JP2007291095A - Water-in-oil type emulsion cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-in-oil type emulsion cosmetic superior in the spreading when being applied and the adhesion to the skin, high in emollient effect, and excellent in the duration of the emollient effect, and satisfactory in the stablility with time. <P>SOLUTION: The water-in-oil type emulsion cosmetic is characterised by containing a compound (a) formed by esterifying carboxyl groups at both the ends of an oligomer ester of a dimer acid and a dimer diol with an isostearyl alcohol, a specific lipophilic surfactant (b) having a HLB of 3-6, an electrolyte (c) and water (d). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a water-in-oil emulsified cosmetic comprising a specific ester compound, a specific HLB 3-6 lipophilic surfactant, an electrolyte, and water. The present invention relates to a water-in-oil emulsified cosmetic having excellent adhesion to water, high emollient effect and durability, and good temporal stability.

Water-in-oil emulsified cosmetics coat the skin surface with an oil film, prevent moisture transpiration, protect the skin from drying, and have high effects on the skin, such as emollient and moisturizing effects. It is applied to various cosmetics because of its breadth, and various base materials are blended in order to obtain the desired quality characteristics.
In particular, those using polyoxyalkylene-modified organopolysiloxane as an emulsifier can use various oil agents such as volatile silicone as the oil agent, and it is known that it has a refreshing feel and stability over time, and has a wide range of quality. (For example, see Patent Documents 1 and 2). Furthermore, it is possible to obtain an arbitrary quality by selecting an oil agent other than the volatile silicone. For example, using a low molecular weight silicone provides a refreshing feel, using triglycerin fatty acid ester or ester oil improves skin familiarity, and using a highly polymerized oil such as α-olefin oligomers adheres to the skin. Techniques such as enhancing the properties and the emollient effect have been known (see, for example, Patent Document 3).
On the other hand, in order to obtain a moisturizing effect, a technique of blending an electrolyte (for example, see Patent Document 4) and dimer dilinoleic acid di (phytostearyl, isostearyl, cetyl, stearyl, behenyl) (for example, see Patent Document 5) is known. It was done.
JP-A-11-279020 JP 2002-316913 A JP 2001-072533 A JP 2003-1113016 A JP 2005-104854 A

However, when silicone oil is added, adhesion to the skin may be inferior. Oils with a high degree of polymerization such as triglycerin fatty acid ester, ester oil, and α-olefin oligomer may not be easy to spread. In addition, when the α-olefin oligomer is exposed to a high temperature condition for a long time, the oil content may be deteriorated to cause a strange odor. In addition, in order to obtain good quality in adhesion to the skin and stability over time, it is necessary to combine a large amount of volatile silicones and combine various oils. It would be difficult to balance the feeling of use and stability, for example, if the stability was secured, the feeling of use would deteriorate.
On the other hand, when an electrolyte or dimer dilinoleate (phytostearyl, isostearyl, cetyl, stearyl, behenyl) is blended to obtain a moisturizing effect, it may be necessary to blend other components to ensure stability. The emollient effect was not sufficient.
Therefore, it has been desired to develop a water-in-oil emulsified cosmetic that is excellent in spreading at the time of application and adhesion to the skin, has a high emollient effect and its sustainability, and has good stability over time.

  Under such circumstances, the present inventors have conducted extensive studies to solve the above problems, and as a result, esterified carboxyl groups at both ends of oligomeric esters of dimer acid and dimer diol, which are specific ester compounds, with isostearyl alcohol. Water-in-oil type cosmetics containing the compound, specific HLB3-6 lipophilic surfactants, electrolytes, and water are excellent in spreading and adhesion to the skin, emollient effect and its persistence The present invention has been completed by finding a water-in-oil emulsified cosmetic that has excellent properties such as high stability and stability over time, and has a balance between usability and stability.

That is, the present invention comprises the following components (a), (b), (c), (d);
(A) Compound R3OCO-R1-(-COO-R2-OCO-R1-) n in which carboxyl groups at both ends of the oligomeric ester of dimer acid and dimer diol represented by the following chemical formula (1) are esterified with isostearyl alcohol -COOR3 (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)
(B) one or more HLB 3-6 lipophilic surfactants selected from the following (b1) to (b3);
(B1) polyoxyethylene dipolyhydroxystearate,
(B2) a silicone compound represented by the following general formula (2);
R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-a-b-c) / 2} (2)
[Wherein, R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or —C _m H _2m —O— (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e R ⁷ is the same or different organic group selected from organic groups represented by R ⁷ , and R ⁵ is —C _m H _2m —O— (C ₂ H ₄ O) _f (C ₃ H ₆ O). _The polyoxyalkylene group represented by _g- R ⁸ , R ⁶ is the following general formula (3)

In which R ⁷ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁹ — (CO) —, and R ⁸ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. Or an organic group represented by R ⁹ — (CO) —, R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5.
(B3) A long-chain hydrocarbon group-containing polyoxyalkylene-modified organopolysiloxane (c) electrolyte (d) A water-in-oil emulsified cosmetic comprising water is provided.
Furthermore, the water-in-oil emulsified cosmetic containing 0.5 to 20% by mass of component (a), 0.1 to 5% by mass of component (b), and 0.01 to 5% by mass of component (c). .

  The water-in-oil emulsified cosmetic of the present invention is excellent in spreading at the time of application and adhesion to the skin, excellent in emollient effect and its sustainability, and excellent in stability over time.

The component (a) used in the present invention is an oil agent having characteristics such as high adhesion, excellent emollient effect and sustainability, and easy blending into a water-in-oil emulsified cosmetic. Dimer acid and dimer A compound obtained by esterifying carboxyl groups at both ends of an oligomer ester with a diol with isostearyl alcohol (hereinafter sometimes simply referred to as “ester compound”) can be represented by the following general formula (1).
R3OCO-R1-(-COO-R2-OCO-R1-) n-COOR3 (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)

The ester compound of component (a) used in the present invention is a compound obtained by esterifying carboxyl groups present at both ends of an oligomer ester obtained from dimer acid and dimer diol with isostearyl alcohol.
Dimer acid, which is a starting material, is obtained by an intermolecular polymerization reaction of unsaturated fatty acid, but is obtained by dimerizing unsaturated fatty acid having 11 to 22 carbon atoms, and mainly a dibasic acid having about 36 carbon atoms. It is an ingredient. The CAS number corresponds to 61788-89-4. Further, in the dimerization reaction, hydrogenated dimer acid obtained by hydrogenating double bonds is preferable. Examples of commercially available products include PRIPOL 1006, 1009, 1015, 1025, etc. (manufactured by Unikema).
The dimer diol is mainly composed of a diol having about 36 carbon atoms in which the dimer acid and / or lower alcohol ester thereof is hydrogenated in the presence of a catalyst and the carboxylic acid portion of the dimer acid is an alcohol. Examples of commercially available products include PRIPOL 2033 (manufactured by Unikema).
Isostearyl alcohol includes those obtained by reducing fatty acids obtained from dimer acid by-products, those obtained by the garvet method, those obtained by the aldol condensation method, and the like. Things can also be used. Examples of commercially available products include Speziol C18 ISOC (manufactured by Cognis).

Although the manufacturing method of the ester compound of a component (a) is not specifically limited, For example, after esterifying dimer acid and dimer diol and obtaining oligomer ester, it obtains by esterifying a carboxyl group with isostearyl alcohol further. be able to. It can also be obtained by esterifying dimer acid, dimer diol and isostearyl alcohol at once.
In the production of component (a), when an oligomer ester is obtained as an intermediate, the oligomer ester of dimer acid and dimer diol, which is an intermediate, can be obtained by changing the respective charging ratios, The average molecular weight can be adjusted. The range of the charging ratio is preferably 0.4 to 0.9 molar equivalent of dimer diol with respect to 1 molar equivalent of dimer acid. Furthermore, when esterifying with isostearyl alcohol, it is preferable that it is 0.8-1.5 mol with respect to the remaining carboxyl group.

  The conditions for the esterification reaction in obtaining the ester compound of component (a) are not particularly limited, and are carried out by a commonly used method. For example, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid, methanesulfonic acid, boron trifluoride diethyl ether complex or the like is used as a catalyst, and heptane, hexane, cyclohexane, toluene, xylene or the like is used as a solvent at 50 to 260 ° C. be able to. Alternatively, esterification can be carried out at 100 to 260 ° C. even without solvent and without catalyst.

  The ester compound of component (a) preferably has a viscosity at 25 ° C. of 10,000 to 20,000 mPa · s. Examples of such ester compounds include LUSPLAN DA-DD-IS (manufactured by Nippon Seika Co., Ltd.). The viscosity was measured using a cone plate viscometer (ROTO visco1 manufactured by Haake Co.) under the conditions of a shear rate of 100 (1 / s), a cone diameter of 35 mm, and an angle of 2 °.

  The blending amount of component (a) in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, but is preferably 0.5 to 20% by mass (hereinafter simply referred to as “%”), and is preferably 3 to 10%. Is particularly preferred. When the blending amount is within this range, the characteristics of the component (a) can be sufficiently exhibited, non-sticky, excellent in adhesion to the skin, and excellent in temporal stability can be obtained.

The component (b) used in the present invention includes the following (b1) to (b3)
(B1) polyoxyethylene dipolyhydroxystearate,
(B2) a silicone compound represented by the following general formula (2);
R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-a-b-c) / 2} (2)

[Wherein, R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or —C _m H _2m —O— (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e R ⁷ is the same or different organic group selected from organic groups represented by R ⁷ , and R ⁵ is —C _m H _2m —O— (C ₂ H ₄ O) _f (C ₃ H ₆ O). _The polyoxyalkylene group represented by _g- R ⁸ , R ⁶ is the following general formula (3)

In which R ⁷ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁹ — (CO) —, and R ⁸ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. Or an organic group represented by R ⁹ — (CO) —, R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5.
(B3) One or more HLB 3-6 lipophilic surfactants selected from polyoxyalkylene-modified organopolysiloxanes containing long chain hydrocarbon groups, which function as emulsifiers for water-in-oil emulsified cosmetics. is there. It can be easily blended into a water-in-oil emulsified cosmetic, has little stickiness, and has good stability over time.

The polyoxyethylene dipolyhydroxystearate of (b1) which is one of the components (b) is a diester of polyhydroxystearic acid and polyethylene glycol. Examples of the preparation method include poly (12-hydroxystearic acid) ) And an acid chloride prepared by reacting a halogenating agent such as thionyl chloride with polyethylene glycol in the presence of an alkali. In this preparation, if the amount of acid chloride is increased, a dipolyester is obtained, and if this amount is small, a product having a low acylation rate such as a monoester is obtained. Moreover, poly (12-hydroxystearic acid) which becomes a hydrophobic group part in (b1) has an average molecular weight of 1000 to 4000 as the degree of polymerization, and polyethylene glycol has an average molecular weight of 400 to 6000. It is preferable from the viewpoint of good handling at the time, emulsification ability, and reduction of stickiness.
As a preferred compound of the polyoxyethylene dipolyhydroxystearate (b1), those having the INCI name listed as PEG-30 dipolyhydroxystearate are preferred. Examples of such a commercially available product (b1) include Aracel P-135 manufactured by Unikema Corporation.

Moreover, the silicone compound of (b2) which is another one of the component (b) of this invention is represented by following General formula (2).
R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-a-b-c) / 2} (2)

[Wherein, R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or —C _m H _2m —O— (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e R ⁷ is the same or different organic group selected from organic groups represented by R ⁷ , and R ⁵ is —C _m H _2m —O— (C ₂ H ₄ O) _f (C ₃ H ₆ O). _The polyoxyalkylene group represented by _g- R ⁸ , R ⁶ is the following general formula (3)

In which R ⁷ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁹ — (CO) —, and R ⁸ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. Or an organic group represented by R ⁹ — (CO) —, R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5. The average molecular weight of the silicone compound represented by the formula is not particularly limited, but is preferably 500 to 200,000, and more preferably 1,000 to 100,000. Moreover, the thing of 3-6 of HLB is used suitably as an emulsifier or emulsification adjuvant of a water-in-oil emulsion cosmetic. Preferable compounds of such poly (oxyethylene / oxypropylene) methylpolysiloxane copolymer include those whose INCI name is listed as PEG-9 polydimethylsiloxyethyl dimethicone, and commercially available products include KF- 6028 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  In addition, the long-chain hydrocarbon group-containing polyoxyalkylene-modified organopolysiloxane (b3), which is still another component (b) of the present invention, includes, for example, the following general formula (4) or (5): The silicone compound shown by these is mentioned.

R ¹¹ _a R ¹² _b R ¹³ _c SiO _{(4-abc) / 2}
... (4)
[Wherein, R ¹¹ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, a hydrogen atom, an aryl group, an aralkyl group, or a fluorine-substituted alkyl group, and R ¹² represents —C _m H _2m —O— A group represented by (C ₂ H ₄ O) _d — (C ₃ H ₆ O) _e —R ¹⁴ , wherein m is an integer of 1 to 5, d and e are integers of 0 or more, and d + e ≧ 1 a to 200 ^{DEG, R 14} is a monovalent hydrocarbon group or a C1-5 hydrogen atom or a carbon - (CO) organic group represented by ^{-R 15, R 15} is a monovalent hydrocarbon group having 1 to 5 carbon atoms R ¹³ is a monovalent hydrocarbon group having 10 to 30 carbon atoms, and a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5,. 001 ≦ c ≦ 1.5. ] The silicone compound represented by this.

R ¹⁶ _a R ¹⁷ _b R ¹⁸ _c SiO _{(4-abc) 2}
... (5)
[Wherein, R ¹⁶ may be the same or different and represents an alkyl group having 1 to 10 carbon atoms, a hydrogen atom, an aryl group, an aralkyl group, or a fluorine-substituted alkyl group, and R ¹⁷ represents —C _m H _2m —O— _{(C 2 H 4 O) d} - (C 3 H 6 O) groups (wherein represented by _e -R ^19, m is an integer of from 1 to 5, d, e is an integer of 0 or more, and, d + e ≧ 1 a to 200 ^{DEG, R 19} is a monovalent hydrocarbon group or a C1-5 hydrogen atom or a carbon - (CO) organic group represented by ^{-R 20, R 20} is a monovalent hydrocarbon group having 1 to 5 carbon atoms R ¹⁸ is —C _n H _2n —O— (C ₂ H ₄ O) _f — (C ₃ H ₆ O) _g —R ²¹ (wherein n is an integer of 1 to 5, f, g It is an integer of 0 or more, and a f + g ≧ ^{0~200, R 21} is the number 10 to 30 monovalent hydrocarbon group) carbon, a, b, c are respectively 1.0 ≦ a ≦ 2. A 0.001 ≦ b ≦ 1.5,0.001 ≦ c ≦ 1.5. ] The silicone compound represented by this.

  Preferred compounds of the long-chain hydrocarbon group-containing polyalkylene-modified organopolysiloxane (b3) that are preferred as the component (b) include those in which the INCI name is listed as cetyl dimethicone copolyol. 4) ABIL EM-90 (manufactured by Goldschmidt) and the like, and the silicone compound of the above general formula (5) (described in JP-A Nos. 04-036324 and 09-059386) And these may be used alone or in combination of two or more as required.

  The blending amount of component (b) in the water-in-oil emulsified cosmetic of the present invention is not particularly limited, and may be appropriately adjusted according to the blending amount of the inner aqueous phase and the quality of the oil agent. % Is preferable, and 0.5 to 3% is particularly preferable. When used in this range, the emulsifiability is good and the stability over time is better.

  The electrolyte of component (c) used in the present invention includes sodium chloride, potassium chloride, magnesium chloride, sodium sulfate, magnesium sulfate, zinc sulfate, sodium sulfite, sodium thiosulfate, sodium monohydrogen phosphate, sodium dihydrogen phosphate. , Inorganic salts such as trisodium phosphate, and ammonium, alkali metals, alkaline earth metals, magnesium, iron, and other organic acids such as lactic acid, acetic acid, benzoic acid, propionic acid, tartaric acid, citric acid, amino acid, ethylenediaminetetraacetic acid Further, ascorbic acid and / or a water-soluble ascorbic acid derivative having a whitening effect, such as a zinc salt, can be blended. Specific examples of the water-soluble ascorbic acid derivative include, for example, L-ascorbic acid sodium phosphate, potassium L-ascorbic acid phosphate, which is a monovalent metal salt of L-ascorbic acid phosphate, divalent Metal salts of L-ascorbic acid phosphate calcium, L-ascorbic acid phosphate magnesium, trivalent metal salt L-ascorbic acid phosphate aluminum, and monovalent metal salt of L-ascorbic acid sulfate Sodium L-ascorbate sulfate, potassium L-ascorbate sulfate, calcium divalent metal salt L-ascorbate sulfate, magnesium L-ascorbate sulfate, aluminum trivalent metal salt L-ascorbate sulfate aluminum And even L Examples include sodium ascorbate, potassium L-ascorbate, calcium L-ascorbate sulfate, magnesium L-ascorbate, aluminum L-ascorbate sulfate, L-ascorbate glucoside, and one or more of these are appropriately selected. Can be used. Among these, sodium chloride, magnesium L-ascorbate phosphate, and L-ascorbic acid glucoside are preferable from the viewpoints of moisturizing effect and stability over time.

The blending amount of the component (c) electrolyte in the present invention is not particularly limited, but is preferably 0.01 to 5%. Especially, the blending amount of ascorbic acid and / or water-soluble ascorbic acid derivative is stable over time or From the feeling of use such as non-stickiness, it is preferably 0.01 to 3%, particularly preferably 0.1 to 3%, based on the total amount.

  The water of component (d) used in the present invention is an essential component for making a water-in-oil emulsified cosmetic. The blending amount is not particularly limited, but is preferably 30 to 80% from the viewpoint of emulsification stability, feeling of use such as touch.

  Further, in the water-in-oil emulsified cosmetic of the present invention, in addition to the above essential components, in order to dilute the component (a), to improve the emulsion stability, to give a more emollient feeling, or to powder by powder An oil agent other than the component (a) can be blended for the purpose of reducing the sharpness. The oil agent used here is not particularly limited as long as it is an oil agent usually used in cosmetics, and origins of animal oil, vegetable oil, synthetic oil, etc., and properties such as solid oil, semi-solid oil, liquid oil, volatile oil, etc. Regardless of oil, oil agents such as hydrocarbons, fats and oils, waxes, hardened oils, ester oils, fatty acids, higher alcohols, silicone oils, fluorine-based oils, lanolin derivatives and the like can be mentioned. Specifically, hydrocarbons such as liquid paraffin, squalane, petrolatum, paraffin wax, ceresin wax, microcrystalline wax, molasses, montan wax, fisher trops wax, olive oil, castor oil, mink oil, macadamian nut oil, etc. Oils, beeswax, lanolin, carnauba wax, candelilla wax, gay wax, waxes such as cetyl isooctanoate, isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, diglyceryl diisostearate, tri Diglyceryl isostearate, glyceryl tribehenate, rosin acid pentaerythritol ester, neopentyl glycol dioctanoate, cholesterol fatty acid ester, N-laur Esters such as yl-L-glutamic acid di (cholesteryl, behenyl, octyldodecyl), stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid, rosin acid, fatty acids such as 12-hydroxystearic acid, Higher alcohols such as stearyl alcohol, cetyl alcohol, lauryl alcohol, oleyl alcohol, isostearyl alcohol, behenyl alcohol, low degree of polymerization dimethylpolysiloxane, high degree of polymerization dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, octamethyl Silicones such as cyclotetrasiloxane and fluorine-modified silicone, fluorine oils such as perfluoropolyether, perfluorodecane and perfluorooctane, lanolin and vinegar Lanolin, lanolin fatty acid isopropyl, lanolin derivatives such as lanolin alcohols, etc., and these can be used singly or in combination. The blending amount of the oil agent in the water-in-oil emulsified cosmetic of the present invention is preferably 0.1 to 80% from the viewpoint of emulsification stability, usability such as touch.

  In addition, the water-in-oil emulsified cosmetic of the present invention contains surfactants such as silicone surfactants, nonionic surfactants, ionic surfactants, and amphoteric surfactants other than component (b). It can also be used in combination as an emulsification aid, a dispersion stabilizer, and a pigment dispersant.

  Furthermore, the water-in-oil emulsified cosmetic composition of the present invention includes, in addition to the above components, a powder, a water-soluble polymer, and a gelled material in a quantitative and qualitative range that does not impair the effects of the present invention. Ingredients commonly used in cosmetics such as humectants, humectants, ultraviolet absorbers, antioxidants, preservatives, chelating agents, fragrances, and cosmetic ingredients can be blended.

  The powder that can be used in the water-in-oil emulsified cosmetic of the present invention is a powder that is blended for the purpose of imparting concealing properties, coloring agents, feel modifiers, pearl agents, UV screening agents, etc. It is blended into the material. Such a powder is not particularly limited by the shape of a sphere, plate, needle or the like, the shape of fumes, fine particles, particle size such as pigment grade, the particle structure such as porous or nonporous, etc. , Glitter powders, organic powders, pigment powders, composite powders, and the like. Specifically, as a colorant, titanium oxide, black titanium oxide, conger, ultramarine, red rose, yellow iron oxide, black iron oxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, barium sulfate , Chromium oxide, chromium hydroxide, carbon black, tar dyes, etc., as a touch modifier, silicon oxide, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic sericite, sericite, talc , Silicon carbide, boron nitride, nylon powder, polymethyl methacrylate, acrylonitrile-methacrylic acid copolymer powder, vinylidene chloride-methacrylic acid copolymer powder, wool powder, silk powder, crystalline cellulose, N-acyl lysine, etc. body Bismuth oxychloride, titanium mica, iron oxide coated mica, iron oxide mica titanium, organic pigment-treated mica titanium, aluminum powder, etc., as an ultraviolet blocking agent, fine particle titanium oxide, fine particle zinc oxide, fine particle titanium oxide coated mica titanium, Examples thereof include composite powders such as fine particle zinc oxide-coated mica titanium and barium sulfate-coated mica titanium, and these can be used alone or in combination. In addition, these powders are treated with a conventionally known method such as silicones, fluorine compounds, metal soaps, oils and the like from a viewpoint of dispersibility, adhesion, and makeup sustainability. It can also be used.

  The form of the water-in-oil emulsified cosmetic of the present invention may be any of cream, gel, emulsion, liquid, etc., and is produced by a conventional method, and any of skin care cosmetics, makeup cosmetics, and hair cosmetics. Cosmetics that are particularly easily effective are eye products such as creams, emulsions, foundations, mascaras, sunscreen cosmetics, and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples. Note that these do not limit the present invention.

(Synthesis Example 1)
"Dimer acid dimer diol oligomer ester isostearyl alcohol ester compound"
Hydrogenated dimer acid (PRIPOL 1006: manufactured by Unikema) 200 g (0.348 mol) and dimer diol (PRIPOL 2033: manufactured by Unikema) 132 g (0.243 mol) were charged into a reactor and heated to 210-220 ° C. in a nitrogen stream. Then, the esterification reaction was carried out for 5 hours while distilling off the generated water to obtain 323 g of an intermediate dimer acid dimer diol oligomer ester (dimer acid: dimer diol = 1: 0.7). Furthermore, 307 g of the oligomer ester and 59 g (0.217 mol) of isostearyl alcohol (Speziol C18 ISOC: manufactured by Cognis) were charged into a reactor, heated to 210 to 220 ° C. in a nitrogen stream, and the generated water was distilled off. Then, the esterification reaction was performed for 10 hours to obtain 351 g of the target ester compound. The obtained ester compound had a hue Gardner 2, an acid value of 5.2, a saponification value of 111, a viscosity of 15,000 mPa · s, and a refractive index of 1.48.

Example 1 (Products 1 to 7 of the present invention and Comparative products 1 to 6): Skin care cream A cream was prepared by the composition shown in Table 1 and the following production method, and “goodness of spread” and “adhesion to the skin” at the time of application. “Emollient effect”, “Persistence of emollient effect”, and “Stability with time” were evaluated by the following evaluation methods 1 and 2, and the results are shown in Table 1.

(Manufacturing method)
A. Components (1) to (10) are heated to 70 ° C. and mixed and dispersed.
B. Components (11) to (17) were added to A and emulsified at room temperature to obtain a skin care cream.

Evaluation items 1. 1. Good quality 2. Adhesion to skin Emollient effect 4. Persistence of emollient effect Stability over time

(Evaluation method 1)
For the above evaluation items 1 to 4, apply skin care creams of the present invention products 1 to 7 and comparative products 1 to 6 to the face of pearls for 2 weeks after face washing twice a day in the morning and evening. We had you use continuously. The sensation during that time was comprehensively evaluated according to the following five-level evaluation criteria, and the average score of the evaluation of all panels was further determined according to the following criteria.
[Evaluation criteria]
Sensory evaluation result: Score Very good: 5 points Good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 point [Criteria]
Average score of all panels: Judgment Over 4 points and below 5 points: ◎
Over 3 points and below 4 points: ○
More than 2 points to 3 points or less: △
1 to 2 points: ×

(Evaluation method 2)
Regarding the stability over time of the evaluation item 5, 100 g of the skin care cream of the present invention is filled in a glass bottle with a diameter of 30 mm, set in an incubator of three levels of 5 ° C., 20 ° C. and 40 ° C. Changes (smell, viscosity) were evaluated according to the following four-stage evaluation criteria.
[smell]
Regarding odor, samples of each level were stored at 20 ° C. for 24 hours after one month, and then the difference in odor appearance was evaluated using a 5 ° C. sample as a standard.
[viscosity]
About a viscosity, after leaving it to stand at 20 ° C. for 24 hours after one month, using a B-type rotational viscometer bismetron (manufactured by Shibaura System Co., Ltd.), appropriately selecting a No. 1-4 rotor and measuring for 60 seconds, a 5 ° C. sample And the difference in viscosity was evaluated.
Evaluation criteria Change with time: Evaluation No change at each level: ◎
There is a slight change in 1 level, but there is no problem in usability: ○
There is a change in 1 level, there is a problem in usability: △
There is a change and there is a problem in usability: ×

The skin care creams of the present invention products 1 to 7 have good spreadability at the time of application, adhesion to the skin, emollient effect, long-lasting emollient effect, no bulky odor, low viscosity change at low and high temperatures It had excellent quality in all items of stability over time such as none. On the other hand, Comparative Product 1 in which liquid paraffin was blended in place of the ester compound of component (a) and the electrolyte of component (c) was not blended was inferior in emollient effect and sustainability, and inferior in stability over time. there were. And even if it mix | blended the electrolyte of the component (c), all the comparative products 2-4 which mix | blended other oil agents instead of the component (a) were not satisfactory. That is, the comparative product 2 containing liquid paraffin instead of the component (a) has insufficient adhesion to the skin and is inferior in the emollient effect and its sustainability, and is purified instead of the component (a). Comparative product 3 blended with lanolin is not sufficient in emollient effect and sustainability, and is inferior in stability over time. Further, comparative product 4 blended with dimethylpolysiloxane instead of component (a) is Although it was excellent in stability over time, the adhesion to the skin was poor and the emollient effect and its sustainability could not be obtained.
Comparative products 5 and 6 containing HLB3.7 sorbitan sesquioleate and diglycerin diisostearate instead of component (b) were much less stable over time.

Example 2: Emulsion (component) (%)
1. Dimethylpolysiloxane 2
2. Decamethylcyclopentasiloxane 15
3. Long chain hydrocarbon group-containing polyoxyalkylene-modified oroganopolysiloxane (Note 6) 5
4). Cetyl isooctanoate 5
5). Ester compound (Note 5) 10
6). Paraoxybenzoic acid ester 0.1
7). Sodium lactate 0.5
8). Purified water remaining amount Note 6: ABIL EM-90 (manufactured by Goldschmidt) (HLB: 4.5)

(Manufacturing method)
A. Components (1) to (6) are mixed and dispersed.
B. Components (7) and (8) were added to A and emulsified at room temperature to obtain an emulsion.

  The emulsion of Example 2 is stable over time, such as good spreading during application, adhesion to skin, emollient effect, sustained emollient effect, no bulky odor, and low viscosity change at low and high temperatures. Good quality and excellent quality in all items.

Example 3: Base cream (ingredient) (%)
1. Dimethylpolysiloxane 2
2. Decamethylcyclopentasiloxane 10
3. PEG-9 polydimethylsiloxyethyl dimethicone (Note 1) 3
4). Cetyl isooctanoate 5
5). Ester compound (Note 5) 5
6). Octyl methoxycinnamate 5
7). Trimethylsiloxysilicic acid 1
8). Organically modified bentonite 0.5
9. Titanium oxide 10
10. Talc 5
11. Nylon powder 1
12 Paraoxybenzoic acid ester 0.1
13. Xanthan gum 0.1
14 L-ascorbic acid phosphate magnesium 0.3
15. Purified water remaining

(Manufacturing method)
A. Components (1) to (12) are mixed and dispersed.
B. Components (13) to (15) were added to A and emulsified at room temperature to obtain a base cream.

  The base cream of Example 3 is good in spreading at the time of application, adhesion to the skin, emollient effect, persistence of the emollient effect, no odor of bulk, little change in viscosity at low and high temperatures. It had excellent quality in all items such as stability.

Example 4: Sunscreen (component) (%)
1. Dimethylpolysiloxane 2
2. Decamethylcyclopentasiloxane 20
3. Long chain hydrocarbon group-containing polyoxyalkylene-modified oroganopolysiloxane (Note 4) 3
4). Polyoxyethylene oleyl ether (6E.O.) 1
5). Cetyl isooctanoate 5
6). Ester compound (Note 5) 10
7). Lanolin alcohol 2
8). Octyl methoxycinnamate 5
9. Acrylate silicone solution (Note 7) 5
10. Organically modified bentonite 0.5
11. Titanium oxide 10
12 Fine particle titanium oxide 15
13. Talc 5
14 Nylon powder 1
15. Paraoxybenzoic acid ester 0.1
16. Guar gum 0.1
17. Sodium chloride 0.5
18. Purified water remaining amount Note 7: KP-545 (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Manufacturing method)
A. Components (1) to (15) are mixed and dispersed.
B. Components (16) to (18) were added to A and emulsified at room temperature to obtain a sunscreen.

  The sunscreen of Example 10 has good spreadability at the time of application, adhesion to the skin, emollient effect, sustained emollient effect, no bulk odor change, low viscosity change at low and high temperatures, etc. It had excellent quality over time.

Example 5: Mascara
(Ingredient) (%)
1. Microcrystalline wax 9
2. Candelilla wax 6
3. Carnauba wax 5
4). 4. Diglyceryl triisostearate remaining amount Ester compound (Note 5) 20
6). Squalane 3
7). PEG-9 polydimethylsiloxyethyl dimethicone (Note 1) 5
8). Perfume appropriate amount 9. Black iron oxide 10
10. Carboxyvinyl polymer 0.2
11. Dipropylene glycol 5.5
12 Purified water 30
13. L-ascorbic acid glucoside 1

(Manufacturing method)
A. Components (1) to (6) are dissolved by heating at 110 to 120 ° C.
B. Add components (7) to (9) to A and mix and disperse uniformly.
C. Components (10) to (13) heated to 70 ° C. are added to B and emulsified at 70 ° C.
D. C was filled into a container to obtain a mascara.

  The mascara of Example 5 had excellent quality at the time of application, good adhesion to eyelashes, emollient effect, sustained emollient effect, and stability over time.

Claims (2)

The following components (a), (b), (c), (d);
(A) Compound R3OCO-R1-(-COO-R2-OCO-R1-) in which carboxyl groups at both ends of the oligomeric ester of dimer acid and dimer diol represented by the following general formula (1) are esterified with isostearyl alcohol n-COOR3 (1)
(In the formula, R ¹ represents a dimer acid residue, R ² represents a dimer diol residue, R ³ represents an isostearyl alcohol residue, and n represents a number of 4 to 6.)
(B) one or more HLB 3-6 lipophilic surfactants selected from the following (b1) to (b3);
(B1) polyoxyethylene dipolyhydroxystearate,
(B2) a silicone compound represented by the following general formula (2);
R ⁴ _a R ⁵ _b R ⁶ _c SiO _{(4-a-b-c) / 2} (2)
[Wherein, R ⁴ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, or —C _m H _2m —O— (C ₂ H ₄ O) _d (C ₃ H ₆ O) _e R ⁷ is the same or different organic group selected from organic groups represented by R ⁷ , and R ⁵ is —C _m H _2m —O— (C ₂ H ₄ O) _f (C ₃ H ₆ O). _The polyoxyalkylene group represented by _g- R ⁸ , R ⁶ is the following general formula (3)
In which R ⁷ is a hydrocarbon group having 4 to 30 carbon atoms or an organic group represented by R ⁹ — (CO) —, and R ⁸ is a hydrogen atom or a hydrocarbon having 1 to 30 carbon atoms. Or an organic group represented by R ⁹ — (CO) —, R ⁹ is a hydrocarbon group having 1 to 30 carbon atoms. a, b and c are 1.0 ≦ a ≦ 2.5, 0.001 ≦ b ≦ 1.5 and 0.001 ≦ c ≦ 1.5, respectively, d and e are 0 ≦ d ≦ 50, An integer of 0 ≦ e ≦ 50, f and g are integers of 2 ≦ f ≦ 200, 0 ≦ g ≦ 200, and f + g is 3 to 200, respectively. M is an integer of 0 ≦ m ≦ 15, h is an integer of 0 ≦ h ≦ 500, and n is an integer of 1 ≦ n ≦ 5. ]
(B3) A long-chain hydrocarbon group-containing polyoxyalkylene-modified organopolysiloxane (c) electrolyte (d) Water-in-oil type emulsified cosmetic comprising water. 0.5-20 mass% of component (a),
0.1 to 5% by mass of component (b),
The water-in-oil emulsified cosmetic according to claim 1, wherein 0.01 to 5% by mass of component (c) is blended.