JP2022175330A - Water-in-oil skin emulsifying cosmetic - Google Patents

Abstract

To provide emulsified cosmetics with excellent high-temperature stability, non-sticky texture, and a feeling of high moisturization even after rinsing.SOLUTION: Provided is a water-in-oil skin emulsifying cosmetic containing specific amounts of each of components (A) to (D): (A) the alkylene oxide derivative of the following formula (1), the ratio of the weight-average molecular weight Mw to the z-average molecular weight Mz being 5≤Mz/Mw≤60; (B) glyceryl oleate and/or glyceryl isostearate; (C) a nonionic surfactant with HLB 10 to 18 selected from the group consisting of POE hydrogenated castor oil, polyoxyalkylene decyltetradecyl ether and POE sorbitan fatty acid ester; and (D) an oily component. Z-[O-(PO)a-{(EO)b/(PO)c}-H]n...(1) (Z is a residue obtained by removing all hydroxyl groups from a compound having 1 to 8 carbon atoms and 1 to 4 hydroxyl groups; n is 1 to 4; EO is an oxyethylene group, PO is an oxypropylene group; 1≤a≤20, 1≤c≤40, 0≤b≤40).SELECTED DRAWING: Figure 1

Description

The formulation of the present invention has excellent high-temperature stability, and when applied to the skin, it does not become sticky and has a high moisturizing feeling even after rinsing. The present invention relates to a water-in-oil type skin emulsifying cosmetic that hardly feels slimy.

BACKGROUND ART Conventionally, various dosage forms of skin care cosmetics have been used for the purpose of moisturizing and preventing rough skin for the skin of the face and body. Emulsified cosmetics are roughly classified into W/O emulsions in which water droplets are contained in oil and O/W emulsions in which oil droplets are contained in water. A W/O type emulsion and an O/W type emulsion have a large difference in feeling when used, and can be used properly depending on the intended use and desired feeling of use.

Due to the recent heightened awareness of hygiene, the number of times of hand washing and the frequency of use of hand sanitary products containing alcohol are increasing. Excessive removal of essential oils from the skin can easily lead to rough hands, so W/O emulsion-type emulsified cosmetics, which are difficult to wash off with water and maintain a moisturizing sensation even after rinsing, seem to be preferred. Became.
For emulsified cosmetics, it is important that the quality does not change even at 50°C so that stability can be guaranteed even at the temperature inside a car or in a warehouse during the summer season. It is difficult, because the outer layer is oil, it is easy to get sticky, and some people who do a lot of water work may experience a problem when they apply emulsified cosmetics to their fingers and wet their hands with water before they are sufficiently dried. There is a problem that the null feeling is uncomfortable.

Patent Document 1 proposes a water-in-oil emulsion composition containing glycerol monooleate, a surfactant having a branched alkyl group, an aqueous component, an oily component, and a perfume component. Patent Document 2 proposes a water-in-oil emulsified cosmetic containing glyceryl isostearate, an aqueous component, and paraffin having 20 or less carbon atoms.

JP 2008-290946 A JP 2010-248173 A

However, in the water-in-oil emulsion compositions described in Patent Document 1 and Patent Document 2, although both high-temperature stability and non-stickiness and a moisturizing feeling after rinsing are good, before the composition is applied and sufficiently dried, The problem is that it becomes slippery when you wet your hands with water.

An object of the present invention is to provide a formulation with excellent high-temperature stability, to have a highly moisturizing feeling even after rinsing without being sticky when applied to the skin, and to wash the hands with water before applying and sufficiently drying. To provide a water-in-oil type skin emulsifying cosmetic which hardly feels slimy when wetted.

The present inventors have found that by using a predetermined amount of a specific alkylene oxide derivative, the formulation has excellent high-temperature stability, and when applied to the skin and used, has a high moisturizing feeling even after rinsing without stickiness. It was found that a water-in-oil skin emulsified cosmetic that does not easily feel slimy when a hand is wetted with water before being applied and sufficiently dried can be obtained.

The water-in-oil type skin emulsion cosmetic according to the present invention is
(A) The ratio Mz/Mw between the weight-average molecular weight (Mw) and the z-average molecular weight (Mz), which is represented by formula (1) and calculated from the chromatogram obtained by gel permeation chromatography measurement, is represented by formula (2). 0.1 to 15% by mass of an alkylene oxide derivative that satisfies the relationship

Z-[O-(PO) _a -{(EO) _b /(PO) _c }-H] _n (1)

(In formula (1),
Z is a residue obtained by removing all the hydroxyl groups from a compound having 1 to 8 carbon atoms and 1 to 4 hydroxyl groups,
n represents a number from 1 to 4,
EO represents an oxyethylene group,
PO represents an oxypropylene group,
a and c are the average number of added moles of the oxypropylene group PO, respectively, and are 1 ≤ a ≤ 20 and 1 ≤ c ≤ 40;
b is the average number of added moles of the oxyethylene group EO, and 0≦b≦40. )
5≦Mz/Mw≦60 (2)
(B) 0.1 to 10% by mass of glyceryl oleate and/or glyceryl isostearate
(C) 0.1 to 5% by mass of a nonionic surfactant having an HLB of 10 to 18 selected from the group consisting of polyoxyethylene hydrogenated castor oil, polyoxyalkylene decyltetradecyl ether and polyoxyethylene sorbitan fatty acid ester, and (D) 3 to 50% by mass of oily components
characterized by containing

According to the present invention, the formulation has excellent high-temperature stability, does not become sticky when applied to the skin, and has a high moisturizing feeling even after rinsing. It is possible to obtain a water-in-oil type skin emulsifying cosmetic that does not feel slimy when wet.

FIG. 1 is a model chromatogram diagram for explaining Mz/Mw defined in the present invention.

Embodiments of the present invention will be described below.
The present invention includes components (A), (B), (C) and (D). The components (A), (B), (C) and (D) are described below in order.

[(A) component]
The component (A) used in the present invention is a compound represented by the formula (1), and has a weight-average molecular weight (Mw) and a z-average molecular weight (Mz ) in which the ratio Mz/Mw satisfies the relationship of formula (2).

Z-[O-(PO) _a -{(EO) _b /(PO) _c }-H] _n (1)

Here, Z is a residue obtained by removing all hydroxyl groups from a compound (Z (OH) n) having 1 to 8 carbon atoms and 1 to 4 hydroxyl groups, and n is the compound (Z (OH) n) is the number of hydroxyl groups of 1 to 4. The number of carbon atoms in the compound is preferably 1-5, more preferably 3-4, and most preferably 4.
The compound (Z(OH)n) having 1 to 4 hydroxyl groups includes methanol, ethanol, butanol when n=1, ethylene glycol, propylene glycol, hexylene glycol when n=2, and n= Examples include glycerin and trimethylolpropane when n=3, and erythritol, pentaerythritol, sorbitan, diglycerin, and alkyl glycosides when n=4. A mixture of these may also be used as the compound having 1 to 4 hydroxyl groups. n is preferably 1-3, more preferably 1-2, and most preferably 1.

EO is an oxyethylene group and PO is an oxypropylene group.
a is the average number of added moles of the oxypropylene group PO, and 1≦a≦20. If a is 0, there is a possibility that the moisturizing feeling and the absence of sliminess when the hand is wetted with water before the application is sufficiently dried, so it is made 1 or more, but 2 or more is preferable, and 3 The above is more preferable. If a exceeds 20, the moisturizing effect is reduced.

b is the average number of added moles of oxyethylene groups, and 0≦b≦40. Since stickiness occurs when b exceeds 40, it is made 40 or less. Also, b is 0 or more, preferably 10 or more, and more preferably 25 or more.

c is the average number of added moles of the oxypropylene group PO, and 1≤c≤40. If c is 0, the moisturizing effect decreases, so it is made 1 or more, preferably 10 or more, more preferably 20 or more. Also, when c exceeds 40, stickiness occurs, so it is made 40 or less, preferably 35 or less.

In formula (1), when n=1, Z is a hydrocarbon group having 1 to 8 carbon atoms. Hydrocarbon groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, or aralkyl groups. An alkyl group or an alkenyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is preferable, an alkyl group having 2 to 5 carbon atoms is preferable, and an alkyl group having 4 carbon atoms is most preferable. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and more preferably linear. Examples of linear alkyl groups having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, butyl group and hexyl group. The hydrocarbon group having 1 to 8 carbon atoms may be of one type or two or more types.

When b>0, {(EO)b/(PO)c} indicates random addition of the oxyethylene group EO and the oxypropylene group PO.
The random rate x of PO and EO is obtained from Equation (3).
x=(b+c)/(a+b+c) (3)
If b>0, the random rate x is set to 0.1≦x≦1. The random rate x is 1 or less, preferably 0.5 ≤ x < 1, more preferably 0.8 ≤ x ≤ 0.99, and 0.85 ≤ x ≤ 0.99 is more preferable, and 0.85≤x≤0.95 is particularly preferable.

(GPC characteristics)
The alkylene oxide derivative of the present invention is defined by the molecular weight obtained from the chromatogram obtained using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between refractive index intensity and elution time.

In the derivatives of the present invention, the ratio Mz/Mw between the weight average molecular weight (Mw) and the z average molecular weight (Mz) obtained from the chromatogram is shown by formula (2).
5≦Mz/Mw≦60 (2)
Here, Mw and Mz are obtained from GPC by the following formulas.

where N is the number of polymer molecules, M is the molecular weight, and C is the sample concentration. Mw is a weighted average using the molecular weight as a weight, and Mz is a weighted average using the square of the molecular weight as a weight. Mw is affected by the presence of high molecular weights, and Mz is even more affected by the presence of high molecular weights than Mw. Therefore, the alkylene oxide derivative of the present invention has Mw and Mz like the chromatogram shown in FIG.

If Mz/Mw is less than 5, in addition to being likely to feel sticky upon application, there is a possibility that feeling of slipperiness may be likely to occur when wetted with water after being applied and sufficiently dried. Mz/Mw is preferably 10 or more, more preferably 20 or more, in order to reduce stickiness during application and sliminess when wetted with water before being applied and sufficiently dried. , 40 or more are more preferred. When Mz/Mw is more than 60, the molecular weight distribution is more biased toward the high molecular weight side, resulting in increased viscosity and the like, making it difficult to disperse and blend in each formulation. From this point of view, Mz/Mw is preferably 60 or less, more preferably 50 or less.

In the present invention, gel permeation chromatography (GPC) for determining Mz / Mw is performed by SHODEX (registered trademark) GPC101 GPC dedicated system as a system, SHODEX RI-71s as a differential refractometer, SHODEX KF-G as a guard column, column Three HODEX KF804L were continuously installed as a column, and tetrahydrofuran was flowed at a flow rate of 1 ml / min as a developing solvent at a column temperature of 40 ° C., and 0.1 ml of a 0.1 mass% tetrahydrofuran solution of the obtained reaction product was injected, and BORWIN GPC was performed. A chromatogram, expressed as refractive index intensity and elution time, is obtained using a calculation program.

(Method for producing component (A))
When producing the component (A) of the present invention, known catalysts such as alkali metal hydroxides such as potassium hydroxide, compounds having a P=N bond such as phosphazene compounds, and double metal cyanide complex catalysts are used. Available. Preferably, a ring-opening addition of an alkylene oxide having 3 carbon atoms, namely propylene oxide, and an alkylene oxide having 2 carbon atoms, namely ethylene oxide, is carried out in the presence of a double metal cyanide catalyst (hereinafter abbreviated as a DMC catalyst) as a catalyst. Let An initiator having at least one hydroxyl group in the molecule and a DMC catalyst are added to a reaction vessel, and propylene oxide or ethylene oxide is added continuously or intermittently under stirring in an inert gas atmosphere for addition polymerization. Propylene oxide and ethylene oxide may be added under pressure or under atmospheric pressure.

The reaction temperature is preferably 50°C to 150°C, more preferably 70°C to 110°C. If the reaction temperature is higher than 150°C, the catalyst may be deactivated. If the reaction temperature is lower than 50°C, the reaction rate will be slow and the productivity will be poor.

As the initiator in the present invention, in formula (1), Z(OH)n is a compound having 1 to 8 carbon atoms and the number x of hydroxyl groups is 1 to 4, or a compound obtained by adding oxypropylene to these compounds. can be done. Examples of initiators include butanol, butylpropylene glycol, polyoxypropylene glycol, polyoxypropylene glyceryl ether, ethylene glycol, propylene glycol, hexylene glycol, glycerin, trimethylolpropane, erythritol, pentaerythritol, sorbitan, and alkyl glycosides. is mentioned.
When Z is R ¹ , a monohydric alcohol (R ¹ OH) having a hydrocarbon group of 1 to 8 carbon atoms represented by R ¹ can be used as the initiator.

There are no particular restrictions on the amount of water contained in the initiator, propylene oxide, and ethylene oxide, but the amount of water contained in the initiator is 0.5 wt% or less, and 0.01 wt% or less for propylene oxide and ethylene oxide. It is desirable to have
The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 wt%, more preferably 0.001 to 0.05 wt%, relative to the component (A) to be produced. The DMC catalyst may be introduced all at once into the reaction system, or may be successively introduced in divided portions. After completion of the polymerization reaction, the composite metal complex catalyst is removed. Removal of the catalyst can be carried out by known methods such as filtration, centrifugation, and treatment with a synthetic adsorbent.

A known DMC catalyst can be used in the present invention, and for example, it can be represented by formula (6).

M _d M′ _y (CN) _z ] _e (H ₂ O) _f (R) _g (6)

In formula (6), M and M' are metals, R is an organic ligand, d, e, y and z are positive integers that vary depending on the valence and coordination number of the metal, and f and g are metal is a positive integer that varies depending on the coordination number of

Metals M include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), W(VI), etc., among which Zn(II) is preferably used.

Metal M′ includes Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II) , V(IV), V(V), etc. Among them, Fe(II), Fe(III), Co(II), and Co(III) are preferably used.
As the organic ligand R, alcohols, ethers, ketones, esters and the like can be used, and alcohols are more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether ( diglyme) and the like. Zn ₃ [Co(CN) ₆ ] ₂ coordinated with tert-butyl alcohol is particularly preferred.

The content of component (A) is 0.1 to 15% by mass when the total amount of the water-in-oil emulsified skin cosmetic of the present invention is 100% by mass. If the content of component (A) is less than 0.1% by mass, the feeling of moisturizing at the time of application is reduced, and the effect of suppressing sliminess when wetted with water before being sufficiently dried after application is reduced. On the other hand, when the content of component (A) exceeds 15% by mass, stickiness and sliminess may occur when wetted with water before being applied and sufficiently dried. Therefore, the amount of component (A) is preferably 1 to 10% by mass, more preferably 1 to 5% by mass, and particularly preferably 2 to 5% by mass.

[(B) Component]
The component (B) used in the present invention is glyceryl oleate and/or glyceryl isostearate. Among these, it is preferable to use glycerin oleate from the viewpoint of touch.

Furthermore, from the viewpoint of emulsion stability and texture, the mass of monoglyceryl monooleate and the mass of monoglyceryl monoisostearate, when the total value of the mass of glyceryl oleate and the mass of glyceryl isostearate is 100% by mass. is preferably 80% by mass or more. Further, when the total value of the mass of glyceryl oleate and the mass of glyceryl isostearate is 100% by mass, glyceryl dioleate, glyceryl trioleate, diisostearic acid Most preferably, the total weight of glycerin and glyceryl triisostearate is 15% by weight or less. Glyceryl dioleate, glyceryl trioleate, glyceryl diisostearate, and glyceryl triisostearate may be included as impurities in component (B), or may be included as a type of oil blended as an oily component in component (D). be. Monoglyceryl monooleate and/or monoglyceryl monoisostearate function as emulsifiers, while glyceryl dioleate, glyceryl trioleate, glyceryl diisostearate, and glyceryl triisostearate all work as oils. Therefore, when the purity of monoglyceryl monooleate and/or monoglyceryl monoisostearate is low and the total mass of glyceryl dioleate, glyceryl trioleate, glyceryl diisostearate and glyceryl triisostearate exceeds 15% by mass, Since the stability of the emulsion may be impaired and the effect of suppressing sliminess when wetted with water before being applied and sufficiently dried may be inferior, the content is preferably 15% by mass or less. There is no particular lower limit for the total mass of glyceryl dioleate, glyceryl trioleate, glyceryl diisostearate and glyceryl triisostearate, and although it may be 0% by mass, it is usually 1% by mass or more.
The purity of glyceryl monoisostearate and glyceryl monooleate can be measured by general methods such as gas chromatography (GC), gel permeation chromatography (GPC), and high performance liquid chromatography (HPLC).

The amount of component (B) is 0.1 to 10% by mass when the total amount of the water-in-oil type emulsified skin cosmetic of the present invention is 100% by mass. The mass of component (B) is preferably 1% by mass or more, more preferably 4% by mass or more, preferably 8% by mass or less, and further preferably 6% by mass or less.

[(C) component]
The component (C) used in the present invention is nonionic surfactants such as polyoxyethylene hydrogenated castor oil, polyoxyalkylenedecyltetradecyl ether, and polyoxyethylene sorbitan fatty acid ester, which are generally blended in cosmetics.

The HLB of component (C) is 10-18.
HLB is an abbreviation for Hyrophile-Lipophile Balance, and is a concept that quantifies the balance between hydrophilic groups and lipophilic groups of surfactants. It is generally expressed from 0 to 20, with higher numbers indicating higher hydrophilicity.

The HLB is calculated by the following formula (7) based on the IOB value.
HLB=IOB×10 (7)
The IOB (inorganic-organic balance) value is a numerical value representing the hydrophilicity of an organic compound, and the larger the numerical value, the higher the hydrophilicity. As a calculation method, organic value (OV), inorganic value (IV ) and can be calculated as IOB value=inorganic value/organic value.

Component (C) is polyoxyethylene hydrogenated castor oil, polyoxyalkylenedecyltetradecyl ether, polyoxyethylene sorbitan fatty acid ester, and component (C) is preferably polyoxyethylene hydrogenated castor oil or polyoxyalkylenedecyltetradecyl ether. Polyoxyethylene hydrogenated castor oil is more preferred. One or two or more selected from these can be used.

The content of component (C) is 0.1 to 5% by mass when the total amount of the water-in-oil type emulsified skin cosmetic of the present invention is 100% by mass. If the content of component (C) is less than 0.1% by mass, the high-temperature stability is impaired, so the content is made 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more. . On the other hand, when the content of component (C) is more than 5% by mass, it causes stickiness and sliminess when wetted with water before being applied and sufficiently dried. Therefore, the content of component (C) is set to 5% by mass or less, preferably 4% by mass or less, and more preferably 3% by mass or less.

In the present invention, the mass ratio (B)/(C) of the component (B) to the component (C) is determined by the high-temperature stability of the formulation, the moist feeling after rinsing, and the addition of water before application and sufficient drying. From the viewpoint of the effect of suppressing nulliness when wetted with, it is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 8.

[(D) component]
The (D) component used in the present invention is an oily component. Oily components include, for example, camellia oil, castor oil, safflower oil, soybean oil, tea seed oil, cacao butter, coconut oil, sunflower oil, hydrogenated coconut oil, palm oil, Japanese wax, hydrogenated castor oil, beeswax, candelilla wax, Natural fats and oils such as carnauba wax, lanolin, liquid lanolin, jojoba wax, hard lanolin, polyoxyethylene lanolin alcohol ether, polyoxyethylene cholesterol ether; liquid paraffin, liquid isoparaffin, ozokerite, squalene, squalane, paraffin, ceresin, vaseline, microcrystalline Hydrocarbon fats and oils such as wax; isopropyl myristate, octyldodecyl myristate, isopropyl palmitate, ethylhexyl palmitate, isononyl isononanoate, pentaerythrityl tetraethylhexanoate, cholesteryl 12-hydroxystearate, di-2-ethylhexyl acid Ethylene glycol, dipentaerythritol fatty acid ester, pentaerythritol tetra-2-ethylhexylate, glyceryl tri-2-ethylhexanoate, trimethylolpropane triisostearate, glyceryl triisostearate, cetyl lactate, cetyl-2-ethylhexanoate, Synthetic oily components such as castor oil fatty acid methyl ester; Chain polysiloxane such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane; decamethylpolysiloxane, decamethylcyclopentasiloxane, dodecamethylpolysiloxane, dodecamethyl Examples include silicones such as cyclic polysiloxanes such as cyclohexasiloxane and tetramethyltetrahydrogenpolysiloxane. One of these may be used, or two or more selected from the above group may be mixed and used.

When the total amount of the water-in-oil type emulsified skin cosmetic of the present invention is 100% by mass, the amount of component (D) is 3 to 50% by mass. %, more preferably 5 to 30% by mass, particularly preferably 10 to 20% by mass.

[(E) component]
Component (E) is water, including purified water, distilled water, and ion-exchanged water.
When the total amount of the water-in-oil type emulsified skin cosmetic of the present invention is 100% by mass, the amount of component (E) is preferably 40 to 98% by mass, more preferably 50 to 95% by mass, from the viewpoint of stability and feel. % is more preferable.

(Method for producing water-in-oil skin emulsified cosmetic)
The method for producing the water-in-oil skin emulsion cosmetic of the present invention includes, for example, the following steps.
(Step of heating and uniformly mixing components (A) to (D) and then gradually adding water while stirring)
The form of the water-in-oil type skin emulsifying cosmetic of the present invention is not particularly limited, and may take any form such as cream, liquid, milky lotion, and gel.
Applications of the water-in-oil type skin emulsion cosmetic of the present invention are not particularly limited, but examples include face cream, body cream, sunscreen cream, moisturizing cream, hand cream, body cream, foot cream, massage cream, emulsion, foundation, It can be suitably used for cleansing agents and the like.

(other additives)
The water-in-oil type skin emulsified cosmetic of the present invention may optionally contain additives commonly used in cosmetics. The additives are not particularly limited as long as they do not interfere with the object of the present invention. organic or inorganic salts such as pyrrolidone carboxylates, citrates, malate salts, salt, colorants, alcohols, UV protection agents, UV absorbers, amino acids, vitamins, natural extracts derived from animals and plants , whitening agents, organic acids, inorganic salts, enzymes, antioxidants, stabilizers, preservatives, bactericides, antiphlogistic agents, skin activators, blood circulation promoters, antiseborrheic agents, anti-inflammatory agents, antioxidants agents, sequestering agents, acids and alkalis that are pH adjusters, astringents, cooling agents, fragrances, dyes, pigments, and the like.
When the total amount of the water-in-oil emulsified skin cosmetic of the present invention is 100% by mass, the amount of additive components other than components (A), (B), (C), (D), and (E) is
20% by mass or less is preferable, and 10% by mass or less is more preferable.

EXAMPLES Next, the present invention will be described in more detail with reference to examples and comparative examples.
First, Example compounds 1 to 3 and Comparative compounds 1 to 2 shown in Table 1 were synthesized as follows.
(Synthesis of double metal cyanide complex catalyst)
Into 2.0 ml of aqueous solution containing 2.1 g of zinc chloride, 15 ml of aqueous solution containing 0.84 g of potassium hexacyanocobaltate K ₃ Co(CN) ₆ was dropped at 40° C. over 15 minutes while stirring. After completion of dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation (first filtration) was performed to obtain a solid. 14 ml of water and 8.0 g of tert-butyl alcohol were added to this solid, and the mixture was stirred for 30 minutes and filtered (second filtration) to obtain a solid.
Again, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid, and after stirring for 30 minutes, a filtration operation (third filtration) was performed, and the obtained solid was dried at 40° C. under reduced pressure for 3 hours. to obtain 0.7 g of a double metal cyanide complex catalyst.

(Synthesis of Example Compound 1)
A 5 L autoclave equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas inlet tube, a stirrer, an evacuation tube, a cooling coil, and a steam jacket was charged with 56 g of butanol and 0.03 g of a double metal cyanide complex catalyst. , the temperature was raised to 110°C, and 176 g of propylene oxide was added dropwise from a nitrogen gas blowing pipe under the conditions of 0.3 MPa or less, and the change in pressure and temperature in the reaction vessel over time was measured. The pressure in the reactor dropped sharply. Thereafter, a mixture of 1,054 g of propylene oxide and 1,164 g of ethylene oxide was gradually added dropwise from a nitrogen gas blowing pipe under conditions of 0.5 MPa or less while maintaining the inside of the reactor at 90°C. After completion of the addition, the mixture was reacted at 90° C. for 1 hour, treated under reduced pressure at 75 to 85° C. for 1 hour, and filtered.
The obtained example compound 1 was measured by gel permeation chromatography.
However, the butanol used was from KH Neochem, the propylene oxide from Sumitomo Chemical, and the ethylene oxide from Nippon Shokubai.

(Synthesis of Example Compounds 2 and 3 and Comparative Example Compound 1)
Alkylene oxide derivatives (Example compounds 2 and 3, Comparative example compound 1) were synthesized in the same manner as Example compound 1, except that the type of starting material and the amounts of ethylene oxide and propylene oxide added were changed.

(Synthesis of Comparative Example Compound 2)
A 5 L autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket was charged with 56 g of butanol and 6.0 g of potassium hydroxide as a catalyst, and then replaced with nitrogen. The temperature was raised to 110° C., and a mixture of 1230 g of propylene oxide and 1164 g of ethylene oxide was gradually added dropwise from a nitrogen gas blowing tube under the condition of 0.5 MPa or less. After completion of the addition, react at 110° C. for 1.5 hours, treat under reduced pressure at 75 to 85° C. for 1 hour, transfer the reactant to a 5 L eggplant flask, quickly neutralize with 1N hydrochloric acid, and dehydrate under nitrogen gas atmosphere. , was filtered.
The obtained Comparative Example Compound 2 was measured by gel permeation chromatography.
Also, the number average molecular weights of ethylene oxide and propylene oxide adducts were obtained from the values obtained by hydroxyl value measurement according to JIS K1557-1, and the values of a, b, and c were specified.

Table 1 shows the Mz/Mw obtained from the chromatograms of Example compounds 1 to 3 and Comparative example compounds 1 and 2, and the properties of the compounds. However, the hydroxyl value was measured according to JIS K-1557-1, and the molecular weight was calculated from the hydroxyl value.

[Example/Comparative example]
The compositions shown in Tables 2 and 3 were prepared as water-in-oil skin emulsified cosmetics and evaluated by the following methods. Tables 2 and 3 show the results. Table 4 shows "common additive components" in Tables 2 and 3. In addition, % in the following notation means % by mass.

[Evaluation items and evaluation criteria]
(1) High Temperature Stability The state of the sample stored at 40° C. and 50° C. for one month was visually observed, and the stability was evaluated by comparing with immediately after preparation.

A: No change in condition after 1 month.
◯: No change in condition after 2 weeks, slight change in condition such as separation only after storage at 50°C after 1 month.
Δ: No change in state after 2 weeks, change in state such as slight separation at 40° C. and 50° C. after 1 month. No change in state after 1 week, slight change in state such as separation after 1 month x: Change in state such as separation at 40°C and 50°C after 2 weeks.

(2) Absence of stickiness A panel of 20 women (ages 22 to 40) was asked to evaluate whether they felt stickiness after applying the water-in-oil skin emulsifying cosmetic (about 2 g) according to the following criteria. rice field. Then, based on the sum of the scores, the following 4-grade evaluation from "A" to "X" was performed, and 30 points or more were judged to be non-sticky water-in-oil skin emulsified cosmetics.

2 points: No stickiness was felt after application to the skin.
1 point: When the skin feels slightly sticky after application.
0 points: When stickiness is felt after application to the skin.

<Five-level evaluation based on the total score>
◎: Total score is 35 points or more ○: Total score is 30 points or more and 34 points or less △: Total score is 20 points or more and less than 29 points ×: Total score is less than 19 points

(3) Moisturizing feeling after rinsing A panel of 20 women (22 to 40 years old) was applied with a water-in-oil skin emulsifying cosmetic (about 2 g), and after application and rinsing the applied area with water. , and whether a highly moisturizing feeling was felt after drying with a towel was evaluated and rated according to the following criteria. Then, based on the sum of the scores, the following 4-grade evaluation from "A" to "X" was performed, and 30 points or more were judged to be a water-in-oil skin emulsified cosmetic with a high moisturizing effect.

2 points: When feeling a very high moisturizing effect after application and after rinsing the applied area with water and drying with a towel.
1 point: The subject felt that the moisturizing effect was high after application, but felt that the moisturizing effect was slightly low after rinsing the applied area with water and drying with a towel.
0 point: When feeling that the moisturizing effect is low after application and after rinsing the applied area with water and drying with a towel.

<Five-level evaluation based on the total score>
◎: Total score is 35 points or more ○: Total score is 30 points or more and 34 points or less △: Total score is 20 points or more and less than 29 points ×: Total score is less than 19 points

(4) Absence of sliminess when hands are wetted with water 20 women (22 to 40 years old) were used as panelists, and a water-in-oil type skin emulsifying cosmetic (about 2 g) was applied. was wetted with water, it was evaluated and rated according to the following criteria. Then, based on the sum of the scores, the following 4-grade evaluation from "A" to "X" was performed, and 30 points or more were judged to be a water-in-oil skin emulsified cosmetic with a high moisturizing effect.

2 points: No slipperiness was felt when the hand was wetted with water.
1 point: A slightly slimy feeling was felt when the hand was wetted with water.
0 points: When feeling slimy when the hand is wetted with water.

<Five-level evaluation based on the total score>
◎: Total score is 35 points or more ○: Total score is 30 points or more and 34 points or less △: Total score is 20 points or more and less than 29 points ×: Total score is less than 19 points

From Examples 1 to 7, the water-in-oil type skin emulsified cosmetic using the component of the present invention has high temperature stability, no stickiness at the time of application, and after rinsing the applied area with water and drying with a towel. It was good in terms of moisturizing feeling and absence of slipperiness when the hands were wetted with water before being sufficiently dried after application.

On the other hand, in Comparative Examples 1 to 5, sufficient performance was not obtained.
That is, in Comparative Examples 1 and 2, since the component (A) was replaced with another component (A'), it was found to be non-sticky and null when the hands were wetted with water before being applied and sufficiently dried. The lack of stickiness was insufficient.
In Comparative Example 3, since the component (A) was not blended, the moisturizing feeling after rinsing the applied part with water and drying with a towel, and the null when the hand was wetted with water before it was applied and sufficiently dried. The lack of stickiness was insufficient.
In Comparative Example 4, since the component (B) was replaced with another component (B'), high-temperature stability, non-stickiness, and when the hand was wetted with water before being applied and sufficiently dried However, the lack of nullness was insufficient.
In Comparative Example 5, the component (A) was highly blended, and the component (C) was replaced with polyglyceryl-5 trioleate (C′) and Solbes tetraisostearate 6 (C′). Insufficient stability, non-stickiness, non-stickiness when hands were wetted with water prior to application and sufficient drying.

Claims (1)

(A) The ratio Mz/Mw between the weight-average molecular weight (Mw) and the z-average molecular weight (Mz), which is represented by formula (1) and calculated from the chromatogram obtained by gel permeation chromatography measurement, is represented by formula (2). 0.1 to 15% by mass of an alkylene oxide derivative that satisfies the relationship

Z-[O-(PO) _a -{(EO) _b /(PO) _c }-H] _n (1)

(In formula (1),
Z is a residue obtained by removing all the hydroxyl groups from a compound having 1 to 8 carbon atoms and 1 to 4 hydroxyl groups,
n represents a number from 1 to 4,
EO represents an oxyethylene group,
PO represents an oxypropylene group,
a and c are the average number of added moles of the oxypropylene group PO, respectively, and are 1 ≤ a ≤ 20 and 1 ≤ c ≤ 40;
b is the average number of added moles of the oxyethylene group EO, and 0≦b≦40. )

5≦Mz/Mw≦60 (2)

(B) 0.1 to 10% by mass of glyceryl oleate and/or glyceryl isostearate
(C) 0.1 to 5% by mass of a nonionic surfactant having an HLB of 10 to 18 selected from the group consisting of polyoxyethylene hydrogenated castor oil, polyoxyalkylene decyltetradecyl ether and polyoxyethylene sorbitan fatty acid ester, and (D) 3 to 50% by mass of oily components
A water-in-oil type skin emulsion cosmetic comprising:

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