Water-in-oil emulsion cosmetic

Abstract

To provide a water-in-oil emulsion cosmetic which is excellent in natural luster, smoothness of a coating film and lack of color unevenness while having excellent makeup durability.SOLUTION: There is provided a water-in-oil emulsion cosmetic which comprises the following components (A) to (C): (A) an acryl-silicone-based graft copolymer, (B) an organic silicon resin containing an M unit represented by R3SiO1 / 2 (R each independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms and a Q unit represented by SiO4 / 2 and (C) 5 to 30 mass% of a branched volatile silicone oil, wherein the total content mass of the component (A) and the component (B) is 5 to 20 mass% and the content mass ratio (C) / (volatile oil solution) of the component (C) to the total amount of a volatile oil solution is 0.3 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a water-in-oil emulsion cosmetic.

Background Art

[0002] Water-in-oil emulsion cosmetics are a dosage form used in various cosmetics such as makeup cosmetics like foundation, makeup base, blush, eyeshadow, mascara, and emulsion, cream, body cream, hair wax, etc. By combining water-based and oil-based components with powder components, various functions can be imparted. Among them, in makeup cosmetics, there is a high demand for cosmetics with excellent makeup retention effects, and various studies have been conducted.

[0003] For example, Patent Document 1 describes that a water-in-oil emulsion cosmetic containing a specific non-volatile silicone oil, a silicone-based film-forming agent, a volatile oil, and an ester oil that are incompatible with squalane is excellent in makeup persistence, and even over time, the finish is maintained and the removal of makeup is suppressed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in water-in-oil emulsion cosmetics containing a film-forming agent, unnatural gloss may occur or the gloss may be impaired. Furthermore, there are problems that color unevenness is likely to occur and the smoothness of the coating film is likely to be impaired.

[0006] Therefore, an object of the present invention is to provide a water-in-oil emulsion cosmetic that is excellent in makeup retention, yet has an excellent natural gloss, smoothness of the coating film, and lack of color unevenness. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that an oil-in-water type emulsified cosmetic obtained by combining an acrylic-silicone graft copolymer, a specific organosilicon resin, and a branched volatile silicone oil at a specific ratio can provide an oil-in-water type emulsified cosmetic that has excellent makeup retention, while also having a natural gloss, smoothness of the coating film, and excellent lack of color unevenness, thus completing the present invention.

[0008] That is, the present invention provides: [1] The following components (A) to (C); (A) An acrylic-silicone graft copolymer (B) An organosilicon resin containing an M unit represented by R3SiO 1 / 2 (wherein each R independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms) and a Q unit represented by SiO 4 / 2 An organosilicon resin containing a Q unit represented by (C) 5 to 30% by mass of a branched volatile silicone oil containing: the total content mass of the component (A) and the component (B) is 1 to 20% by mass, and provides an oil-in-water type emulsified cosmetic in which the content mass ratio of the component (C) to the total amount of the volatile oil agent is 0.3 or more. [2] The component (B) is a crosslinked organosilicon resin which is an addition reaction product of the following component (X) and component (Y), and the amount of hydrogen gas generated per mass of this crosslinked organosilicon resin is 1.5 mL / g or less under standard conditions. The present invention provides the oil-in-water type emulsified cosmetic according to [1], which is a crosslinked organosilicon resin. (X) component; an alkenyl group-containing organosilicon resin represented by the following formula (1) and having one or more alkenyl groups in one molecule [Chemical formula] [In the formula, R 1is an alkenyl group having 2 to 8 carbon atoms, R 2 are each independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. 3 are each independently an organopolysiloxane-containing group, and the R 2 Each R 3 3SiO 1 / 2 R in units 3 At least one of a1, a2, a3, b, c, and d is an organopolysiloxane-containing group. <a1≦5、0<a2≦400、0≦a3≦400、0≦b≦320、0≦c≦320、0<d≦1,000であり、かつ、0.5≦(a1+a2+a3) / d≦1.5を満たす数である。] Component (Y): an organohydrogenpolysiloxane represented by the following formula (2) having two or more hydrosilyl groups in each molecule: [ka] [In the formula, R 2 is the same as above, and R 4 are each independently a hydrogen atom or the above R 2 and all R 4 At least two of the groups are hydrogen atoms, and e, f, g, and h are 0 or positive numbers, with the proviso that 2≦e+f+g+h<32 is satisfied. [3] The present invention further provides a water-in-oil emulsion cosmetic composition according to [1] or [2], which contains alumina as component (D). [4] The present invention provides a water-in-oil emulsion cosmetic according to [1] or [2], wherein the content of the component (B) is 1 to 10 mass %. [5] The present invention provides a water-in-oil emulsion cosmetic according to [1] or [2], wherein the mass ratio (C) / (volatile oil) of component (C) to the total amount of volatile oils is 0.4 or more. [6] The present invention provides a water-in-oil emulsion cosmetic according to [1] or [2], which is a makeup cosmetic.

Advantages of the Invention

[0009] According to the present invention, it is possible to provide an oil-in-water type emulsified cosmetic that is excellent in makeup retention, and also excellent in natural gloss, smoothness of the coating film, and lack of color unevenness.

Embodiments for Carrying Out the Invention

[0010] Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following preferred embodiments and can be freely changed within the scope of the present invention. In this specification, "~" means a range including the numerical values before and after it.

[0011] Component (A): Acrylic-silicone graft copolymer The acrylic-silicone graft copolymer as Component (A) used in the present invention is an acrylic-silicone graft copolymer obtained by copolymerizing an organopolysiloxane compound having a radically polymerizable group in the molecule and one or more other radically polymerizable monomers. Any one can be used as long as it forms a film. Specifically, those described in JP-A-2-25411, JP-A-2-132141, etc., and acrylic-silicone graft copolymers described in JP-A-3-162442, JP-A-2003-104825, etc. can be used. Specifically, (acrylates / dimethicone) copolymer, (acrylates / stearyl acrylate / dimethyl methicone) copolymer, (acrylates / behenyl acrylate / dimethyl methicone) copolymer, etc. can be mentioned, and (acrylates / dimethicone) copolymer is preferable from the viewpoint of natural gloss. Commercially available products include KP-541 (isopropanol solution), KP-543 (butyl acetate solution), KP-545 (decamethylcyclopentasiloxane solution), KP-549 (methyltrimethicone solution), KP-550 (isododecane solution) (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0012] The content of component (A) in the present invention is not particularly limited, but is preferably 0.5 to 18%, more preferably 1 to 15%, and even more preferably 1.5 to 10% based on the total amount of the water-in-oil emulsion cosmetic. Within this range, it is preferable because it is more excellent in makeup retention, natural gloss, and lack of color unevenness.

[0013] Component (B): R3SiO 1 / 2 (R independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms) and the M unit represented by, SiO 4 / 2 An organosilicon resin containing a Q unit represented by Component (B) used in the present invention is: R3SiO 1 / 2 (R independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms) and the M unit represented by, SiO 4 / 2 It is an organosilicon resin containing a Q unit represented by. Component (B) in the present invention is not particularly limited, and any one can be used. For example, trimethylsiloxysilicic acid, a crosslinked organosilicon resin which is an addition reaction product of the following component (X) and component (Y), and the amount of hydrogen gas per mass generated from this crosslinked organosilicon resin is 1.5 mL / g or less under standard conditions (hereinafter, may be simply referred to as a crosslinked organosilicon resin), etc. can be mentioned. From the viewpoints of lack of color unevenness, smoothness of the coating film, etc., a crosslinked organosilicon resin is preferable.

[0014] [Component (X)] Component (X) is an alkenyl group-containing organosilicon resin represented by the following average composition formula (1) and having one or more alkenyl groups in one molecule, and can be used alone or in combination of two or more. [Chemical formula] [In the formula, R 1 independently represents an alkenyl group having 2 to 8 carbon atoms, R 2are, independently of each other, groups selected from alkyl groups having 1 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and aralkyl groups having 7 to 30 carbon atoms. R 3 are, independently of each other, organopolysiloxane-containing groups and the above R 2 selected from groups, and each R 3 3SiO 1 / 2 In the unit, one or more of R 3 are organopolysiloxane-containing groups. a1, a2, a3, b, c, and d are numbers such that 0 < a1 ≤ 5, 0 < a2 ≤ 400, 0 ≤ a3 ≤ 400, 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, 0 < d ≤ 1,000, and satisfy 0.5 ≤ (a1 + a2 + a3) / d ≤ 1.5.]

[0015] [(Y) component] (The (Y) component) is an organohydrogenpolysiloxane represented by the following average composition formula (2) and having two or more hydrosilyl groups in one molecule, and can be used alone or in combination of two or more. The addition reaction amount is an amount such that the amount of hydrosilyl groups is 0.5 to 1.2 moles with respect to 1 mole of the amount of alkenyl groups in the above (X) component, preferably 0.5 to 1.2 moles, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. [Chemical formula] [In the formula, R 2 is the same as above, and R 4 are, independently of each other, a hydrogen atom or a group represented by the above R 2 , and two or more of all R 4 are hydrogen atoms, and e, f, g, h are 0 or positive numbers, provided that 2 ≤ e + f + g + h < 32 is satisfied.]

[0016] In the above formula, R 1 are, independently of each other, alkenyl groups having 2 to 8 carbon atoms. More specifically, vinyl group, allyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group, cyclohexenyl group, octenyl group, etc. can be mentioned. In particular, vinyl group and allyl group are preferred.

[0017] In the above formula, R 2 is, independently of one another, a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Among them, an alkyl group, aryl group, aralkyl group, or fluorine-substituted alkyl group having 1 to 10 carbon atoms is preferable. More specifically, a methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, etc., and a trifluoropropyl group, etc. can be mentioned. In particular, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a trifluoropropyl group is preferable. Further, optionally, a part of R 2 may contain one or more groups selected from a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms.

[0018] In the alkenyl group-containing organosilicon resin represented by the above formula (1), a1, a2, a3, b, c, and d satisfy 0 < a1 ≤ 5, preferably 0 < a1 ≤ 4.5, more preferably 1 ≤ a1 ≤ 4, and even more preferably 1 ≤ a1 ≤ 3. When a1 is greater than 5, the possibility of gelation increases and film-forming properties are also lacking. 0 ≤ a2 ≤ 400, preferably 0 ≤ a2 ≤ 100, more preferably 0 ≤ a2 ≤ 50. 0 ≤ a3 ≤ 400, preferably 0 ≤ a3 ≤ 100, more preferably 0 ≤ a3 ≤ 50. When a3 is greater than 400, the melting point of the resin becomes low and film-forming properties are lacking. 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, and b = 0 and c = 0 are preferable. 0 < d ≤ 1,000, and it is a number that satisfies 0.5 ≤ (a1 + a2 + a3) / d ≤ 1.5, preferably a number that satisfies 0.7 ≤ (a1 + a2 + a3) / d ≤ 1.2. When the value of (a1 + a2 + a3) / d is less than the above lower limit, the degree of crosslinking increases and the molecular weight becomes large, resulting in a gel state. When it exceeds the above upper limit, the molecular weight becomes small and film-forming properties are lacking.

[0019] The alkenyl group-containing organosilicon resin represented by the above formula (1) has Q units (SiO 4 / 2 ), M units (R 2 3SiO 1 / 2 and R 1 R 2 2SiO 1 / 2 ) as essential structures, and D units (R 2 2SiO2 / 2 ), T unit (R 2 SiO 3 / 2 ) has a structure with an arbitrary structure. It may be solid or liquid at 25 °C, but a solid form is preferred from the viewpoint of film-forming properties. For example, MQ resin, MTQ resin, MDQ resin, MDTQ resin can be mentioned. Its weight-average molecular weight is preferably in the range of 1,000 to 30,000, and more preferably in the range of 3,000 to 15,000 from the viewpoints of performance and workability such as filtration. The weight-average molecular weight can be determined as the weight-average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis.

[0020] In the organohydrogenpolysiloxane having two or more hydrosilyl groups in one molecule represented by the above formula (2), R 4 is, independently of each other, a monovalent hydrocarbon group having no aliphatic unsaturated bond with 1 to 30 carbon atoms, and two or more of all R 4 are hydrogen atoms.

[0021] In the above formula (2), e, f, g, h are 0 or positive numbers, and may be selected so as to satisfy 2 ≤ e + f + g + h < 32. Preferably g = 0 and h = 0, more preferably e = 2, 0 ≤ f < 30, g = 0, h = 0, and even more preferably e = 2, 0 ≤ f ≤ 20, g = 0, h = 0. If the number of silicon atoms contained in the (Y) component is 32 or more, the crosslinked organosilicon resin is likely to gel due to incorporating the solvent, and thus it is likely to form a sticky film after the solvent volatilizes. If the number of silicon atoms contained in the (Y) component is less than 32, the crosslinked organosilicon resin is likely to dissolve in the solvent and thus is likely to have a liquid property. Therefore, it is easy to obtain a non-sticky film after the solvent volatilizes.

[0022] The above R 3 is, independently of each other, an organopolysiloxane-containing group, or a group selected from the above R 2 . Examples of the organopolysiloxane-containing group include groups represented by the following general formulas (3) to (6). R 3 3SiO1 / 2 In each of the units, there is one or more R 3 is an organopolysiloxane-containing group. Optionally, a part of R 3 may be a hydroxyl group. [Chemical formula] (In the formula, R 2 is the same as above, n and i are integers satisfying 0 ≤ n ≤ 5, 0 ≤ i ≤ 500, and j1 to j3 are each an integer of 0 or more and 2 or less.)

[0023] m is an integer of 0 ≤ m ≤ 5, preferably 0 ≤ m ≤ 2, i is an integer of 0 ≤ i ≤ 500, preferably 1 ≤ i ≤ 100, and more preferably 1 ≤ i ≤ 50. When i is greater than 500, the melting point of the resin becomes low, resulting in a lack of film-forming properties. j1 to j3 are each an integer of 0 or more and 2 or less.

[0024] In the above formula (1), it is preferable that b = 0 and c = 0. When b and c are 0, the alkenyl group-containing organosilicon resin does not contain a flexible skeleton such as a D unit or a T unit, and is composed only of M units and Q units. By using an alkenyl group-containing organosilicon resin that does not contain a D unit or a T unit as a raw material, the crosslinked organosilicon resin that is an addition reaction product can form a strong film.

[0025] In the above formula (2), it is preferable that g = 0 and h = 0. When g and h are 0, the organohydrogenpolysiloxane does not contain branched components such as T units and Q units, and becomes a linear molecule composed only of M units and D units. By using a linear organohydrogenpolysiloxane as a raw material, the crosslinked organosilicon resin that is an addition reaction product can form a flexible film.

[0026] Also, two or more groups represented by the formula (2) may be present. The group represented by the formula (2) has an effect of imparting flexibility to the organosilicon resin as the chain length increases. Therefore, for example, by including two types of groups represented by the formula (2) having different chain lengths, the film physical properties can be controlled.

[0027] [Physical Properties of Crosslinked Organosilicon Resin] The weight average molecular weight of the crosslinked organosilicon resin is preferably 5,000 to 1,000,000, more preferably 8,000 to 500,000, and even more preferably 10,000 to 500,000. Being within such a range is more preferable in terms of performance and workability such as filtration. The weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene conversion in gel permeation chromatography (GPC) analysis (hereinafter the same).

[0028] The crosslinked organosilicon resin may be in a solid state, a gel state, or a liquid state at 25°C. For example, it can be dissolved in a liquid oil agent and the oil agent can be volatilized to easily form a film. This film is a strong and brittle film before crosslinking, but after crosslinking, its brittleness is improved and a non-sticky and flexible film can be obtained. From the viewpoint of film-forming property, a solid state or a gel state is preferable, and a solid state is more preferable. The film-forming ability can be determined by dropping 1.5 g of a dissolved product diluted to 30% by mass with isododecane or decamethylcyclopentasiloxane onto PTFE (fluororesin) and drying it at 105°C for 3 hours to form a self-supporting film. If a film is not formed, oil will seep out due to cracks in the film, etc., and the oil resistance will be significantly reduced, and the followability with the skin will be low, resulting in an unnatural finish.

[0029] The crosslinked organosilicon resin can be more preferably used as a film-forming agent. The organosilicon resin before crosslinking forms a strong and brittle film, while the crosslinked organosilicon resin after crosslinking has improved brittleness and forms a non-sticky and flexible film. This is because the organosilicon resin before crosslinking forms a strong film, but by crosslinking with flexible chains, flexibility is imparted to the film. Generally, a hard film has low flexibility, and a film with high flexibility tends to be soft, so the strength and flexibility of the film have been considered to be in an antinomic relationship. However, the crosslinked organosilicon resin has the characteristic of excellent followability due to its high flexibility despite forming a strong film.

[0030] In addition, the film formed of the crosslinked organosilicon resin has significantly improved oil resistance against oil agents such as sebum compared to the film formed of the organosilicon resin before crosslinking. Although the oil resistance of organosilicon resins tends to improve as the molecular weight increases, since there is a limit to increasing the molecular weight of organosilicon resins, there is also a limit to the oil resistance. Crosslinking of the organosilicon resin with a crosslinking agent leads to a pseudo-increase in the molecular weight of the organosilicon resin, and thus has the effect of raising that limit point. Therefore, the crosslinked organosilicon resin has oil resistance that cannot be achieved with conventional organosilicon resins.

[0031] The crosslinked organosilicon resin in which f in the above formula (2) is an integer satisfying 0 < f < 30 is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained.

[0032] In addition, when f in the above formula (2) satisfies 0 ≤ f < 30 and two of R 4 are hydrogen atoms, the crosslinked organosilicon resin is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained. When f is 30 or more, or when three or more of R 4 are hydrogen atoms, there is a high possibility of becoming gel-like when the diluting solvent is removed. In this case, although there is film-forming property, it has the feel derived from gel.

[0033] In the above formula (1), when a1 satisfies 0 < a1 ≤ 3, f in the above formula (2) satisfies 0 ≤ f < 20, and two of R 4 are hydrogen atoms, the crosslinked organosilicon resin is solid at 25°C, and a crosslinked organosilicon resin with particularly excellent film-forming properties can be obtained. The obtained film exhibits particularly excellent flex resistance and oil resistance.

[0034] The amount of hydrogen gas generated per mass of the crosslinked organosilicon resin is 1.5 mL or less under standard conditions. If it exceeds 1.5 mL / g, the generation of hydrogen gas over time, or the reaction of remaining hydroxy groups or alkoxy groups with hydrosilyl groups, may increase the likelihood of thickening over time and deteriorate the stability over time. The amount of hydrogen gas generated is preferably 0.01 to 1.2 mL / g, more preferably 0.02 to 1.0 mL / g.

[0035] The amount of hydrogen gas per mass can be calculated from the volume of hydrogen gas generated by the reaction of a hydrosilyl group with a base. For example, the following method can be mentioned, but the calculation method is not limited to this. <Measurement method of hydrogen gas amount> To a mixed solution of 50 g of a crosslinked organosilicon resin diluted to 50% by mass with decamethylcyclopentasiloxane and 10 g of 1-butanol, 10 g of a 20% by mass aqueous sodium hydroxide solution is added dropwise. The amount of hydrogen gas per mass can be obtained by dividing the volume of the generated hydrogen gas by the pure content of the crosslinked organosilicon resin.

[0036] [Manufacturing method] The crosslinked organosilicon resin can be synthesized by various formulations known in the art. For example, crosslinking can be achieved by reacting an organopolysiloxane having hydroxyl groups at both ends with the surface silanol groups of the organosilicon resin. However, since it is difficult to completely control the amount of silanol groups on the surface of the organosilicon resin, there is a problem that it is difficult to accurately control the amount of the organopolysiloxane to be crosslinked. Also, synthesis is possible by an addition reaction of an organosilicon resin having a hydrosilyl group and an organopolysiloxane having alkenyl groups at both ends. However, the hydrosilyl groups in the organosilicon resin have low reactivity, and there is a problem that the remaining hydrosilyl groups react over time, causing an increase in viscosity and the generation of hydrogen gas. Therefore, as a method for producing a crosslinked organosilicon resin crosslinked with silicone, a synthesis method by an addition reaction of an organosilicon resin having an alkenyl group and an organopolysiloxane having hydrosilyl groups at both ends is preferred.

[0037] The method for producing the crosslinked organosilicon resin by the above hydrosilylation reaction will be described in more detail below. In the hydrosilylation reaction step of the alkenyl group-containing organosilicon resin represented by the above average composition formula (1) and the organohydrogenpolysiloxane represented by the above formula (2), the molar ratio of the terminal hydrosilyl group / unsaturated group can be selected from the range of 0.5 to 2.0, preferably 0.5 to 1.2 moles, more preferably 0.8 to 1.2, and even more preferably 0.9 to 1.1. If the above ratio is too large, the residual amount of the hydrosilyl group will increase, and the stability over time may deteriorate.

[0038] This hydrosilylation reaction is preferably carried out in the presence of a platinum catalyst or a rhodium catalyst. For example, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, etc. are preferred. Also, if the amount of the catalyst used is excessive, the sample will be colored, so the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0039] Furthermore, the addition reaction may be carried out in the presence of an organic solvent if necessary. Examples of the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane; short-chain silicone oils such as methyltrimethicone and short-chain dimethicone; aromatic hydrocarbons such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane, decane, isododecane, and cyclohexane; aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Ethanol, 1-propanol, and 2-propanol are particularly preferred from the viewpoint of reactivity.

[0040] The amount of the solvent used is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, of the entire reaction solution (system). When within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

[0041] The crosslinked organosilicon resin can be dissolved in an organic solvent and used as a pre-dissolved product. The organic solvent used during the addition reaction may be used as it is, or may be replaced after the addition reaction, and an organic solvent for replacement can be selected according to the application. The replacement solvent is not particularly limited and can be selected from the aforementioned organic solvents.

[0042] The addition reaction conditions are not particularly limited, but it is preferable to heat at a temperature of 50 to 150°C, more preferably 80 to 120°C, for about 1 to 10 hours under reflux.

[0043] After the addition reaction, it is also possible to include a step of removing the rhodium catalyst or platinum catalyst used with activated carbon. The amount of activated carbon used is preferably 0.001 to 5.0% by mass of the whole system, and more preferably 0.01 to 1.0% by mass. When within the above range, coloring of the sample can be more suppressed.

[0044] After the addition reaction, it is possible to include a step of removing the remaining hydrosilyl groups as necessary. Particularly when used in applications such as cosmetics, the hydrosilyl groups may be deactivated by dehydrogenation reaction over time. Since hydrogen gas is generated, it is a problem from the viewpoint of safety, so it is preferable to include a step of removing the hydrosilyl groups.

[0045] Examples of the step of removing the hydrosilyl groups include a formulation in which a basic catalyst is added to hydrolyze the unreacted hydrosilyl groups, and then an acidic catalyst equivalent to the molar equivalent of the basic catalyst is added for neutralization. Examples of the basic catalyst include strong basic catalysts and weak basic catalysts. Examples of strong basic catalysts include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weak basic catalysts include alkali metal carbonates such as sodium carbonate and calcium carbonate, and alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate. In terms of promoting the dehydrogenation reaction, it is particularly preferable to use a strong basic catalyst, and specifically sodium hydroxide is preferable. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, and carboxylic acids such as oxalic acid, formic acid, acetic acid, propionic acid, benzoic acid, citric acid, and trifluoroacetic acid.

[0046] In general, it is preferable to use an acid or a base in combination with water and heat at a temperature below the boiling point of water rather than using the acid or the base alone. By this step, a hydrosilyl group (SiH group) is converted into a hydroxysilyl group (SiOH group). However, when a crosslinked organosilicon resin is treated with a base catalyst, the physical properties change due to the reaction of silanol groups or alkoxy groups in the organosilicon resin, so it is not preferable to remove the hydrosilyl group by this method.

[0047] The content of component (B) in the present invention is not particularly limited, but is preferably 0.5 to 18%, more preferably 0.75 to 15%, and even more preferably 1 to 10% based on the total amount of the water-in-oil type emulsified cosmetic. Within this range, it is preferable because the makeup retention, natural glossiness, and lack of color unevenness are more excellent.

[0048] In the present invention, the total content mass of components (A) and (B) is 1 to 20% based on the total amount of the water-in-oil type emulsified cosmetic, preferably 2 to 15%, more preferably 2.5 to 10%, and even more preferably 3 to 7%. Within this range, it is more preferable because the smoothness of the coating film, natural glossiness, etc. are more excellent.

[0049] Component (C): Branched volatile silicone oil Component (C) in the present invention is a branched volatile silicone oil. In the present invention, "volatile" means that the boiling point at 1 atm is 250°C or lower. Component (C) in the present invention is not particularly limited as long as it is usually used in cosmetics, and any of them can be used. For example, methyltrimethicone, ethyltrisiloxane, etc. can be mentioned, and these can be used alone or in combination of two. Among these, methyltrimethicone is preferable from the viewpoint of makeup retention and the like.

[0050] The content of component (C) in the present invention is 5 to 30% based on the total amount of the water-in-oil type emulsified cosmetic, preferably 7 to 25%, and more preferably 10 to 20%. Within this range, it is preferable because the lack of color unevenness, smoothness of the coating film, and natural glossiness are excellent.

[0051] In the present invention, the content mass ratio of component (C) to the total amount of the volatile oil, (C) / (volatile oil), has a lower limit of 0.3 or more, preferably 0.35 or more, and more preferably 0.4 or more. If it is within this range, it is preferable because it is excellent in natural gloss, lack of color unevenness, and smoothness of the coating film.

[0052] As the volatile oil, in addition to component (C), for example, hydrocarbons such as light fluid isoparaffin, isododecane, and isohexadecane; cyclic silicones such as decamethylcyclopentasiloxane, octamethylcyclotetrasiloxane, and dodecamethylcyclohexasiloxane; linear silicones such as dimethylpolysiloxane and decamethyltetrasiloxane can be mentioned.

[0053] The present invention preferably further contains component (D) alumina. Component (D) in the present invention is not particularly limited as long as it is usually used in cosmetics, and any one can be used. By containing component (D), it is preferable because it is excellent in lack of color unevenness, smoothness of the coating film, and natural gloss.

[0054] The content of component (D) in the present invention is not particularly limited, but is 0.1 to 15%, preferably 0.5 to 10%, and more preferably 1 to 5% with respect to the total amount of the water-in-oil type emulsified cosmetic. If it is within this range, it is preferable because it is excellent in lack of color unevenness, smoothness of the coating film, and natural gloss.

[0055] In addition to the above components (A) to (D), the water-in-oil type emulsified cosmetic of the present invention can be appropriately contained within a range that does not impair the effects of the present invention. For example, it can contain oily components other than component (C), water-soluble polymers, ultraviolet absorbers, antioxidants, antibacterial agents, preservatives, moisturizers, pH adjusters, cooling agents, powders other than component (D), vitamins, beauty components, fragrances, etc.

[0056] The water-in-oil type emulsion cosmetic of the present invention can be produced according to a known production method. Further, it can have various properties such as a gel form, a cream form, a liquid form, etc. Further, it can be a makeup cosmetic such as a base, a foundation, a BB cream, a lotion, a sunscreen cosmetic, etc., preferably a makeup cosmetic such as a base, a foundation, a BB cream, etc., and more preferably a foundation.

[0057] Further, the present invention can have the following constitution. <1> The following components (A) to (C); (A) Acrylic-silicone graft copolymer (B) R3SiO 1 / 2 (R independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms) M unit represented by, and SiO 4 / 2 Organic silicon resin containing Q unit represented by (C) Branched volatile silicone oil 5 to 30% by mass Containing The total content mass of the component (A) and the component (B) is 1 to 20% by mass, A water-in-oil type emulsion cosmetic in which the content mass ratio (C) / (volatile oil agent) of the component (C) to the total amount of the volatile oil agent is 0.3 or more. <2> The water-in-oil type emulsion cosmetic according to <1>, wherein the component (B) is a crosslinked organic silicon resin which is an addition reaction product of the following component (X) and component (Y), and the amount of hydrogen gas generated per mass of this crosslinked organic silicon resin is 1.5 mL / g or less under standard conditions. (X) component; An alkenyl group-containing organic silicon resin represented by the following formula (1) and having one or more alkenyl groups in one molecule

Chemical formula

Chemical formula

Examples

[0058] Hereinafter, examples will be given to specifically describe the present invention, but the present invention is not limited to these examples and the like. Also, unless otherwise specified, the content is shown as mass% with respect to the composition containing the component.

[0059] [Production Example 1] Method for producing a 30% solution of crosslinked organosilicon resin / decamethylcyclopentasiloxane 1,000 g of a 50% decamethylcyclopentasiloxane solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 7,430, vinyl value: 0.229 mmol / g) represented by the following average composition formula (E1), 700 g of decamethylcyclopentasiloxane, 126.9 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E2) (hydrogen gas generation amount: 20.3 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid were charged into a reactor and reacted by heating at 120°C for 8 hours. Then, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin. Further, the obtained decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was heated to 120 to 130°C under reduced pressure to remove decamethylcyclopentasiloxane, and the resulting product was a solid powder (weight average molecular weight 221,000). The reaction rate of the alkenyl group was 92%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 0.8 mL / g. Formula (E1):

Chemical formula

Chemical formula

[0060] [Production Example 2] Method for producing a 30% solution of crosslinked organosilicon resin / decamethylcyclopentasiloxane 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight: 8,050, vinyl value: 0.224 mmol / g) represented by the following average compositional formula (E3) in decamethylcyclopentasiloxane, 700 g of decamethylcyclopentasiloxane, 53.8 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E4) (hydrogen gas generation amount: 51.3 mL / g, hydrosilyl group / vinyl group = 1.1), and 0.6 g of a 0.5% solution of chloroplatinic acid in 2-propanol were charged into a reactor and reacted by heating at 110°C for 5 hours. Thereafter, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a solution of a crosslinked organosilicon resin in decamethylcyclopentasiloxane.

[0061] Further, the solution of the obtained crosslinked organosilicon resin in decamethylcyclopentasiloxane was heated to 120 to 130°C under reduced pressure to remove decamethylcyclopentasiloxane, and the resulting product was a solid powder (weight average molecular weight: 154,000). The reaction rate of the alkenyl group was 93%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 1.0 mL / g. Formula (E3): [Chemical formula] Formula (E4): [Chemical formula]

[0062] [Production Example 3] Production method of crosslinked organosilicon resin / 30% solution of decamethylcyclopentasiloxane 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 14,860, vinyl value: 0.323 mmol / g) represented by the following average compositional formula (E5) in decamethylcyclopentasiloxane, 700 g of decamethylcyclopentasiloxane, 160.0 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E6) (hydrogen gas generation amount: 22.6 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% solution of chloroplatinic acid in 2-propanol were charged into a reactor and reacted by heating at 110 °C for 3 hours. Thereafter, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a solution of a crosslinked organosilicon resin in decamethylcyclopentasiloxane.

[0063] Further, the product obtained by heating the solution of the crosslinked organosilicon resin in decamethylcyclopentasiloxane at 120 to 130 °C under reduced pressure to remove decamethylcyclopentasiloxane was a solid powder (weight average molecular weight 168,500). The reaction rate of the alkenyl group was 92%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 0.5 mL / g. Formula (E5): [Chemical formula] Formula (E6): [Chemical formula]

[0064] [Production Example 4] Method for producing a 30% solution of a crosslinked organosilicon resin in decamethylcyclopentasiloxane 1,000 g of a 50% solution of a powdery alkenyl group-containing organosilicon resin (weight average molecular weight 11,730, vinyl value: 0.307 mmol / g) represented by the following average compositional formula (E7) in decamethylcyclopentasiloxane, 700 g of decamethylcyclopentasiloxane, 78.5 g of an organopolysiloxane having hydrosilyl groups at both ends represented by the following formula (E8) (hydrogen gas generation amount: 43.8 mL / g, hydrosilyl group / vinyl group = 1.0), and 0.6 g of a 0.5% solution of chloroplatinic acid in 2-propanol were charged into a reactor and reacted by heating at 120 °C for 5 hours. Then, the solvent was distilled off by heating under reduced pressure. After adjusting by adding decamethylcyclopentasiloxane so that the concentration became 30%, filtration was performed to obtain a solution of a crosslinked organosilicon resin in decamethylcyclopentasiloxane.

[0065] Further, the solution of the crosslinked organosilicon resin in decamethylcyclopentasiloxane obtained was heated to 120 to 130 °C under reduced pressure to remove decamethylcyclopentasiloxane, and the resulting product was a solid powder (weight average molecular weight 96,500). The reaction rate of the alkenyl group was 97%, and the amount of hydrogen gas generated from the remaining hydrosilyl groups was 0.9 mL / g. Formula (E7):

Chemical formula

Chemical formula

[0066] Examples 1 to 15 and Comparative Examples 1 to 5: Water-in-oil emulsion cosmetics (foundation) A makeup base having the composition shown in Tables 1 and 2 was produced by the following production method, and evaluation and determination were performed on i: color unevenness, ii: smoothness of the coating film, iii: natural gloss, and iv: makeup retention by the following methods. The results are shown in Tables 1 and 2 together.

[0067]

Table 1

[0068]

Table 2

[0069] (Manufacturing method) A: Add Components (13) to (16) and part of Components (12) and (18), and uniformly mix and disperse them using a roll mill. B: Uniformly mix and disperse Component (19) and part of Components (8) to (10) and (12) using a roll mill. C: Add B to A, Components (1) to (7), (11) and (17), and the rest of Components (8) to (10), (12), (18), and uniformly mix and disperse them. D: Add Components (20) to (22) to C, and emulsify at 2000 rpm for 5 minutes at room temperature using a disperser. E: Fill D into a container to obtain a water-in-oil emulsion cosmetic (foundation).

[0070] (Evaluation method) Ten professional cosmetic evaluation panelists who had received sensory evaluation training and were able to evaluate according to certain criteria were selected from women in their 20s to 40s. Each panelist applied 0.5 g of each sample to their forearm by hand, and for each sample, evaluated and scored "a. Absence of color unevenness", "b. Smoothness of the coating film", "c. Natural glossiness", and "d. Makeup retention" in the following absolute evaluation in four levels. From the total scores of all panelists for each sample, the average value was calculated and judged according to the following four-level judgment criteria.

[0071] (Evaluation items) a. Absence of color unevenness: Whether there is color unevenness in the coating film b. Smoothness of the coating film: Whether the coating film is smooth c. Natural glossiness: Whether the gloss of the coating film is natural (the glossiness is not too low or too high) d. Makeup retention: Whether makeup breakdown has occurred 8 hours after applying the sample

[0072] <Absolute evaluation criteria> (Score): (Evaluation) 4 points: Very good 3 points: Good 2 points: Bad 1 point: Very bad <Four - level judgment criteria> (Judgment): (Average score) A: Exceeds 3.5 points B: Exceeds 3 points and is 3.5 points or less C: Exceeds 2 points and is 3 points or less D: 2 points or less

[0073] As is clear from the results in Tables 1 and 2, the water - in - oil emulsified cosmetics of Examples 1 to 15 were excellent in terms of color unevenness, smoothness of the coating film, natural gloss, and makeup retention. On the other hand, Comparative Example 1 that did not contain component (A) did not obtain satisfactory quality in terms of natural gloss and makeup retention. Also, Comparative Example 2 that contained polymethylsilsesquioxane instead of component (B) did not obtain satisfactory quality in terms of color unevenness, smoothness of the coating film, and makeup retention. Further, Comparative Example 3 in which the total content mass of component (A) and component (B) exceeded 20% did not obtain satisfactory quality in terms of color unevenness, smoothness of the coating film, and natural gloss. Comparative Example 4 that did not contain component (C) did not obtain satisfactory quality in terms of color unevenness, smoothness of the coating film, and natural gloss.

[0074] Example 16: Water - in - oil emulsified cosmetic (foundation) (Components) (mass%) 1. Purified water Remaining amount 2. Ethanol 10 3. 1,3 - Butylene glycol 1 4. Glycerin 1 5. Glycosyl trehalose 0.1 6. EDTA - 2Na 0.01 7. Dipropylene glycol 5 8. Triethanolamine 0.1 9. Sodium chloride 0.5 10. Hydrophobically treated titanium oxide 10 11. Hydrophobically treated fine - particle titanium oxide 5 12. Hydrophobically treated red iron oxide 1 13. Hydrophobically Treated Yellow Iron Oxide 4 14. Hydrophobically Treated Black Iron Oxide 0.5 15. Mica 1 16. Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone 0.5 17. PEG-9 Polydimethylsiloxyethyl Dimethicone 5 18. Decamethylcyclopentasiloxane 5 19. Methyltrimethicone 15 20. Neopentyl Glycol Diethylhexanoate 2 21. Dimethicone (10CS) 5 22. Squalane 2 23. Ceramide NG 0.1 24. Dimethyldistearylammonium Hectorite 0.6 25. Benzyldimethylstearylammonium Hectorite 0.5 26. Dextrin Palmitate 0.5 27. (Acrylates / Dimethicone) Copolymer 2 28. Crosslinked Organosilicon Resin Solid Content of Production Example 1 2

[0075] (Production Method) A. Mix and dissolve Components 1 to 9 uniformly. B. Disperse Components 10 to 19 uniformly with a roll mill. C. Add 20 to 28 to B and disperse uniformly at 60°C. D. Add A to C and emulsify at room temperature to obtain an oil-in-water type foundation.

[0076] The oil-in-water type emulsified cosmetic (foundation) of Example 16 was excellent in color uniformity, smoothness of the coating film, natural gloss, and makeup retention.

Claims

1. The following components (A) to (C); (A) Acrylic-silicone graft copolymer (B) R ３ SiO １／２ (R independently represents a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms), an M unit represented by, and SiO ４／２ An organosilicon resin containing a Q unit represented by (C) Branched volatile silicone oil: 5 to 30% by mass Containing The total content of the above components (A) and (B) is 1 to 20% by mass, An oil-in-water type emulsified cosmetic in which the content mass ratio of component (C) to the total amount of the volatile oil agent (C) / (volatile oil agent) is 0.3 or more.

2. The oil-in-water type emulsified cosmetic according to Claim 1, wherein the component (B) is a crosslinked organosilicon resin which is an addition reaction product of the following component (X) and component (Y), and the amount of hydrogen gas generated per mass from this crosslinked organosilicon resin is 1.5 mL / g or less under standard conditions. (X) component; An alkenyl group-containing organosilicon resin represented by the following formula (1) and having one or more alkenyl groups in one molecule 【Chemical 1】 [In the formula, R １ is an alkenyl group having 2 to 8 carbon atoms, R ２ are each independently a group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. ３ are each independently an organopolysiloxane-containing group, and the R ２ Each R ３ ３ SiO １／２ R in units ３ At least one of the above is an organopolysiloxane-containing group. a1, a2, a3, b, c, and d are numbers that satisfy 0<a1≦5, 0<a2≦400, 0≦a3≦400, 0≦b≦320, 0≦c≦320, and 0<d≦1,000, and 0.5≦(a1+a2+a3) / d≦1.

5. (Y) component; An organohydropolysiloxane represented by the following formula (2) and having two or more hydrosilyl groups in one molecule 【Chemical Formula 2】 [wherein, R ２ is the same as described above, and R ４ are, independently of one another, a hydrogen atom or a group represented by the above R ２ , and two or more of all R ４ are hydrogen atoms, and e, f, g, and h are 0 or positive numbers, provided that 2 ≦ e + f + g + h < 32 is satisfied.]

3. The oil-in-water type emulsified cosmetic according to Claim 1 or 2, further containing component (D) alumina.

4. The oil-in-water type emulsified cosmetic according to Claim 1 or 2, wherein the content of the component (B) is 1 to 10% by mass.

5. The oil-in-water type emulsified cosmetic according to Claim 1 or 2, wherein the content mass ratio of component (C) to the total amount of the volatile oil agent (C) / (volatile oil agent) is 0.4 or more.

6. The oil-in-water type emulsified cosmetic according to Claim 1 or 2, wherein the oil-in-water type emulsified cosmetic is a makeup cosmetic.

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