atoms or functional groups are set, and “inorganic value” and “organic value” of all atoms and functional groups in the organic compound. Can be calculated to calculate the IOB value of the organic compound (see, for example, Fujita, “Chemical Domain”, Vol. 11, No. 10, pages 719 to 725, 1957).

  Specific polar oily components used in the present invention include, for example, isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethyloctane Hexyldecyl acid, 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 , Neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylol tri-2-ethylhexanoate Lopane, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, naphthalene dicarboxylic acid Diethylhexyl acid, benzoic acid (C12-15) alkyl, cetearyl isononanoate, tri (caprylic acid / capric acid) glycerin, (dicaprylic acid / capric acid) butylene glycol, glyceryl trimyristate, tri-2-heptyl Undecanoic acid glyceride, castor oil fatty acid methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptyl undecyl palmitate, diisobutyl adipate, -Lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, adipic acid 2 -Hexyldecyl, diisopropyl sebacate, di-2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, 2-ethylhexyl paramethoxycinnamate, tripropylene glycol dipivalate and the like.

  Among the polar oil components, in particular, 2-methoxyhexyl paramethoxycinnamate, tripropylene glycol dipivalate, cetyl octoate, trimethylolpropane tri-2-ethylhexanoate, pentane erythritol tetra-2-ethylhexanoate, Glyceryl tri-2-ethylhexanoate, diethylhexyl naphthalene dicarboxylate, alkyl benzoate (12 to 15 carbon atoms), tri (capryl / capric) glycerin, di (capryl / capric) propylene glycol, di-2-ethylhexyl succinate Can be suitably used in the present invention.

  In the water-in-oil skin external composition of the present invention, one or more of the above polar oily components may be selected and blended. The blending amount of the polar oil component is preferably 0.1 to 90.0% by mass, and more preferably 1.0 to 70.0% by mass with respect to the total amount of the composition. If the amount of the polar oil component is too small, it may be sticky, and if it is too much, emulsification may be poor.

  Moreover, a silicone oil can be suitably mix | blended with the said essential component in the water-in-oil type skin external composition of this invention. Examples of the silicone oil used in the present invention include chain polysiloxanes such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, Examples thereof include cyclic polysiloxanes such as tetramethyltetrahydrogencyclotetrasiloxane.

  In the water-in-oil skin external composition of the present invention, one or more of the above silicone oils may be selected and blended. The blending amount of the silicone oil is preferably 0.1 to 90% by mass, and more preferably 1.0 to 70.0% by mass with respect to the total amount of the composition. If the amount of silicone oil is too small, it may become sticky, and if it is too much, emulsification may be poor.

  In addition, it is preferable that the oil phase which comprises the water-in-oil type skin external composition of this invention has the said polar oil component and silicone oil as a main component substantially. However, other oil components may be blended within a range that does not impair the effects of the present invention.

  Further, the water-in-oil type skin external composition of the present invention includes 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl)-. 1,3,5-triazine {trade name: Tinosorb S (Ciba)}, 2,4,6-trianilino- (p-carbo-2′-ethylhexyl-1′-oxy) -1,3,5-triazine {(Trade name: Yubinal T150 (BASF))} These ultraviolet absorbers are solid ultraviolet absorbers at room temperature.

  You may mix | blend 1 type (s) or 2 or more types as said ultraviolet absorber. The blending amount of the ultraviolet absorber is preferably 0.1 to 20.0% by mass, and more preferably 0.5 to 10.0% by mass with respect to the total amount of the composition. If the blending amount of the UV absorber is too small, a sufficient UV protection effect may not be seen, and if it is too much, the UV absorber may precipitate over time.

  Moreover, an ultraviolet scattering agent can be suitably mix | blended with the water-in-oil type skin external composition of this invention. Examples of the ultraviolet light scattering agent used in the present invention include inorganic powders such as titanium oxide and zinc oxide, or the surface of the inorganic powder such as aluminum stearate and zinc palmitate and other fatty acid soaps, stearic acid, myristic acid, palmitic acid and the like. And surface-coated inorganic powder coated with a fatty acid ester such as dextrin palmitate and dextrin palmitate.

  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 composition. 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. In addition, the water-in-oil type skin external composition of this invention has the outstanding effect that an ultraviolet-scattering agent powder is disperse | distributed very favorably.

  The usage of the water-in-oil type external composition of the present invention is not particularly limited. For example, it can be applied to various products such as lotions, emulsions, creams, foundations, and lipsticks. In particular, it is preferably used as a sunscreen cosmetic.

  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)

A synthesis scheme of Synthesis Examples 1 to 5 is shown in FIG. FIG. 2 shows an IR spectrum of the compound obtained in Synthesis 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.

  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 water-in-oil cream and the results are shown in “Table 1” 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 1”, Examples 1 and 2 of the present invention are more stable with time and temperature stability of the emulsion composition than Comparative Examples 1 and 2 using a conventional water-in-oil emulsifier. It turns out that it is very excellent.

“Relationship between HLB and molecular weight of silicone modified glycerin (emulsifier) at both ends”
The emulsification stability (time stability and temperature stability) of a W / O emulsified composition using polar oil (di-2-ethylhexyl succinate) in the water-in-oil skin external composition of the following formulation was tested as described above. And evaluated in the same manner.
For the emulsifier, both-end silicone-modified glycerin obtained by synthesis in the same manner as in Synthesis Example 1 and a polyether-modified silicone (trade name: KF-6017, manufactured by Shin-Etsu Chemical Co., Ltd., polyether modification rate: 20% molecular weight: about 6000 HLB value: 4.0). The results are shown in “Table 2” and “Table 3”.
"Formulation of water-in-oil type skin external composition"
Ion-exchanged water 58.9%
Ethanol 8.0
1,3-butylene glycol 5.0
Preservative 0.1
Polyethylene glycol 1.0
2,4-bis-[{4- (2-ethylhexyloxy) 1.0
-2-hydroxy} -phenyl] -6
(2-Methoxyphenyl) -1,3,5-triazine di-2-ethylhexyl succinate 15.0
2-Ethylhexyl paramethoxycinnamate 10.0
Emulsifier 2.0

  Other examples of the present invention will be given below. Both are water-in-oil emulsified cosmetics with excellent emulsification stability.

Example 3
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Benzoic acid (C12-15) alkyl 10.0
Glyceryl tri-2-ethylhexanoate 10.0
2-Octyldodecanol 5.0
Octyl methoxycinnamate 5.0
4-tert-butyl-4′-methoxydibenzoylmethane 1.0
2,4-Bis-[[4- (2-ethylhexyloxy) 4.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil type sunscreen of Example 3 had good spread and the stability over time of the emulsion was very good.

Example 4
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Benzoic acid (C12-15) alkyl 10.0
Glyceryl tri-2-ethylhexanoate 10.0
2-Octyldodecanol 5.0
2-Ethylhexyl paramethoxycinnamate 5.0
1- [4- (1,1-Dimethylethyl) phenyl] 1.0
-3- (4-Methoxyphenyl) -1,3-propanedione 2,4-bis-[[4- (2-ethylhexyloxy) 4.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 4 had good spread and the emulsion stability over time was very good.

Example 5
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Benzoic acid (C12-15) alkyl 20.0
2-Cyano-3,3-diphenylacrylic acid 5.0
2-ethylhexyl 2-methoxyhexyl paramethoxycinnamate 10.0
2,4-bis-[[4- (2-ethylhexyloxy) 10.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water balance (C)
Hydrophobized zinc oxide 15.0
(Manufacturing method)
(A) A component is heated to 70 ° C. and dissolved, and then (C) is added and uniformly dispersed with a disper. The (B) phase is heated to 70 ° C., added to the (A) phase under stirring with a disper, and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 5 had good spread and the stability of the emulsion over time was very good.

Example 6
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Decamethylcyclopentasiloxane 5.0
Benzoic acid (C12-15) alkyl 5.0
Di (capryl / capric acid) propylene glycol 5.0
Tripropylene glycol dipivalate 5.0
Tri (capryl / capric acid) glycerin 5.0
Cetyl octanoate 5.0
Isononyl isononanoate 5.0
2-Ethylhexyl paramethoxycinnamate 5.0
2,4,6-trianilino- (p-carbo-2'-1.0
Ethylhexyl-1′-oxy) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil type sunscreen of Example 6 had good spread and the stability over time of the emulsion was very good.

Example 7
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Decamethylcyclopentasiloxane 5.0
Trimethylolpropane tri-2-ethylhexanoate 5.0
Di (capryl / capric acid) propylene glycol 5.0
Tripropylene glycol dipivalate 5.0
Tri (capryl / capric acid) glycerin 5.0
Tetra 2-ethylhexanoic acid 5.0
Pentane Eryslit Diethylhexyl naphthalene dicarboxylate 5.0
2-Ethylhexyl paramethoxycinnamate 8.0
2,4-bis-[{4- (2-ethylhexyloxy) 1.0
-2-hydroxy} -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine 2,4,6-trianilino- (p-carbo-2′-1.0
Ethylhexyl-1′-oxy) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 7 had good spreading and the stability over time of the emulsion was very good.

Example 8
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Benzoic acid (C12-15) alkyl 15.0
2-Cyano-3,3-diphenylacrylic acid 5.0
2-Ethylhexyl di-2-ethylhexyl succinate 5.0
2-Ethylhexyl paramethoxycinnamate 10.0
2,4,6-trianilino- (p-carbo-2'- 10.0
Ethylhexyl-1′-oxy) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water balance (C)
Hydrophobized zinc oxide 10.0
(Manufacturing method)
(A) A component is heated to 70 ° C. and dissolved, and then (C) is added and uniformly dispersed with a disper. The (B) phase is heated to 70 ° C., added to the (A) phase under stirring with a disper, and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 8 had good spread and the emulsion stability over time was very good.

Example 9
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 1
Decamethylcyclopentasiloxane 10.0
Glyceryl tri-2-ethylhexanoate 10.0
Diethylhexyl naphthalene dicarboxylate 5.0
2-Ethylhexyl paramethoxycinnamate 5.0
1- [4- (1,1-dimethylethyl) phenyl] 0.5
-3- (4-Methoxyphenyl) -1,3-propanedione 2,4-bis-[[4- (2-ethylhexyloxy) 0.5
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 9 had good spread and the stability of the emulsion over time was very good.

Example 10
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin 3.0 of Synthesis Example 2
Benzoic acid (C12-15) alkyl 10.0
Glyceryl tri-2-ethylhexanoate 10.0
2-Octyldodecanol 5.0
Octyl methoxycinnamate 5.0
4-tert-butyl-4′-methoxydibenzoylmethane 1.0
2,4-Bis-[[4- (2-ethylhexyloxy) 4.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 10 had good spreading and the stability of the emulsion over time was very good.

Example 11
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin of Synthesis Example 3 3.0
Benzoic acid (C12-15) alkyl 10.0
Glyceryl tri-2-ethylhexanoate 10.0
2-Octyldodecanol 5.0
2-Ethylhexyl paramethoxycinnamate 5.0
1- [4- (1,1-Dimethylethyl) phenyl] 1.0
-3- (4-Methoxyphenyl) -1,3-propanedione 2,4-bis-[[4- (2-ethylhexyloxy) 4.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil type sunscreen of Example 11 had good spread and the stability over time of the emulsion was very good.

Example 12
Oil-in-water sunscreen mass%
(A)
Both-ends silicone-modified glycerin 3.0 of synthesis example 4
Benzoic acid (C12-15) alkyl 20.0
2-Cyano-3,3-diphenylacrylic acid 5.0
2-ethylhexyl 2-methoxyhexyl paramethoxycinnamate 10.0
2,4-bis-[[4- (2-ethylhexyloxy) 10.0
-2-hydroxy] -phenyl] -6
(4-Methoxyphenyl) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water balance (C)
Hydrophobized zinc oxide 15.0
(Manufacturing method)
(A) A component is heated to 70 ° C. and dissolved, and then (C) is added and uniformly dispersed with a disper. The (B) phase is heated to 70 ° C., added to the (A) phase under stirring with a disper, and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil type sunscreen of Example 12 had good spread and the stability of the emulsion over time was very good.

Example 13
Oil-in-water sunscreen mass%
(A)
Both-end silicone-modified glycerin of Synthesis Example 5 3.0
Decamethylcyclopentasiloxane 5.0
Benzoic acid (C12-15) alkyl 5.0
Di (capryl / capric acid) propylene glycol 5.0
Tripropylene glycol dipivalate 5.0
Tri (capryl / capric acid) glycerin 5.0
Cetyl octanoate 5.0
Isononyl isononanoate 5.0
2-Ethylhexyl paramethoxycinnamate 5.0
2,4,6-trianilino- (p-carbo-2'-1.0
Ethylhexyl-1′-oxy) -1,3,5-triazine Fragrance Amount (B)
Butylene glycol 5.0
Purified water residue (production method)
After the component (A) is heated to 70 ° C. and dissolved, the phase (B) is heated to 70 ° C. and added to the phase (A) under stirring with a disper and mixed well. Then, it cooled to 30 degreeC and obtained the water-in-oil type sunscreen.
The water-in-oil sunscreen of Example 13 had good spread and the emulsion stability over time was very good.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the water-in-oil type skin external composition excellent in the emulsification stability at the time of mix | blending a polar oil component especially. The water-in-oil type composition for external use of the present invention can be preferably used for various applications including sunscreen cosmetics.

It is a figure explaining the synthetic scheme of both terminal silicone modified glycerol. 2 is an IR spectrum of both-end silicone-modified glycerin of Synthesis Example 1.

Claims (6)

(A) a double-end silicone-modified glycerin represented by the following general formula (a);
(B) a polar oil component;
(C) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and / or 2,4 , 6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine.
(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. . (A) Both-ends silicone-modified glycerin represented by the following general formula (b);
(B) a polar oil component;
(C) 2,4-bis-[{4- (2-ethylhexyloxy) -2-hydroxy} -phenyl] -6- (4-methoxyphenyl) -1,3,5-triazine and / or 2,4 , 6-trianilino- (p-carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine.
(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 water-in-oil type skin external composition according to claim 1 or 2, wherein the polar oil component is one or more selected from polar oils having an IOB of 0.05 to 0.80. .   The polar oil component is 2-ethylhexyl paramethoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, tripropylene glycol dipivalate, cetyl octoate, trimethylolpropane tri-2-ethylhexanoate, Tetra-2-ethylhexanoic acid pentane erythritol, tri-2-ethylhexanoic acid glyceryl, naphthalene dicarboxylate diethylhexyl, benzoic acid (12 to 15 carbon atoms) alkyl, tri (capryl / capric acid) glycerin, di (capryl / capric acid 4. The water-in-oil type skin external composition according to claim 1, 2 or 3, wherein the composition is one or more selected from the group consisting of propylene glycol and di-2-ethylhexyl succinate.   Furthermore, silicone oil is contained, The water-in-oil type skin external composition of Claim 1, 2, 3 or 4 characterized by the above-mentioned. Furthermore, the ultraviolet-ray scattering agent is contained, The water-in-oil type skin external composition of Claim 1, 2, 3, 4 or 5 characterized by the above-mentioned.

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