Water-in-oil emulsion cosmetics

Abstract

The purpose is to provide a water-in-oil emulsion cosmetic that has excellent dispersibility of solidified sebum powder in a liquid phase and that will not come off easily even in a hot, humid environment, such as when wearing a mask. The water-in-oil emulsion cosmetic contains the following components (A) to (D): (A) at least one selected from the group consisting of fine metal oxide particles, hydroxyapatite, and composite powders containing metal oxide and hydroxyapatite, (B) at least one selected from the group consisting of amino acids and salts thereof, (C) a crosslinked organic silicon resin represented by average composition formula (1), and (D) a spherical powder having an average particle size of 5-50 μm, the content of the component (A) in the cosmetic being 3 mass% or more.

Description

[Technical Field]

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

[0002] Emulsion cosmetics are a commonly used formulation for cosmetics, and water-in-oil emulsion cosmetics in particular are widely used in foundations, primers, sunscreens, and the like because of the light spreadability of the oily outer phase and the long-lasting makeup properties.

[0003] For cosmetics, maintaining the cosmetic film formed over time (cosmetic wear) is a very important quality. A decrease in cosmetic wear, or in other words, makeup breakdown, occurs when external factors such as sweat, sebum, or external water or irritation (e.g., friction) cause the applied cosmetic to lose its affinity with the skin, or its affinity to the skin weakens, causing the cosmetic to float or run off the skin.

[0004] Various approaches have been taken to prevent makeup from coming off. For example, Patent Document 1 proposes a composite powder of hydroxyapatite and zinc oxide, which has sebum-adsorbing properties. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-315467 Summary of the Invention

[0006] In recent years, an increasing number of people are wearing masks on a daily basis to prevent infection and the spread of infectious diseases such as COVID-19, and many consumers are concerned about makeup transferring to the mask.When wearing a mask, the inside of the mask is in a high-temperature, high-humidity environment, making makeup more likely to come off, which in turn makes it easier for makeup to adhere to the mask.

[0007] To prevent such makeup from coming off, it is necessary to incorporate a certain amount of fine particle metal oxide or hydroxyapatite, which can be used as a powder with sebum adsorption properties (hereinafter also referred to as sebum-solidifying powder), into the water-in-oil cosmetic. If the amount of sebum-solidifying powder incorporated is increased, the powder becomes difficult to disperse in the external phase of the water-in-oil emulsion cosmetic, or, in the case of a multi-layered cosmetic in which the powder has settled, the settled powder becomes difficult to redisperse in the external phase. If the dispersibility or redispersibility of the sebum-solidifying powder decreases, the cosmetic becomes non-uniform, and the expected cosmetic effect may not be achieved.

[0008] Therefore, an object of the present invention is to provide a water-in-oil emulsion cosmetic that has excellent powder dispersibility in the external phase and is resistant to makeup smearing even in a high-temperature, high-humidity environment, such as when wearing a mask.

[0009] Another object of the present invention is to provide a water-in-oil emulsion cosmetic that has a long-lasting pore-covering effect and does not or hardly leaves a dry feeling even after application of the cosmetic.

[0010] The present invention provides a water-in-oil emulsion cosmetic according to one aspect of the present invention that solves the above-mentioned problems, as follows. 1. The following ingredients (A) to (D): (A) At least one selected from the group consisting of fine particle metal oxides, hydroxyapatite, and composite powders containing metal oxides and hydroxyapatite (B) at least one selected from the group consisting of amino acids and amino acid salts (C) a crosslinked organosilicon resin represented by the following average composition formula (1):

[0011] [ka]

[0012] [In the formula, R 1are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having no aliphatic unsaturated bond and having 1 to 30 carbon atoms, R 2 are, independently of each other, polyoxyalkylene-containing groups, polyglycerin-containing groups, or groups selected from the options of R 1 and at least one R in each R 2 3SiO 1 / 2 unit is a polyoxyalkylene-containing group or a polyglycerin-containing group, R 2 are, independently of each other, organopolysiloxane-containing groups, or groups selected from the options of R 3 and at least one R in each R 1 unit is an organopolysiloxane-containing group, X is a divalent group represented by the following general formula (2), and in this case, (R 3 3SiO 1 / 2 )(X 3 ) 1 3-p (X 1 / 2 ) p SiO 1 / 2 ) may be a plurality of different structural units, and optionally, part of R 2 , R 3 , and X may be a hydroxyl group,

[0013]

Chemical formula

[0014] (In the formula, R 4 are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having no aliphatic unsaturated bond and having 1 to 30 carbon atoms, e is 0 ≦ e ≦ 500, and k is an integer of 0 ≦ k ≦ 5) a1, a2, a3, a4, b, c, and d are numbers satisfying 0 < a1 ≦ 400, 0 ≦ a2 ≦ 200, 0 ≦ a3 ≦ 400, 0 < a4 ≦ 10, 0 ≦ b ≦ 320, 0 ≦ c ≦ 320, 0 < d ≦ 1,000, 0.5 ≦ (a1 + a2 + a3 + a4) / d ≦ 1.5, and p is 1) (D) Spherical powder having an average particle diameter of 5 to 50 μm is contained, An oil-in-water type emulsified cosmetic in which the content of the component (A) in the cosmetic is 3% by mass or more.

[0015] 2. The water-in-oil emulsion cosmetic according to 1., wherein component (A) comprises at least one selected from the group consisting of zinc oxide, hydroxyapatite, and composite powders containing a metal oxide and hydroxyapatite.

[0016] 3. The water-in-oil emulsion cosmetic according to 1. or 2., wherein the amino acid of component (B) is at least one selected from the group consisting of amino acids (salts) having a hydroxyl group and amino acids (salts) having an amide bond.

[0017] 4. The water-in-oil emulsion cosmetic according to any one of 1. to 3., wherein the weight-average molecular weight of component (C) is 1,000 to 1,000,000.

[0018] 5. The water-in-oil emulsion cosmetic according to any one of 1. to 4., wherein component (D) is at least one powder selected from the group consisting of silicone resin powder, urethane, nylon, cellulose acetate, cellulose, starch, polylactic acid, acrylic resin powder, and silica.

[0019] 6. The water-in-oil emulsion cosmetic according to any one of 1. to 5., wherein the content of component (B) in the cosmetic is 0.1 to 1% by mass.

[0020] 7. The water-in-oil emulsion cosmetic according to any one of 1. to 6., wherein the content of component (C) in the cosmetic is 0.1 to 20% by mass.

[0021] 8. The water-in-oil emulsion cosmetic according to any one of 1. to 7., wherein the content of the component (D) in the cosmetic is 0.1 to 20% by mass.

[0022] 9. The water-in-oil emulsion cosmetic according to any one of 1. to 8., having a viscosity of 10,000 mPa·s or less at 30°C. DETAILED DESCRIPTION OF THE INVENTION

[0023] 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 modified within the scope of the present invention. In this specification, percentages are expressed by mass unless otherwise specified. In this specification, when a numerical range is expressed using "to" (a number of characters), the range includes both ends. In addition, the "average particle size" in this specification refers to the number-based standard value (D50) obtained by observing the surface condition using a scanning electron microscope (JEOL Ltd., JSM-7800prime) and measuring 1,000 particles using an image analyzer (Luzex AP, Nireco Corporation), unless otherwise specified. In the case of asymmetric shapes, the average particle size in this specification is the median diameter D50 obtained from the distribution of the largest particle diameter. In this specification, the range "X to Y" means "X or more and Y or less." In addition, unless otherwise specified, operations and measurements of physical properties are performed at room temperature (20 to 25°C) and a relative humidity of 45 to 55% RH.

[0024] One embodiment of the present invention comprises: The following components (A) to (D): (A) At least one selected from the group consisting of fine particle metal oxides, hydroxyapatite, and composite powders containing metal oxides and hydroxyapatite (B) at least one selected from the group consisting of amino acids and amino acid salts (C) a crosslinked organosilicon resin represented by the following average composition formula (1):

[0025] [ka]

[0026] [In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bond, and R 2 are each independently a polyoxyalkylene-containing group, a polyglycerin-containing group, or R 1 and each R 2 3SiO 1 / 2At least one R in the unit 2 is a polyoxyalkylene-containing group or a polyglycerin-containing group, and R 3 is, independently of each other, an organopolysiloxane-containing group, or a group selected from the options of R 1 , and each R 3 3SiO 1 / 2 At least one R in the unit 3 is an organopolysiloxane-containing group, X is a divalent group represented by the following general formula (2), and in this case, (R 1 3-p (X 1 / 2 ) p SiO 1 / 2 ) may be a plurality of different structural units, and optionally, part of R 2 , R 3 , and X may be a hydroxyl group,

[0027]

Chemical formula

[0028] (In the formula, R 4 is, independently of each other, a monovalent hydrocarbon group having no aliphatic unsaturated bond with 1 to 30 carbon atoms, which may be substituted or unsubstituted, e is 0 ≦ e ≦ 500, and k is an integer of 0 ≦ k ≦ 5) a1, a2, a3, a4, b, c, and d are numbers satisfying 0 < a1 ≦ 400, 0 ≦ a2 ≦ 200, 0 ≦ a3 ≦ 400, 0 < a4 ≦ 10, 0 ≦ b ≦ 320, 0 ≦ c ≦ 320, 0 < d ≦ 1,000, and 0.5 ≦ (a1 + a2 + a3 + a4) / d ≦ 1.5, and p is 1) (D) Spherical powder with an average particle diameter of 5 to 50 μm contains An oil-in-water type emulsified cosmetic in which the content of the component (A) in the cosmetic is 3% by mass or more.

[0029] The water-in-oil emulsion cosmetic of this embodiment has excellent dispersibility of powder in the external phase, and is resistant to makeup smearing even in high-temperature, high-humidity environments such as when wearing a mask, resulting in minimal transfer of the cosmetic to the mask. Furthermore, the water-in-oil emulsion cosmetic of this embodiment has a sustained pore-covering effect, and does not or is unlikely to cause a dry feeling even after application of the cosmetic.

[0030] By incorporating components (B), (C), and (D), in water-in-oil cosmetics containing a certain amount of component (A), such as 3% by mass or more, the (re)dispersibility of the powder in the external phase is improved, and the effect of preventing makeup from coming off in a high-temperature, high-humidity environment is exerted. On the other hand, if any one of components (B), (C), and (D) is missing, the dispersibility of the powder and / or the makeup staying power in a high-temperature, high-humidity environment is significantly reduced. Although the detailed mechanism for this effect is unknown, it is believed that the electrostatic interaction of the amino and carboxyl groups in component (B) causes component (B) to adsorb to the surface of powder component (A), suppressing aggregation between the powder particles, and that the high molecular weight and bulky structure unique to component (C) effectively prevent the sedimentation of component (A) adsorbed by component (B). Furthermore, even if partial sedimentation does occur, the incorporation of component (D), a spherical powder with an average particle size of 5 to 50 μm, prevents dense sedimentation of component (A), improving the (re)dispersibility of the powder in the external phase. Furthermore, after forming a cosmetic film in a well-dispersed state, component (C) is thought to maintain a densely oriented state of the uniformly dispersed component (A) with sebum adsorption ability and component (D) with pore-covering effect. Furthermore, by adsorbing component (B) to component (A), the moisture-retaining ability of the amino acid (salt) makes it difficult to feel the squeaky or dry feeling caused by component (A) for a long time, and even in harsh environments such as high temperature and humidity, the evenly distributed component (A) effectively adsorbs sebum secreted from the inside, and even under high humidity, component (C) does not mix with water, maintaining an evenly distributed cosmetic film, which is thought to result in significant suppression of cosmetic adhesion to the mask. Note that the above mechanism does not in any way restrict the technical scope of the present invention.

[0031] Each component will be described below.

[0032] <Component (A): At least one selected from the group consisting of fine particle metal oxide, hydroxyapatite, and composite powder containing metal oxide and hydroxyapatite> Component (A) specifically adsorbs, in particular, fatty acids contained in sebum secreted from the skin and turns them into a gel.

[0033] From the viewpoints of powder dispersibility, difficulty in adhering to the mask, and lack of dryness, component (A) preferably contains at least one selected from the group consisting of fine particle zinc oxide, hydroxyapatite, and composite powders containing a metal oxide and hydroxyapatite. From the viewpoint of the effects of the present invention, the content of at least one selected from the group consisting of fine particle zinc oxide, hydroxyapatite, and composite powders containing a metal oxide and hydroxyapatite contained in component (A) is preferably 50% by mass or more (upper limit 100% by mass), but is not particularly limited.

[0034] The metal oxide is not particularly limited as long as it is a metal oxide used in cosmetics, and any metal oxide can be used regardless of its particle shape (spherical, acicular, plate-like, irregular, etc.) or particle structure (porous, non-porous, etc.). Examples of metal oxides include zinc oxide, titanium oxide, cerium oxide, and iron oxide, and these can be used alone or in combination of two or more. Among these, from the viewpoint of improving the function of makeup staying power by solidifying sebum (the effect of suppressing makeup from coming off), it is preferable that component (A) contains at least one selected from the group consisting of zinc oxide and titanium oxide. Furthermore, zinc oxide is more preferable as the metal oxide.

[0035] Metal oxides and hydroxyapatite (described below) may be surface-treated. Examples of surface treatments include fluorine compound treatment, silica treatment, hydrous silica treatment, alumina treatment, aluminum hydroxide treatment, silicone treatment (e.g., methicone treatment, dimethicone (dimethylpolysiloxane) treatment, hydrogen dimethicone treatment), silicone resin treatment, pendant treatment, silane coupling agent treatment (e.g., trimethoxyhexylsilane treatment, triethoxycaprylylsilane treatment, trimethoxyoctylsilane treatment, triethoxyoctylsilane treatment), titanium coupling agent treatment, silane treatment, oil treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, and metal oxide treatment. These surface treatments may be used alone or in combination of two or more. The total amount of surface treatment agent is preferably 0.1 to 30% by mass of the untreated powder. When the metal oxide is surface-treated, the surface-treated metal oxide is counted as the content of component (A), excluding the surface treatment with component (B).

[0036] Component (A) may also be surface-treated with component (B). Specific examples include fine particle metal oxides surface-treated with component (B) and hydroxyapatite surface-treated with component (B). In this case, the content of the amino acid (salt) serving as the surface treatment agent is defined as the content of component (B), and the content of the metal oxide (or metal oxide surface-treated with another surface treatment agent) excluding the amount of the amino acid (salt) serving as the surface treatment agent is defined as the content of component (A). Furthermore, component (A) does not necessarily have to be surface-treated with component (B).

[0037] The surface treatment can be carried out by a conventionally known method. For example, a surface treatment agent and powder particles to be treated are added to a solvent, and the mixture is stirred using a ball mill, a bead mill, a mixer, a pulverizer, or the like. The mixture is then dried, washed with water, and filtered repeatedly as necessary to remove impurities, followed by drying and pulverization, thereby obtaining the desired surface-treated powder. Furthermore, several types of compounds serving as surface treatment agents can be used simultaneously for surface treatment, or one compound can be used for surface treatment first, followed by another compound for surface treatment.

[0038] The term "microparticle metal oxide" refers to particles having a particle diameter of 0.2 μm or less. To prevent makeup from smearing, the microparticle metal oxide is preferably a metal oxide having an average particle diameter of 0.01 to 0.15 μm, more preferably a metal oxide having an average particle diameter of 0.01 to 0.1 μm, and even more preferably a metal oxide having an average particle diameter of 0.01 to 0.05 μm. Here, the average particle diameter of the metal oxide particles refers to the average particle diameter of the surface-treated metal oxide particles, if any.

[0039] Commercially available fine particle metal oxide products include, for example, FINEX-50 (manufactured by Sakai Chemical Industry Co., Ltd.), XZ-100F (manufactured by Sakai Chemical Industry Co., Ltd.: average particle size 0.1 μm), ZnO-350 (manufactured by Sumitomo Osaka Cement Co., Ltd.), fine particle zinc oxide MZ-500 (manufactured by Teika Co., Ltd.), MZY-505S (manufactured by Teika Co., Ltd.), MZY-505M (manufactured by Teika Co., Ltd.), MZ-500FT (manufactured by Teika Co., Ltd.), and MZY-303 (manufactured by Teika Corporation), MZY-303S (manufactured by Teika Corporation: average particle size 0.035 μm), and other zinc oxides; MT-05 (manufactured by Teika Corporation), MT-100SA (manufactured by Teika Corporation), MTY-100SAS (manufactured by Teika Corporation), SMT-100SAS (manufactured by Teika Corporation), MT-500B (manufactured by Teika Corporation), SMT-500SAS (manufactured by Teika Corporation), SMT-500SAM (manufactured by Teika Corporation), MICRO TITANIUM DIOXIDE MT-500SA (manufactured by Teika Corporation), and other titanium oxides; and these can be used alone or in combination of two or more.

[0040] Hydroxyapatite is defined as calcium phosphate with an apatite structure and is composed of Ca5(PO4)3(OH), Ca10(PO4)6(OH)2, Ca4(PO4)2O, Ca 10 (PO4)6F2, Ca3(PO4)2.

[0041] The shape of the hydroxyapatite is not particularly limited, but may be, for example, a plate shape, with an aspect ratio of, for example, 2 to 200. The average particle size of the hydroxyapatite is, for example, 1 to 100 μm, or 10 to 80 μm.

[0042] An example of a composite powder containing hydroxyapatite and a metal oxide is a composite powder in which the surface of a base powder is coated with hydroxyapatite and zinc oxide.

[0043] A composite powder (hereinafter simply referred to as composite powder) in which the surface of a base powder is coated with hydroxyapatite and zinc oxide will be described below.

[0044] The order of coating may be either simultaneous or multi-layer, and any form may be used as long as both are coated on the surface of the base powder.

[0045] From the viewpoint of (re)dispersibility in the external phase, the base powder is preferably a flaky powder. The average particle size of the base powder is preferably 0.1 to 50 μm, more preferably 0.3 to 30 μm, particularly preferably 1 to 20 μm, and most preferably 2 to 15 μm. The aspect ratio (average plate ratio) of the base flaky powder is preferably 50 or more. Such a flaky powder may be a flaky powder or a powder obtained by processing granular or irregularly shaped powder into flaky form. Specific examples of the flaky powder include talc, kaolin, sericite, mica, synthetic mica (synthetic phlogopite, fluorine tetrasilicic mica, etc.), magnesium carbonate, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, silicic acid anhydride, boron nitride, magnesium oxide, alumina, titanium oxide, barium sulfate, carmine, bentonite, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated titanium mica, organic pigment-coated titanium mica, bismuth oxychloride, glass powder, cellulose, etc. These may be used alone or in combination of two or more. Among these flaky powders, at least one selected from the group consisting of talc, sericite, mica, synthetic mica (synthetic phlogopite, tetrasilicic fluoride mica, etc.), boron nitride, barium sulfate, silica, cellulose, titanium oxide-coated mica, iron oxide-coated mica, iron oxide-coated mica titanium, and organic pigment-coated mica titanium is more preferred, as it has high (re)dispersibility of the powder in the external phase, and at least one selected from the group consisting of mica and sericite is even more preferred.

[0046] The zinc oxide in the composite powder should be zinc oxide on the surface of the flaky powder. The average particle size of the zinc oxide is preferably 0.01 to 1 μm, from the viewpoint of effectively gelling fatty acids contained in sebum, which are the primary cause of greasiness. Hydroxyapatite is similar to the hydroxyapatite described above. The shape of the hydroxyapatite used in the composite powder is preferably needle-like, and in this case, the average major axis is preferably about 0.1 to 10 μm, more preferably about 0.1 to 5 μm, and even more preferably about 0.1 to 2 μm, and the average minor axis is preferably about 0.01 to 0.06 μm, more preferably about 0.01 to 0.04 μm, and even more preferably about 0.02 to 0.04 μm. The coating amounts of hydroxyapatite and zinc oxide are not particularly limited, but from the viewpoint of good usability and rapid adsorption and gelation of sebum-derived fatty acids, the composition ratio of the flaky powder, hydroxyapatite, and zinc oxide (mass, total of flaky powder, hydroxyapatite, and zinc oxide = 100) is preferably flaky powder:hydroxyapatite:zinc oxide = 20-85:5-30:10-50, more preferably 50-80:5-20:15-30, and even more preferably 60-75:10-15:15-25. Furthermore, the mass ratio of hydroxyapatite to zinc oxide in the composite powder is preferably hydroxyapatite < zinc oxide, and the total mass percent of hydroxyapatite and zinc oxide in the composite powder is preferably 15-80 mass%, more preferably 20-50 mass%, and even more preferably 25-40 mass%. The method for coating the surface of the flaky powder with hydroxyapatite and zinc oxide is not particularly limited, but may be, for example, a method such as that described in JP 2004-315467 A. Specifically, calcium acetate is added to a liquid in which the flaky powder is dispersed, and the mixture is heated (e.g., to 85°C), after which a mixed solution of sodium hydroxide and dibasic sodium phosphate is added to adjust the pH to about 9 to 10. Sodium hydroxide solution is then added to adjust the pH to about 11 to 12, and the mixture is aged at about 85°C. After aging is complete, the reaction solution is cooled and set to about 60°C.When the temperature reaches 60°C, 5N sodium hydroxide solution is added to adjust the pH to about 12, and then 1M zinc chloride solution and 5N sodium hydroxide solution are added dropwise simultaneously to maintain the pH at about 12. Thereafter, the mixture is cooled, filtered, and washed with water repeatedly, dried at about 120°C for about 16 hours, and then pulverized to obtain the desired product.

[0047] The content of component (A) in the cosmetic is 3% by mass or more, preferably 5% by mass or more, and more preferably 7% by mass or more, from the viewpoint of solidifying secreted sebum and preventing adhesion to the mask, particularly in a high-temperature, high-humidity environment. Furthermore, the content of component (A) in the cosmetic is preferably 30% by mass or less, 25% by mass or less, 18% by mass or less, and 15% by mass or less, in order of preference, to further improve powder dispersibility. The content of component (A) is preferably 5 to 30% by mass, 7 to 25% by mass, and 7 to 18% by mass, respectively.

[0048] <Component (B): At least one selected from the group consisting of amino acids and amino acid salts> In this specification, amino acids and / or amino acid salts are also referred to as amino acids (salts).

[0049] The amino acids may be acidic, neutral, or basic amino acids, as well as salts thereof, typically used in cosmetics and topical skin preparations. Specific examples include neutral amino acids (amino acids with the same number of amino groups (-NH) and carboxy groups (-COOH)) such as glycine, trimethylglycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, tryptophan, thyroxine, methionine, cysteine, asparagine, glutamine, pyrrolidonecarboxylic acid, theanine, sarcosine, and tranexamic acid; acidic amino acids (amino acids with more carboxy groups) such as aspartic acid and glutamic acid; and basic amino acids (amino acids with more amino groups) such as lysine, arginine, and histidine. In the case of amino acid salts, counter bases include sodium, potassium, ammonium, and triethanolamine. The amino acids (salts) may be used alone or in combination. In particular, since this further improves powder redispersibility, the amino acid (salt) is preferably a neutral amino acid, more preferably at least one selected from the group consisting of amino acids having a hydroxyl group (such as serine, threonine, and tyrosine) and their salts, and amino acids having an amide bond (such as glutamine, asparagine, and theanine) and their salts, and even more preferably at least one selected from the group consisting of serine, threonine, and theanine and their salts. Furthermore, in terms of powder redispersibility, an embodiment in which component (B) contains theanine (salt) is also preferred. When using a fine particle metal oxide surface-treated with an amino acid (salt) or hydroxyapatite surface-treated with an amino acid (salt), the content of the amino acid (salt) as the surface treatment agent is defined as the content of component (B), and the content of the metal oxide excluding the amount of the amino acid (salt) as the surface treatment agent is defined as the content of component (A).

[0050] The content of component (B) is preferably 0.001% by mass or more, 0.005% by mass or more, 0.01% by mass or more, or 0.05% by mass or more, as this further improves the redispersibility of the powder. Furthermore, the content of component (B) is preferably 3% by mass or less, 2% by mass or less, 1.5% by mass or less, 1% by mass or less, or 0.5% by mass or less, as this suppresses adhesion of the cosmetic to the mask under high-humidity conditions. The content of component (B) is preferably 0.001 to 3% by mass, 0.005 to 2% by mass, 0.01 to 1.5% by mass, or 0.1 to 1% by mass, respectively, and more preferably 0.1 to 0.5% by mass.

[0051] <(C): A crosslinked organosilicon resin represented by average composition formula (1) (hereinafter also referred to simply as a crosslinked organosilicon resin or the crosslinked organosilicon resin of the present invention)> The component (C) used in the present invention is a crosslinked organosilicon resin represented by the following average composition formula (1):

[0052] [ka]

[0053] [In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bond, and R 2 are each independently a polyoxyalkylene-containing group, a polyglycerin-containing group, or R 1 R 2 3SiO 1 / 2 At least one R in each of the units 2 is a polyoxyalkylene-containing group or a polyglycerin-containing group, and R 3 are, independently of each other, an organopolysiloxane-containing group, or R 1 R 3 3SiO 1 / 2 At least one R in each of the units 3 is an organopolysiloxane-containing group, and X is a divalent group represented by the following general formula (2), where (R 13-p (X 1 / 2 ) p SiO 1 / 2 ) may be composed of a plurality of different structural units, and optionally, part of R 2 , R 3 , and X may be hydroxyl groups,

[0054] [Chemical formula]

[0055] (In the formula, R 4 are, independently of each other, unsubstituted or substituted monovalent hydrocarbon groups having no aliphatic unsaturated bond and having 1 to 30 carbon atoms, e is an integer satisfying 0 ≦ e ≦ 500, and k is an integer satisfying 0 ≦ k ≦ 5) a1, a2, a3, a4, b, c, and d are numbers satisfying 0 < a1 ≦ 400, 0 ≦ a2 ≦ 200, 0 ≦ a3 ≦ 400, 0 < a4 ≦ 10, 0 ≦ b ≦ 320, 0 ≦ c ≦ 320, 0 < d ≦ 1,000, and 0.5 ≦ (a1 + a2 + a3 + a4) / d ≦ 1.5, and p is 1].

[0056] In the above formula, R 1 are, independently of each other, substituted or unsubstituted monovalent hydrocarbon groups having no aliphatic unsaturated bond and having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms. R 1 is, for example, an alkyl group, aryl group, aralkyl group having 1 to 30 carbon atoms, or a group in which a hydrogen atom bonded to a carbon atom of these groups is substituted with a halogen atom, amino group or carboxyl group. Among them, R 1 is preferably an alkyl group, aryl group, aralkyl group, fluorine-substituted alkyl group, chloro-substituted alkyl group, amino-substituted alkyl group, or carboxyl-substituted alkyl group having 1 to 10 carbon atoms. More specifically, R 1 can include a methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, etc., a trifluoropropyl group, a heptadecafluorodecyl group, a chloropropyl group, a chlorophenyl group, etc. In particular, R 1 is preferably an alkyl group, phenyl group or trifluoropropyl group having 1 to 5 carbon atoms.

[0057] R 2 is, independently of each other, a group selected from a polyoxyalkylene-containing group, a polyglycerin-containing group, or R 1 and in each of the R 2 3SiO 1 / 2 units, at least one R 2 is a polyoxyalkylene-containing group or a polyglycerin-containing group. R 1 is as described above. Note that R 2 and R 3 may be a hydroxyl group in part. The polyoxyalkylene-containing group is preferably represented by the following general formula (4).

[0058]

Chemical formula

[0059] (In the formula, R 5 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, and m, g1, and g2 are integers satisfying 0 ≦ m ≦ 15, 0 ≦ g1 < 200, 0 ≦ g2 < 200, and 0 < g1 + g2 ≦ 200).

[0060] Also, the polyglycerin-containing group is preferably represented by the following general formula (5).

[0061]

Chemical formula

[0062] (In the formula, R 5 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom, and m and h are integers satisfying 0 ≦ m ≦ 15 and 0 < h ≦ 5).

[0063] The above R 5 are, independently of each other, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms or a hydrogen atom. R 5is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Alternatively, a hydrogen atom bonded to a carbon atom of these groups may be a group substituted with a halogen atom, an amino group or a carboxyl group, for example, a fluorine-substituted alkyl group, a chloro-substituted alkyl group, an amino-substituted alkyl group, or a carboxyl-substituted alkyl group.

[0064] In the above formulas (4) and (5), m satisfies 0 ≦ m ≦ 15, and 0 ≦ m ≦ 2 is preferred. g1 satisfies 0 ≦ g1 < 200, 0 ≦ g1 ≦ 100 is preferred, and 0 ≦ g1 ≦ 50 is more preferred. When g1 is 200 or more, the melting point of the resin becomes low, which is not preferable in terms of lack of film-forming property. g2 satisfies 0 ≦ g2 < 200, 0 ≦ g2 ≦ 100 is preferred, and 0 ≦ g2 ≦ 50 is more preferred. When g2 is 200 or more, the melting point of the resin becomes low, which is not preferable in terms of lack of film-forming property. g1 + g2 satisfies 0 ≦ g1 + g2 < 200, 0 ≦ g1 + g2 ≦ 100 is preferred, and 0 ≦ g1 + g2 ≦ 50 is more preferred. When g1 + g2 is greater than 50, the melting point of the resin becomes low, which is not preferable in terms of lack of film-forming property. When the polyoxyalkylene moiety consists of both ethylene oxide units and propylene oxide units, either a block copolymer or a random copolymer of these two units may be used. h satisfies 0 < h ≦ 5, 0 < h ≦ 4 is preferred, and 0 < h ≦ 3 is more preferred. When h is greater than 5, the melting point of the resin becomes low, which is not preferable in terms of lack of film-forming property.

[0065] In the above R 3 the organopolysiloxane-containing group is a group represented by the following general formula (6), general formula (7), general formula (8), or general formula (9). R 3 3SiO 1 / 2 In each of the units, at least one R 3 is a group represented by the following general formula (6), general formula (7), general formula (8) or general formula (9).

[0066]

Chemical formula

[0067] (In the formula, R 6 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and containing no aliphatic unsaturated bonds, n and i are integers satisfying the conditions 0≦n≦5 and 0≦i≦500, and j1 to j3 are each an integer of 0 or more and 2 or less.

[0068] R 6 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms. 6 is, for example, an alkyl group, an aryl group, an aralkyl group, or a group in which a hydrogen atom bonded to a carbon atom of these groups has been substituted with a halogen atom, an amino group, or a carboxyl group. 6 is preferably an alkyl group, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, a chloro-substituted alkyl group, an amino-substituted alkyl group, or a carboxyl-substituted alkyl group. 6 Examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a trifluoropropyl group, a heptadecafluorodecyl group, a chloropropyl group, and a chlorophenyl group. 6 is more preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group or a trifluoropropyl group.

[0069] n is 0≦n≦5, preferably 0≦n≦2, and i is 0≦i≦500, preferably 1≦i≦100, more preferably 1≦i≦50. If i is greater than 500, the melting point of the resin will be low, resulting in poor film-forming properties. j1 to j3 are each integers that satisfy 0≦j1 to j3≦2.

[0070] X is a divalent group represented by the following general formula (2).

[0071] [ka]

[0072] (In the formula, R 4 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, e is an integer of 0≦e≦500, and k is an integer of 0≦k≦5), provided that optionally, some of the Xs may be hydroxyl groups, and in this case, X may be monovalent.

[0073] Also, (R 1 3-p (X 1 / 2 ) p SiO 1 / 2 ) may be a number of different structural units. That is, for example, (R 1 3-p (X 1 1 / 2 ) p SiO 1 / 2 ) and (R 1 3-p (X 2 1 / 2 ) p SiO 1 / 2 ) (where X 1 , X 2 are divalent groups represented by general formula (2), and may be structural units with (R 1 3-p (X 1 1 / 2 ) p SiO 1 / 2 ) a4’ and (R 1 3-p (X 2 1 / 2 ) p SiO 1 / 2 ) a4’’ When expressed as above, a4 is the sum of a4' and a4''.

[0074] In the above formula (2), R 4 R are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 10 carbon atoms, and containing no aliphatic unsaturated bonds. 4is, for example, an alkyl group, an aryl group, an aralkyl group, or a group in which one or more hydrogen atoms bonded to the carbon atoms of these groups are replaced with a halogen atom, an amino group, or a carboxyl group. 4 is preferably an alkyl group, an aryl group, an aralkyl group, a fluorine-substituted alkyl group, a chloro-substituted alkyl group, an amino-substituted alkyl group, or a carboxyl-substituted alkyl group. 4 Examples of R include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a tolyl group, a trifluoropropyl group, a heptadecafluorodecyl group, a chloropropyl group, and a chlorophenyl group. 4 is more preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a trifluoropropyl group.

[0075] In the above formula (2), e is 0≦e≦500, preferably 0≦e≦100, and more preferably 0≦e≦50. If e is greater than the upper limit, the melting point of the resin decreases, resulting in a lack of film-forming properties, which is undesirable. k is 0≦k≦5, preferably 0≦k≦3, and more preferably 0≦k≦1.

[0076] The crosslinked organosilicon resin of the present invention necessarily contains a group represented by the above formula (2). The group represented by formula (2) has a flexible skeleton, and therefore can impart flexibility to the organosilicon resin that enables it to form a free-standing film.

[0077] The resin may contain two or more types of groups represented by formula (2). As the chain length of the group represented by formula (2) increases, the organosilicon resin has the effect of imparting flexibility.

[0078] In the crosslinked organosilicon resin represented by the above formula (1), a1 satisfies 0 < a1 ≤ 400, preferably 1 ≤ a1 ≤ 100, more preferably 1 ≤ a1 ≤ 50. In the crosslinked organosilicon resin represented by the above formula (1), a2 satisfies 0 ≤ a2 ≤ 200, preferably 0 ≤ a2 ≤ 100, more preferably 0 ≤ a2 ≤ 50. In the crosslinked organosilicon resin represented by the above formula (1), a3 satisfies 0 ≤ a3 ≤ 400, preferably 0 ≤ a3 ≤ 100, more preferably 0 ≤ a3 ≤ 50. When a3 is greater than 200, the melting point of the resin becomes low and it lacks film-forming properties. In the crosslinked organosilicon resin represented by the above formula (1), a4 satisfies 0 < a4 ≤ 50, preferably 0 < a4 ≤ 30, more preferably 0 < a4 ≤ 10. When a4 is greater than 50, the crosslinking degree increases and the molecular weight becomes large, so the possibility of gelation increases. 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, 0 < d ≤ 1,000, and it is a number that satisfies 0.5 ≤ (a1 + a2 + a3 + a4) / d ≤ 1.5, preferably a number that satisfies 0.7 ≤ (a1 + a2 + a3 + a4) / d ≤ 1.2. When the value of (a1 + a2 + a3 + a4) / d is less than the above lower limit, the crosslinking degree increases and the molecular weight becomes large, so it becomes gel-like. When the value of (a1 + a2 + a3 + a4) / d exceeds the above upper limit, the molecular weight becomes small and it lacks film-forming properties. p is 1.

[0079] The crosslinked organosilicon resin of the present invention preferably has a weight average molecular weight of 1,000 to 1,000,000, more preferably 1,000 to 500,000, still more preferably 3,000 to 300,000, and even more preferably 50,000 to 300,000. By being within the above range, it is more preferable in terms of performance and workability such as filtration. In the present invention, the weight average molecular weight can be determined as the weight average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) analysis (hereinafter the same).

[0080] In the above average compositional formula (1), when a4 in the average compositional formula (1) satisfies 0 < a4 ≤ 5, and e in the general formula (2) is an integer satisfying 0 < e < 40, or when a4 in the average compositional formula (1) satisfies 0 < a4 ≤ 5, and the crosslinked organic silicon resin having a plurality of groups with different structures represented by the general formula (2), and at least one e of the plurality of groups satisfies 0 < e < 40, a crosslinked organic silicon resin that is solid at 25°C and has excellent film-forming properties can be obtained. If it only has a part where a4 is greater than 5 and e is greater than 40, there is a high possibility of becoming gel-like when the diluting solvent is removed. In this case, although it has film-forming properties, it has a feeling derived from gel.

[0081] In particular, when a4 in the average compositional formula (1) satisfies 0 < a4 ≤ 3, and e in the general formula (2) is a number satisfying 0 < e ≤ 20, or when a4 in the average compositional formula (1) satisfies 0 < a4 ≤ 3, and the crosslinked organic silicon resin having a plurality of groups with different structures represented by the general formula (2), and at least one e of the plurality of groups satisfies 0 < e < 40, it is a crosslinked organic silicon resin that is solid at 25°C and has more excellent film-forming properties. The obtained film exhibits excellent flexural resistance and oil resistance.

[0082] [Manufacturing method] Crosslinked organic silicon resins 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 organic silicon resin. However, since it is difficult to completely control the amount of silanol groups on the surface of the organic silicon resin, there is a problem that it is difficult to accurately control the amount of the organopolysiloxane to be crosslinked. Therefore, a synthesis method by an addition reaction of an organic silicon resin having a hydrosilyl group and an organopolysiloxane having unsaturated groups at both ends, or an addition reaction of an organic silicon resin having unsaturated groups and an organopolysiloxane having hydrosilyl groups at both ends is preferred.

[0083] Regarding the details of the addition reaction between an organosilicon resin having a hydrosilyl group and an organopolysiloxane having unsaturated groups at both ends, the crosslinked organosilicon resin represented by the above average composition formula (1) is obtained by subjecting a hydrosilyl group-containing organosilicon resin represented by the following average composition formula (13) and being solid or liquid at 25°C and one or more terminal alkenyl group-containing compounds represented by the following general formulas (11), (14), (15), (16), (17), (18) or (19) (provided that it contains at least one kind of group represented by the following formula (11)) to a hydrosilylation reaction. The hydrosilylation reaction may also be carried out in the presence of a platinum catalyst or a rhodium catalyst.

[0084]

Chemical formula

[0085] [In the formula, R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bond, and examples of the monovalent hydrocarbon group exemplified by R1 above can be mentioned. a1, a2, a3, a4, b, c, and d are numbers satisfying 0 < a1 ≤ 400, 0 ≤ a2 ≤ 200, 0 ≤ a3 ≤ 400, 0 < a4 ≤ 10, 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, 0 < d ≤ 1,000, 0.5 ≤ (a1 + a2 + a3 + a4) / d ≤ 1.5, and p is 1.]

[0086]

Chemical formula

[0087] (In the formula, R 4 , e, and k are as defined above.)

[0088]

Chemical formula

[0089] (In the formula, R 5 , m, g1 and g2 are as defined above.)

[0090] [ka]

[0091] (In the formula, R 5 , m and h are as above)

[0092] [ka]

[0093] (In the formula, R 6 , n, i and j1 to j3 are as above).

[0094] The hydrosilyl group-containing organosilicon resin represented by the above average composition formula (13) is a resin having a Q unit (SiO 4 / 2 ),M units ((R 1 3SiO 1 / 2 ) and (H p R 1 3-p SiO 1 / 2 )) is an essential component, and D units (R 1 2SiO 2 / 2 ),T units(R 1 SiO 3 / 2 The hydrosilyl group-containing organosilicon resin represented by the average compositional formula (13) may be solid or liquid at 25°C, but is preferably solid from the viewpoint of film-forming properties. Examples of the hydrosilyl group-containing organosilicon resin represented by the average compositional formula (13) include MQ resin, MTQ resin, MDQ resin, and MDTQ resin. The weight-average molecular weight is preferably in the range of 2,000 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 converted into polystyrene by gel permeation chromatography (GPC) analysis.

[0095] The method for producing a crosslinked organosilicon resin by the hydrosilylation reaction will now be described in more detail.

[0096] In the hydrosilylation reaction step between the hydrosilyl group-containing organosilicon resin represented by the above average composition formula (13) and the terminally unsaturated group-containing compound represented by the above general formula (11), (14), (15), (16), (17), (18) or (19), the molar ratio of hydrosilyl group / terminally unsaturated group is preferably 0.5 to 2.0, more preferably 0.8 to 1.2.

[0097] The hydrosilylation reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Examples of suitable catalysts include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complexes. Since an excessive amount of catalyst will discolor the sample, the amount of platinum or rhodium used is preferably 50 ppm or less, and more preferably 20 ppm or less.

[0098] 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, and dodecamethylcyclohexasiloxane; 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, and cyclohexane; and 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. In particular, ethanol, 1-propanol, and 2-propanol are preferred from the viewpoint of reactivity.

[0099] The amount of the solvent used is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, of the entire reaction liquid (system). Within this range, the reaction system is maintained uniformly, and the reaction proceeds efficiently.

[0100] The addition reaction conditions are not particularly limited, but it is preferable to heat under reflux at a temperature of 50 to 150°C, more preferably 80 to 120°C, for about 1 to 10 hours.

[0101] After the addition reaction, a step of removing the rhodium catalyst or platinum catalyst used with activated carbon may be included. The amount of activated carbon used is preferably 0.001 to 5.0% by mass, and more preferably 0.01 to 1.0% by mass, of the entire system. By keeping the amount within this range, coloration of the sample can be further suppressed.

[0102] After the addition reaction, a step of removing remaining hydrosilyl groups can be included as needed. In particular, when used in applications such as cosmetics, the hydrosilyl groups may be deactivated over time by dehydrogenation, so it is preferable to include a step of removing the hydrosilyl groups.

[0103] The process for removing hydrosilyl groups involves adding a basic catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide to hydrolyze unreacted hydrosilyl groups, followed by neutralization by adding an acidic catalyst in an amount equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide, and weak basic catalysts such as sodium carbonate, calcium carbonate, and sodium bicarbonate. In terms of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, and sodium hydroxide is particularly preferred. Specific examples of acidic catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, oleum, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. In general, rather than using an acid or base alone, it is preferable to use them in combination with water and heat them at a temperature below the boiling point of water. Through this step, the hydrosilyl group (SiH group) becomes a hydroxysilyl group (SiOH group).

[0104] After the addition reaction, a deodorizing treatment step can be included to reduce odor, if necessary. In particular, when used in applications such as cosmetics, a deodorizing treatment step is preferable due to the tendency for odor to develop over time. The odor-developing mechanism of typical polyether-modified silicones can be explained as follows: When an addition reaction between an allyl-etherified polyether and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, a side reaction occurs in which the allyl group undergoes internal rearrangement to produce a propenyl-etherified polyether. This propenyl-etherified polyether is not reactive with the hydrogen polyorganosiloxane and therefore remains in the system as an impurity. When water acts on this propenyl-etherified polyether, the propenyl ether is hydrolyzed, generating propionaldehyde, which is responsible for the unpleasant odor. Furthermore, the above hydrolysis reaction is known to be accelerated in the presence of an acid catalyst. When polyether-modified silicones are used in aqueous cosmetics, the liquid becomes more acidic over time due to oxidative degradation of the polyether, accelerating the hydrolysis reaction described above and causing the unpleasant odor.

[0105] There are two typical examples of deodorization treatment processes: The first method involves adding an acidic catalyst to the solution after the addition reaction to hydrolyze all of the propenyl ether remaining in the system, and then removing the resulting propionaldehyde by strip purification (Japanese Patent No. 2137062).

[0106] Specific examples of the acid catalyst used in the first formulation include hydrochloric acid, sulfuric acid, sulfurous acid, oleum, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. These acids are used in combination with water, but when it is necessary to remove the used acid, it is preferable to use an acid with a low boiling point, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Furthermore, from the viewpoint of treatment efficiency, it is preferable to use a strong acid, such as hydrochloric acid or trifluoroacetic acid.

[0107] The treatment temperature is preferably 80° C. or less to prevent oxidation of the hydrophilic groups. The amount of the acidic aqueous solution added is preferably 0.1 to 100%, more preferably 5 to 30%, based on the amount of the organic group-modified organosilicon resin.

[0108] From the viewpoint of productivity, a preferred method is to add an aqueous solution to the reaction solution so that the pH is 7 or less, heat and stir the solution, and then perform strip purification. The strip purification may be carried out at room temperature or under reduced pressure, but the temperature condition is preferably 120°C or less. For efficient strip purification under these temperature conditions, it is preferable to carry out the strip purification under reduced pressure, or, in the case of normal pressure, under a stream of an inert gas such as nitrogen or argon.

[0109] The second method is to add hydrogen to the solution after the addition reaction to alkylate the unsaturated double bonds (a so-called hydrogenation reaction), thereby stably controlling the generation of propionaldehyde over time (U.S. Pat. No. 5,225,509, JP-A-7-330907).

[0110] Hydrogenation reactions can be carried out using hydrogen or metal hydrides, and can also be carried out using homogeneous or heterogeneous reactions. These can be carried out alone or in combination. However, heterogeneous catalytic hydrogenation using a solid catalyst is most preferred, as it has the advantage that the catalyst used does not remain in the product.

[0111] Solid catalysts include elements or compounds of nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron, etc. In this case, a catalyst carrier is not necessary, but if one is used, activated carbon, silica, silica alumina, alumina, zeolite, etc. are used. These catalysts can be used alone or in combination. The most preferred catalyst is Raney nickel, which is economically advantageous. Raney nickel is usually developed with alkali, so the pH of the reaction solution must be carefully monitored. In addition, because the reaction system becomes weakly alkaline, hydrolysis reactions using acidic aqueous solutions are particularly effective for deodorization.

[0112] The hydrogenation reaction is generally preferably carried out at 1 to 100 MPa and 50 to 200°C. The hydrogenation reaction may be batchwise or continuous. In the case of a batchwise reaction, the reaction time depends on the amount of catalyst, temperature, etc., but is generally 3 to 12 hours. The hydrogen pressure can be adjusted to a constant pressure as needed, but the end point of the hydrogenation reaction is the point at which the hydrogen pressure no longer changes, which can be determined by carefully observing the pressure gauge.

[0113] The amount of aldehyde contained in the organic group-modified organosilicon resin purified by such acid treatment or hydrogenation reaction treatment can be reduced to 70 ppm or less, 20 ppm or less, or even 10 ppm or less.

[0114] Furthermore, it is possible to combine the two types of deodorizing treatment steps mentioned above. While acid treatment can decompose and remove aldehyde compounds, there are limitations to completely removing unsaturated double bonds, making it impossible to completely suppress the generation of aldehydes, which cause odors. Furthermore, hydrogenation treatment can eliminate unsaturated double bonds and thereby reduce the amount of aldehyde compounds generated. However, aldehyde condensates, which are generated by condensation of some of the aldehydes, remain in the system even after the above treatment and are difficult to remove by strip purification. Therefore, complete deodorization is possible by subjecting the solution after the addition reaction to a hydrogenation reaction to alkylate the remaining unsaturated double bonds, and then adding an acid catalyst to decompose the aldehyde condensates in the system (WO 2002 / 055588 (U.S. Patent Application Publication No. 2003 / 158363, the disclosure of which is incorporated by reference in its entirety)).

[0115] [Method for producing raw material hydrosilyl group-containing organosilicon resin] The hydrosilyl group-containing organosilicon resin represented by the average composition formula (13) above may be in a solid or liquid form at 25°C, but a solid form is preferred from the viewpoint of film-forming properties. From the viewpoint of ease of use, it is preferable to dilute it with an organic solvent. It is also preferable to use a solvent with a boiling point higher than the reflux temperature during hydrolysis.

[0116] Examples of organic solvents used for dilution include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; 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, and cyclohexane; and 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. In particular, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred from the viewpoint of storage stability and non-volatility.

[0117] The hydrosilyl group-containing organosilicon resin represented by the average composition formula (13) can be produced by known methods, such as those described in JP 2017-75283 A (the disclosure of which is incorporated herein by reference in its entirety, U.S. Patent Publication No. 2018 / 0298148).

[0118] More specifically, the compound can be obtained by hydrolyzing a mixture of one or more organic silicon compounds represented by the following general formula (20) or (21), one or more hydrosilyl group-containing organic silicon compounds represented by the following general formula (22) or (23), and one or more hydrolyzable silanes represented by the following general formula (24), partial hydrolysis condensates of the hydrolyzable silanes, and metal salts of the hydrolyzable silanes, in the presence of an acid catalyst, followed by neutralization by adding a base catalyst in an amount greater than the molar equivalent of the acid catalyst, and then condensing in the presence of a base catalyst.

[0119] R 1 3SiOSiR 13(20) R 1 3SiX 1 (twenty one) H p R 1 (3-p) SiOSiR 1 (3-p) H p (twenty two) H p R 1 (3-p) Six 2 (twenty three) Six 3 4(24) (In the formula, R 1 is as above, and X 1 , X 2 , and X 3 are each independently a hydrolyzable functional group, and p=1).

[0120] In the general formulae (21), (23), and (24), X 1 , X 2 , and X 3 are, independently of one another, hydrolyzable functional groups directly bonded to a silicon atom, and examples thereof include halogen atoms such as chlorine and bromine atoms; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; alkenoxy groups; acyloxy groups; amide groups; and oxime groups. Among these, methoxy, ethoxy, and chlorine atoms are particularly preferred from the viewpoints of availability and hydrolysis rate.

[0121] Examples of organosilicon compounds represented by the general formula (20) include 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,1,3,3-pentavinylmethyldisiloxane, 1,1,1,3,3-n-octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldisiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane, and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Particularly preferred are 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane.

[0122] Examples of organosilicon compounds represented by the general formula (21) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, etc. Trimethylchlorosilane, trimethylethoxysilane, etc. are particularly preferred.

[0123] Examples of hydrosilyl group-containing organosilicon compounds represented by the general formula (22) include 1,1,3,3-tetramethyldisiloxane and 1,1,1,3,3-pentamethyldisiloxane. 1,1,3,3-tetramethyldisiloxane is particularly preferred. In the general formulas (22) and (23), p is in the range of 1≦p≦3. However, in the general formula (22), the number of H and R bonded to one silicon atom is 1≦p≦3. 1 The p related to the H, R bonded to the other silicon atom 1 It may be the same as or different from p according to the above.

[0124] Examples of the hydrosilyl group-containing organosilicon compound represented by the general formula (23) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane, dimethylethoxysilane, etc. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

[0125] Examples of hydrolyzable silanes represented by the general formula (24) include tetrachlorosilane, tetramethoxysilane, and tetraethoxysilane. Examples of partial hydrolyzed condensates of the hydrolyzable silanes include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of the hydrolyzable silanes include water glass, sodium silicate, and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

[0126] Furthermore, in the process for producing the hydrosilyl group-containing organosilicon resin represented by the above average composition formula (13), a mixture of one or more compounds selected from the compounds represented by the above general formulas (20) to (24) can be added under an acid catalyst before hydrolysis, or after the hydrolysis but before the second hydrolysis described below, to a mixture of one or more compounds selected from the organosilicon compounds represented by the following general formula (25) or (26):

[0127] R 1 Six 4 3(25) R 1 2SiX 5 2(26) (In the formula, R 1 is as above) In the general formulas (25) and (26), X 4 and X 5 are, independently of one another, hydrolyzable functional groups directly bonded to a silicon atom, and examples thereof include halogen atoms such as chlorine and bromine atoms; alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy; alkenoxy groups; acyloxy groups; amide groups; and oxime groups. Among these, methoxy, ethoxy, and chlorine atoms are particularly preferred from the viewpoints of availability and hydrolysis rate.

[0128] Examples of silicon compounds represented by general formula (25) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, trifluoropropyltrimethoxysilane, methyltrichlorosilane, etc. Methyltrimethoxysilane, methyltriethoxysilane, and methyltrichlorosilane are particularly preferred.

[0129] Examples of silicon compounds represented by general formula (26) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane, dimethyldichlorosilane, etc. Dimethyldimethoxysilane, dimethyldiethoxysilane, and dimethyldichlorosilane are particularly preferred.

[0130] A more detailed example of a method for producing a hydrosilyl group-containing organosilicon resin represented by the average composition formula (13) is described below. A solvent (particularly an organic solvent) and hydrolysis raw materials (i.e., a mixture of one or more organosilicon compounds represented by the general formula (20) or (21) above, one or more hydrosilyl group-containing organosilicon compounds represented by the general formula (22) or (23) above, and one or more hydrolyzable silanes represented by the general formula (24) above, partial hydrolyzed condensates of the hydrolyzable silanes, and metal salts of the hydrolyzable silanes) are charged into a reactor, an acid catalyst is added, and water is added dropwise with stirring. In this case, the organic solvent may be added after the water addition is complete. Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

[0131] The temperature at which water is added dropwise is preferably 0 to 80°C, and particularly preferably 0 to 50°C. By keeping the temperature within this range, the heat of reaction resulting from the hydrolysis reaction of the hydrolysis raw material in the system can be suppressed. The amount of water to be added dropwise is in the range of 0.6 to 2, preferably 1.0 to 1.8, in terms of molar ratio to the hydrolyzable functional group (alkoxy group, etc.). By keeping the temperature within this range, it is possible to further suppress the deactivation of the hydrosilyl group.

[0132] The solvent used in the hydrolysis reaction is preferably an organic solvent, in order to maintain a homogeneous reaction system and prevent a decrease in the reaction rate due to an increase in viscosity during the hydrolysis reaction. It is also desirable to use a solvent with a boiling point higher than the reflux temperature during hydrolysis.

[0133] Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-based organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane.

[0134] In some cases, an alcohol solvent having 1 to 10 carbon atoms can also be used in combination. Examples include 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. Since alcohol solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of long-chain alcohol solvents can limit the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol, and 2-propanol are particularly preferred.

[0135] The amount of the solvent used is preferably 1 to 80% (mass %, hereinafter the same) of the entire reaction solution (system), particularly preferably 5 to 50%. Within this range, the reaction system is maintained uniformly, and the reaction proceeds efficiently.

[0136] Examples of the acid catalyst include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, citric acid, etc. The amount of the acid catalyst used may be small, preferably in the range of 0.001 to 10% of the entire reaction solution (system).

[0137] After the dropwise addition of water as described above, the hydrolysis reaction is carried out by heating for about 2 to 8 hours at a temperature of, for example, 50 to 150°C, more preferably 80 to 120°C. In this case, deactivation of the hydrosilyl group can be further suppressed by carrying out the reaction at a temperature below the boiling point of the hydrosilyl group-containing organic compound used.

[0138] After the raw material for hydrolysis has been hydrolyzed in this manner under an acid catalyst, it is cooled to 10 to 100°C, preferably 10 to 60°C, more preferably 10 to 30°C, and even more preferably to 25°C.

[0139] After the hydrolysis, the reaction mixture is neutralized at 10 to 40°C with a base catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide. Using a strong base catalyst in combination with a weak base catalyst further inhibits deactivation of the hydrosilyl groups and accelerates the condensation reaction of the organosilicon resin. Examples of strong base catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide. Examples of weak base catalysts include sodium carbonate, calcium carbonate, and sodium bicarbonate. A combination of sodium hydroxide and calcium carbonate is particularly desirable as a strong base catalyst and a weak base catalyst, as this facilitates high molecular weight production. This combination significantly increases the molecular weight, making it possible to more reliably obtain a high molecular weight hydrosilyl group-containing organosilicon resin.

[0140] The amount of base catalyst used must be greater than the molar equivalent of the acid catalyst. Neutralizing with a base catalyst in excess of the acid catalyst's equivalent allows the condensation reaction of the organosilicon resin to take precedence, resulting in an increase in molecular weight and the production of a high-molecular-weight hydrosilyl group-containing organosilicon resin. The amount of base catalyst used is preferably in the range of 1.1 to 3.0 molar equivalents of the acid catalyst. By keeping the amount added within this range, the condensation reaction of the hydrosilyl group-containing organosilicon resin takes precedence, resulting in the production of a resin with the desired molecular weight.

[0141] After neutralization, the resulting alcohols, solvent, and excess water may be removed by heating at 95 to 120°C under normal or reduced pressure. After confirming that the resulting alcohols, solvent, and excess water have been removed, the mixture is heated, for example, at 120 to 150°C for 2 to 5 hours to carry out a condensation reaction. This produces a hydrosilyl group-containing organosilicon resin.

[0142] In the method for producing the hydrosilyl group-containing organosilicon resin described above, the total amount of the compounds of the general formulas (20), (21), (22) and (23) and the SiO of the compound of the general formula (24) are 4 / 2 The molar ratio (((20), (21), (22) + (23)):(24)) of the amount of each compound represented by formula (20) and (21) to the amount of each compound represented by formula (22) and (23) is preferably 0.3:1 to 2:1, more preferably 0.6:1 to 1.3:1. Furthermore, the molar ratio (((20) + (21)):((22) + (23))) of the amount of each compound represented by formula (20) and (21) to the amount of each compound represented by formula (22) and (23) is preferably 0.3:1.0 to 2.0:1.0, more preferably 0.6:1.0 to 1.3:1.0. By keeping the ratio within the above range, the amount of hydrosilyl groups contained in the hydrosilyl group-containing organosilicon resin can be quantitatively varied more accurately. Thus, in the present invention, the amount of hydrosilyl groups contained in the organosilicon resin can be quantitatively varied by changing the amount of compounds represented by formula (22) and formula (23) added.

[0143] In the process for producing hydrosilyl group-containing organosilicon resins, a reaction may occur in which some of the hydrosilyl groups are deactivated, as shown in the reaction formula below.

[0144] SiO 1 / 2 H p’ R 3-p’ (M unit) + ~Si-OH → ~Si-O-SiO 1 / 2 H p’-1 R 3-p’ (D unit) (wherein R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and p' is an integer of 1 to 3) Therefore, in the above-described method for producing a hydrosilyl group-containing organosilicon resin, a mixture of one or more organosilicon compounds represented by the general formulae (20) and (21) above and one or more hydrolyzable silanes represented by the general formula (22) above, partial hydrolysis condensates of the hydrolyzable silanes, and metal salts of the hydrolyzable silanes is hydrolyzed under an acid catalyst, and then one or more hydrosilyl group-containing organosilicon compounds represented by the general formulae (22) and (23) above are gradually added dropwise to carry out another hydrolysis, thereby preventing deactivation of the hydrosilyl groups.

[0145] The second hydrolysis reaction is preferably carried out by heating below the boiling point of the hydrosilyl group-containing organic compound to be reacted, for example, at a temperature of 40 to 150°C, more preferably 40 to 120°C, for about 2 to 8 hours. By carrying out the reaction within the above temperature range, deactivation of the hydrosilyl group can be further suppressed. Furthermore, deactivation of the hydrosilyl group can be further suppressed by adjusting the amounts of raw materials added and the type of catalyst.

[0146] The amount of hydrosilyl groups contained in the hydrosilyl group-containing organosilicon resin represented by the above average composition formula (13) can be easily adjusted by changing the amount of hydrosilyl group-containing organosilicon compound added, and large amounts can also be introduced. Furthermore, by changing the amount of hydrolysis raw material, the type and amount of acid catalyst added, reaction temperature, reaction time, and the amount and method of solvent addition, the molecular weight distribution and shape of the organosilicon resin can be adjusted, allowing the production of hydrosilyl group-containing organosilicon resins suited to specific applications.

[0147] The production method by addition reaction of an organosilicon resin having an unsaturated group with an organopolysiloxane having hydrosilyl groups at both ends will be explained in more detail below.

[0148] [ka]

[0149] [In the formula, R 1’ is an alkenyl group having 2 to 8 carbon atoms, and R 1 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, and R 2 are each independently a polyoxyalkylene-containing group, a polyglycerin-containing group, or R 1 R 2 3SiO 1 / 2 At least one R in each of the units 2 is a polyoxyalkylene-containing group or a polyglycerin-containing group, and R 3 are each independently an organopolysiloxane-containing group or R 1 and each R 3 3SiO 1 / 2 R in units 3One or more of them are organopolysiloxane-containing groups. a1, a2, a3, b, c, and d are numbers such that 0 < a5 ≤ 5, 0 < a1 ≤ 400, 0 ≤ a2 ≤ 200, 0 ≤ a3 ≤ 400, 0 ≤ b ≤ 320, 0 ≤ c ≤ 320, 0 < d ≤ 1,000, and satisfy 0.5 ≤ (a1 + a2 + a3 + a5) / d ≤ 1.5.

[0150]

Chemical formula

[0151] [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 one of all R 4 is a hydrogen atom, e = 2, f is 0 or a positive number, provided that 2 ≤ e + f < 32 is satisfied. In the hydrosilylation reaction step of the alkenyl group-containing organosilicon resin represented by the above average composition formula (30) and the organohydrogenpolysiloxane represented by the above formula (31), 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 remaining amount of the hydrosilyl group will increase, and the stability over time may deteriorate.

[0152] 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 excessively included, 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.

[0153] 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, and dodecamethylcyclohexasiloxane; 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, and cyclohexane; and 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. In particular, ethanol, 1-propanol, and 2-propanol are preferred from the viewpoint of reactivity.

[0154] The amount of the solvent used is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, of the entire reaction liquid (system). Within this range, the reaction system is maintained uniformly, and the reaction proceeds efficiently.

[0155] The addition reaction conditions are not particularly limited, but it is preferable to heat under reflux at a temperature of 50 to 150°C, more preferably 80 to 120°C, for about 1 to 10 hours.

[0156] After the addition reaction, the rhodium catalyst or platinum catalyst and the hydrosilyl groups used can be removed by a method similar to that used in the addition reaction of an organosilicon resin having hydrosilyl groups and an organopolysiloxane having unsaturated groups at both ends.

[0157] [Physical properties of cross-linked organosilicon resin] The crosslinked organosilicon resin may be in a solid state, a gel state, or a liquid state at 25°C. However, from the perspective of film-forming properties, a solid state or a gel state is preferred, and a solid state is particularly preferred. In particular, the crosslinked organosilicon resin in which a4 in the above average composition formula (1) is a number satisfying 0 < a4 ≤ 5 and e in the above general formula (2) is a number satisfying 0 < e ≤ 20, or the crosslinked organosilicon resin in which a4 in the above average composition formula (1) is a number satisfying 0 < a4 ≤ 5, has a plurality of groups with different structures represented by the above general formula (2), and at least one e of the plurality of groups is a number satisfying 0 < e ≤ 20, is in a solid state at 25°C and has a weight average molecular weight in the range of 1,000 to 1,000,000, so it is preferred. In particular, having a weight average molecular weight of 3,000 to 500,000 is more preferred in terms of performance and workability such as filtration.

[0158] The crosslinked organosilicon resin preferably has a solid property at 25°C and forms a film. Whether a film is formed can be determined by dropping 1.5 g of a solution diluted to 60% with isododecane or decamethylcyclopentasiloxane on 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.

[0159] From the perspective of the convenience of blending into aqueous or emulsion compositions, the crosslinked organosilicon resin may be made into an O / W type emulsion and used as an intermediate composition. That is, an O / W type emulsion in which a solution of any oil agent of the crosslinked organosilicon resin is used as the dispersed phase and dispersed in the aqueous phase, which is the continuous phase, is first adjusted as an intermediate composition, and a cosmetic containing this can be adjusted. The method for producing the O / W type emulsion as the intermediate composition is not particularly limited and can be produced by a known method. For example, a method of emulsifying using one or more surfactants with an HLB of 10 or more can be mentioned, and a surfactant with an HLB of less than 10 or a higher alcohol etc. may be used as a stabilizer. Also, the aqueous phase may be thickened using carbomer etc.

[0160] The blending amount of the crosslinked organosilicon resin is preferably in the range of 0.1 to 40% by mass of the entire cosmetic, more preferably 0.1 to 20% by mass, even more preferably 0.3 to 15% by mass, and even more preferably 1 to 10% by mass. If it is 0.1% by mass or more, effects such as secondary adhesion, sustained pore covering effect, and no dry feeling are likely to be obtained, while if it is 40% by mass or less, the feel in use (particularly no dry feeling) will be good.

[0161] The crosslinked organosilicon resin of the present invention can be dissolved in any oil and provided as a dissolved product. When the oil is volatile, the evaporation of the oil allows the formation of a film, thereby exerting its effect as a film-forming agent. It is preferable for the volatile oil to form a film and exert its effect quickly after application of the cosmetic. From this perspective, it is preferable to incorporate a volatile oil with a boiling point of 240°C or less. Among these, silicone oils such as decamethylpentasiloxane and dimethicone, isododecane, and ethanol are particularly preferred, and can be appropriately selected and combined depending on the type of base base of the cosmetic. For example, when the base base is silicone-based, selecting a silicone oil is appropriate, as it improves the compatibility of the entire cosmetic composition. Silicone oils are preferred because they provide a pleasant feel to the touch. Commercially available products include TMF-1.5, KF-995, KF-96L-1cs, KF-96L-1.5cs, and KF-96L-2cs, manufactured by Shin-Etsu Chemical Co., Ltd.

[0162] <Component (D): Spherical powder with an average particle size of 5 to 50 μm> Component (D) is a spherical powder with an average particle size of 5 to 50 μm. By including this powder in combination with components (B) and (C), the powder dispersibility of component (A) is improved. Furthermore, by including component (D), the durability of the pore-covering effect is improved.

[0163] Although the cosmetic of the present invention contains spherical powders with an average particle size of 5 to 50 μm, this does not exclude the cosmetic from containing spherical powders with an average particle size of less than 5 μm and / or spherical powders with an average particle size of more than 50 μm, and these powders may be contained as long as the effects of the present invention are not impaired. The blending amount of spherical powders with an average particle size of less than 5 μm and / or spherical powders with an average particle size of more than 50 μm in the cosmetic is preferably 5% by mass or less (lower limit: 0% by mass), more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0164] The spherical shape of the spherical powder does not only mean a perfect sphere, but also includes an elliptical or approximately spherical shape, and shapes with minute holes or irregularities on the surface. A spherical shape is preferably one in which the ratio of the minor axis to the major axis is 1:1 to 1:2.

[0165] Specific examples of the spherical powder include inorganic powders such as zinc oxide, aluminum oxide, silicon dioxide (silica, silicic anhydride), magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, calcium sulfate, chromium oxide, chromium hydroxide, carbon black, aluminum silicate, magnesium silicate, aluminum magnesium silicate, talc, kaolin, silicon carbide, barium sulfate, bentonite, smectite, and boron nitride; and acrylic resin powders such as polymethyl methacrylate, methyl methacrylate crosspolymer, acrylonitrile-methacrylic acid copolymer, and vinylidene chloride-methacrylic acid copolymer. Examples of the powder include silicone resin powders such as (dimethicone / vinyl dimethicone) crosspolymer, (vinyl dimethicone / methicone silsesquioxane) crosspolymer, (diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer, and polymethyl silsesquioxane; organic powders such as nylon, cellulose acetate, cellulose, polylactic acid, polyurethane, polyethylene, polystyrene, and (HDI / PPG / polycaprolactone) crosspolymer; and composite powders such as titanium oxide-containing silica and zinc oxide-containing silica, and these can be used alone or in combination of two or more.

[0166] From the viewpoint of powder dispersibility, component (D) is preferably at least one powder selected from the group consisting of silicone resin powder, urethane, nylon, cellulose acetate, cellulose, starch, polylactic acid, acrylic resin powder, and silica, more preferably at least one powder selected from the group consisting of cellulose acetate, cellulose, starch, polylactic acid, acrylic resin powder, and silica, and even more preferably at least one powder selected from the group consisting of cellulose, acrylic resin powder, and silica. Furthermore, embodiments in which the component is a plant-derived powder or an inorganic powder are also preferred, and specifically at least one powder selected from the group consisting of cellulose, starch, and silica is preferred.

[0167] From the viewpoints of powder dispersibility and duration of the pore-covering effect, component (D) is preferably a powder having an average particle size of 15 to 50 μm, more preferably a spherical powder having an average particle size of 20 to 40 μm. Ingredients (A)~(D): (A) At least one selected from the group consisting of fine particle metal oxides, hydroxyapatite, and composite powders containing metal oxides and hydroxyapatite (B) at least one selected from the group consisting of amino acids and amino acid salts (C) Crosslinked organosilicon resin represented by average composition formula (1) (D) Spherical powder with an average particle size of 20 to 40 μm The cosmetic is a water-in-oil emulsion cosmetic, containing the component (A), and the content of the component (A) in the cosmetic is 3 mass % or more.

[0168] The particle size of the spherical powder can be measured using a laser diffraction particle size distribution analyzer. Furthermore, when the particle size distribution has one peak, the average particle size is taken as the volume average particle size. Here, spherical powders with small particle sizes may be combined, as in the examples below. That is, the particle size distribution may have two (or more) peaks, but in this case, it is sufficient that at least one peak (mode diameter) is between 5 and 50 μm. In other words, the phrase "spherical powders with an average particle size of 5 to 50 μm" does not refer to the average particle size of all spherical powders, but rather refers to the inclusion of spherical powders with an average particle size of 5 to 50 μm as a particle group.

[0169] The spherical powder may be a commercially available product.

[0170] The spherical powder may be surface-treated. Examples of surface treatments include fluorine compound treatment, silica treatment, alumina treatment, aluminum hydroxide treatment, silicone treatment (methicone treatment, dimethicone treatment, hydrogen dimethicone treatment, etc.), silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, silane treatment, oil treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment, and metal oxide treatment. These surface treatments may be used alone or in combination of two or more. The treatment amount (total) of the surface treatment agent is preferably 0.1 to 30 mass% based on the untreated powder.

[0171] Component (D) may also be surface-treated with component (B). In this case, the content of the amino acid (salt) as the surface treatment agent is defined as the content of component (B), and the content of the spherical powder (or spherical powder surface-treated with another surface treatment agent) excluding the amount of the amino acid (salt) as the surface treatment agent is defined as the content of component (D).

[0172] The surface treatment method is the same as that described in the section for component (A) above.

[0173] The content of component (D) is, in order of preference, 0.1% by mass or more, 0.5% by mass or more, and 1% by mass or more, as this further improves the dispersibility of the powder. Also, in order of preference, the content of component (D) is 20% by mass or less, 15% by mass or less, 10% by mass or less, and 5% by mass or less, from the viewpoint of the lack of dryness. The content of component (D) is preferably 0.1 to 20% by mass, 0.5 to 15% by mass, and 1 to 10% by mass, respectively.

[0174] <Component (E): Water> Since the present invention is a water-in-oil emulsion cosmetic, it usually contains component (E) water.

[0175] Water is used as a dispersion medium, and is not particularly limited, but examples thereof include purified water, distilled water, ion-exchanged water, tap water, hot spring water, and deep sea water.

[0176] The water content is not particularly limited, but from the viewpoint of formulation stability of the water-in-oil emulsion cosmetic, it is preferably 5 to 60 mass % and more preferably 10 to 45 mass % in the water-in-oil emulsion cosmetic.

[0177] Alternatively, a lower alcohol having 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms (e.g., ethanol) and / or a polyhydric alcohol may be used in combination with water. Examples of polyhydric alcohols include propylene glycol, 1,3-butylene glycol, dipropylene glycol, and tripropylene glycol. These may be used alone or in combination of two or more. The content of the lower alcohol and / or polyhydric alcohol in the cosmetic is, for example, 1 to 20% by mass.

[0178] <Component (F): Oil> The present invention is a water-in-oil emulsion cosmetic, and therefore typically contains an oily ingredient (F).

[0179] The oils include, but are not limited to, organopolysiloxanes such as dimethylpolysiloxane (dimethicone), methylhydrogenpolysiloxane, methyltrimethicone, methylphenylpolysiloxane, and dimethylsiloxane-methylphenylsiloxane copolymers; cyclic siloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetramethyltetrahydrogencyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, tetramethyltetratrifluoropropylcyclotetrasiloxane, pentamethylpentatrifluoropropylcyclopentasiloxane, and diphenylsiloxyphenyltrimethicone; silicone oils such as modified organopolysiloxanes such as polyether-modified dimethylpolysiloxane, oleyl-modified dimethylpolysiloxane, polyvinylpyrrolidone-modified dimethylpolysiloxane, and alkyl-modified dimethylpolysiloxane;Glyceryl Tri-2-Ethylhexanoate, Isotridecyl Isononanoate, Isononyl Isononanoate, Cetyl 2-Ethylhexanoate, Isopropyl Myristate, Isopropyl Palmitate, 2-Ethylhexyl Palmitate, Octyldodecyl Myristate, Glyceryl Trioctanoate, Caprylic / Capric Triglyceride, Glyceryl Diisostearate, Glyceryl Triisostearate, Decaglyceryl Decaisostearate (Polyglyceryl-10 Decaisostearate), Propylene Glycol Dicaprate, Niacin Dicaprate Pentyl glycol, polyglyceryl triisostearate, diisostearyl malate, neopentyl glycol diethylhexanoate, polyglyceryl-10 decaisostearate, pentaerythrityl tetraisostearate, pentaerythrityl tetra-2-ethylhexanoate (pentaerythrityl tetraethylhexanoate), dipentaerythrityl pentaisostearate, dipentaerythrityl hexa(hydroxystearate / stearic acid / rosin acid), dialkyl carbonate, tridecyl trimellitate, cyclohexane-1,4 - Ester oils such as bisethoxydiglycol dicarboxylate, dimer dilinoleyl hydrogenated rosin condensate, hydrogenated castor oil monostearate, cetyl palmitate, polyethylene glycol distearate, glyceryl tribehenate, 2-ethylhexyl paramethoxycinnamate, and ethylhexyl salicylate; carbonized oils such as isododecane, isohexadecane, light isoparaffin, liquid paraffin, squalane, squalene, α-olefin oligomer, polybutene, liquid isoparaffin, heavy liquid isoparaffin, polyisobutylene, and hydrogenated polyisobutene. Hydrogenated oils; fatty acids such as oleic acid, isostearic acid, myristic acid, palmitic acid, isopalmitic acid, lauric acid, stearic acid, behenic acid, and polyhydroxystearic acid; higher alcohols such as oleyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, isostearyl alcohol, and 2-hexyldecanol; fluorinated oils such as perfluoropolyether, perfluorodecane, and perfluorooctane; liquid oils such as fragrances; paste-like oils such as cocoa butter, shea butter, castor oil, hydrogenated castor oil, hydrogenated coconut oil, and petrolatum;Examples of solid oils include paraffin wax, ceresin wax, microcrystalline wax, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, (ethylene / propylene) copolymer, cholesterol, phytosterol, stearyl-modified polysiloxane, hydrogenated oil, petrolatum, palm oil, etc.;

[0180] Among these, from the viewpoint of preventing secondary adhesion, the viscosity (kinematic viscosity) of the oil at 25°C is 1 to 50 mm 2 Preferably, the silicone contains a nonvolatile silicone having a viscosity (kinematic viscosity) of 1 to 50 mm / s (=centistokes (cS)) at 25°C. 2 Examples of commercially available products include KF-96A-6CS, KF-96-10CS, KF-96-50CS, and KF-56 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BELSIL DM 1 PLUS (manufactured by Wacker Asahi Kasei Silicone Co., Ltd.). Viscosity (kinematic viscosity) at 25°C: 1 to 50 mm 2 The content of non-volatile silicone in the cosmetic material is, for example, 1 to 30 mass %.

[0181] The content of the oil is not particularly limited, but from the viewpoints of preventing secondary adhesion and preventing dryness, it is preferably 20 to 90% by mass, and more preferably 30 to 70% by mass, in the water-in-oil emulsion cosmetic.

[0182] <Component (G): Surfactant> The present invention is a water-in-oil emulsion cosmetic, and therefore typically contains component (G) a surfactant.

[0183] The surfactants include, but are not limited to, PEG-9 dimethicone, PEG-9 methyl ether dimethicone, PEG-10 dimethicone, cetyl PEG / PPG-10 / 1 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, lauryl PEG-9 polydimethylsiloxyethyl dimethicone, cetyl PEG-9 polydimethylsiloxyethyl dimethicone, lauryl polyglyceryl 3-polydimethylsiloxyethyl dimethicone, and bis(PEG / PPG-14 / 14) dimethicone. , cetyl PEG / PPG-10 / 1 dimethicone, PEG-30 dipolyhydroxystearate, sorbitan monooleate, sorbitan sesquioleate, sorbitan dioleate, sorbitan monoisostearate, sorbitan diisostearate, sorbitan triisostearate, sorbitan monostearate, sorbitan sesquistearate, sorbitan distearate, polyglyceryl-2 triisostearate, etc., and one or more of these can be used.

[0184] The content of the surfactant is not particularly limited, but from the viewpoint of (re)dispersibility of the powder in the external phase, it is preferably 0.01 to 10% by mass, and more preferably 0.5 to 5% by mass in the water-in-oil emulsion cosmetic.

[0185] <Component (H): Acrylic-silicone graft copolymer> In the present invention, an acrylic-silicone graft copolymer may be further combined. The acrylic-silicone graft copolymer possesses the properties of both acrylic acid groups and dimethylpolysiloxane groups. The structure of these copolymers is not particularly limited, but may be a graft copolymer having dimethylpolysiloxane groups as the main chain and acrylic acid groups as side chains, a linear block copolymer or crosslinked polymer in which dimethylpolysiloxane groups and acrylic acid groups are alternately bonded, or a copolymer having acrylic acid as the main chain and dimethylpolysiloxane groups as side chains. The dimethylpolysiloxane groups may be linear or branched, or may be co-modified with an organic group such as an alkyl group. The properties are not particularly limited, but it is more preferable to use a copolymer that is liquid at 25°C. Specific examples include (acrylates / dimethicone) copolymer, (acrylates / stearyl acrylate / dimethicone methacrylate) copolymer, (acrylates / ethylhexyl acrylate / dimethicone methacrylate) copolymer, (acrylates / behenyl acrylate / dimethicone methacrylate) copolymer, etc. Commercially available products include KP-540, KP-545L, KP-550, KP-545, KP-562, KP-561P, KP-578 (manufactured by Shin-Etsu Chemical Co., Ltd.). Particularly preferred is (acrylates / ethylhexyl acrylate / dimethicone methacrylate) copolymer.

[0186] When an acrylic-silicone graft copolymer is used, the content in the cosmetic is, for example, 0.01 to 5% by mass, and may be 0.05 to 1% by mass.

[0187] <Optional ingredients> Cosmetics can contain various ingredients typically used in cosmetics, including thickeners (gelling agents, polymers), colorants, powders other than colorants, lower alcohols such as ethanol, polyhydric alcohols, UV absorbers, pH adjusters, antioxidants, metal chelating agents, preservatives, fragrances, and various pharmaceuticals.

[0188] Examples of ultraviolet absorbers include cinnamic acid derivatives, aminobenzoic acid derivatives, salicylic acid derivatives, benzophenone derivatives, phenylbenzimidazole derivatives, phenylbenzotriazole derivatives, and silicone derivatives. Specific examples include 2-ethylhexyl paramethoxycinnamate, octocrylene, polysilicone-15, t-butylmethoxydibenzoylmethane, ethylhexyl triazone, diethylaminohydroxybenzoylhexylbenzoate, bisethylhexyloxyphenol methoxyphenyl triazine, oxybenzone, methylenebisbenzotriazolyltetramethylbutylphenol, phenylbenzimidazole sulfonic acid, homosalate, and ethylhexyl salicylate. The ultraviolet absorber also includes oil-based agents. The ultraviolet absorbers may be used alone or in combination of two or more.

[0189] <Manufacturing method> The method for producing the water-in-oil cosmetic of the present invention is not particularly limited, but it can be prepared at room temperature, and examples include a method in which components (A), (B), and (D) are pre-dispersed in an oil agent containing component (C), and then an aqueous component is further added and emulsified.

[0190] <shape> The cosmetic of the present invention is not particularly limited, and examples thereof include makeup cosmetics such as a makeup base, foundation, eye color, lipstick, and lip cream, as well as skin care cosmetics such as lotion, emulsion, serum, pack, facial cleanser, and sunscreen. Among these, the cosmetic of the present invention is preferably used in makeup cosmetics such as sunscreen, makeup base (including BB cream), foundation, eye color, lipstick, and lip cream, and more preferably in sunscreen, makeup base, and foundation, because the effects of the present invention are significantly exhibited.

[0191] The shape of the item is not particularly limited, and examples include paste, cream, liquid, and multi-layered forms. Multi-layered refers to a type in which the powder settles, and the container is shaken before use. Furthermore, a propellant can be added to the water-in-oil emulsion cosmetic of the present invention to make it into an aerosol or spray formulation. The propellant is not particularly limited, as long as it is one typically used in cosmetics. Specific examples include liquefied petroleum gas, dimethyl ether, nitrogen, nitrous oxide, and carbon dioxide.

[0192] The viscosity of the water-in-oil emulsion cosmetic of the present invention (if a propellant is used, the viscosity of the base before the propellant is added) is preferably 25,000 mPa·s or less at 30°C, and more preferably 10,000 mPa·s or less. The higher the viscosity of the formulation, the better the powder dispersibility, but high viscosity also makes the cosmetic more likely to adhere to the mask. The configuration of the present invention makes it possible to achieve both powder redispersibility and reduced adhesion of the cosmetic to the mask, even in the low viscosity range where powder dispersibility is often an issue. [Example]

[0193] The effects of the present invention will be explained using the following examples and comparative examples. In the examples, the units "parts" and "%" are sometimes used, but unless otherwise specified, they represent "parts by mass" or "% by mass." Unless otherwise specified, each operation is carried out at room temperature (25°C).

[0194] Examples 1 to 48: Water-in-oil emulsion cosmetics (base sunscreen) A water-in-oil emulsion cosmetic (base sunscreen) having the composition shown in Table 1 (% by mass relative to 100% by mass of the total cosmetic, same below) was prepared using the manufacturing method described below, and the following items were evaluated using the evaluation methods and criteria shown below for powder redispersibility in the liquid, prevention of secondary adhesion (room temperature 33°C, humidity 60%), prevention of secondary adhesion (room temperature 25°C, humidity 90%), viscosity, duration of pore-covering effect, and lack of dryness (moisturizing feeling). The results are also shown in Table 1.

[0195] The crosslinked organosilicon resins of Production Examples 1 to 4, the theanine-treated zinc oxide of Production Example 5, and the theanine-treated hydroxyapatite of Production Example 6 in the table were produced by the following methods.

[0196] [Production Example 1: Decamethylcyclopentasiloxane solution of cross-linked organosilicon resin] Manufacturing method for cross-linked organosilicon resin / decamethylcyclopentasiloxane 60% solution A reactor was charged with 1,000 g of a 50% decamethylcyclopentasiloxane solution of a powdered hydrosilyl group-containing organosilicon resin (weight average molecular weight 4,430, hydrogen gas generation rate: 9.1 mL / g) represented by the average composition formula (E1) below, 98.6 g of an organopolysiloxane having vinyl groups at both ends represented by the formula (E2) below, 1,000 g of 2-propanol, and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid. The reaction was carried out by heating at 80°C for 6 hours. The solvent was then distilled off by heating under reduced pressure. 250 g of ethanol was then added, followed by 5 g of a 5% aqueous sodium hydroxide solution to hydrolyze the unreacted hydrosilyl groups, and 0.63 g of concentrated hydrochloric acid was added for neutralization. The reaction mixture was heated under reduced pressure to remove the solvent and then filtered to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin (60% resin purity) represented by the following formula (E3). The resulting decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was then heated to 120-130°C under reduced pressure to remove the decamethylcyclopentasiloxane, yielding a solid powder product (weight average molecular weight 156,000).

[0197] Formula (E1):(Me3SiO 1 / 2 ) 26.5 (HMe2SiO 1 / 2 ) 1.8 (SiO2) 36.0 Formula (E2):

[0198] [ka]

[0199] Formula (E3): (MeSiO 1 / 2 ) 26.5 (X 1 / 2 Me2SiO 1 / 2 ) 1.8 (SiO2) 36

[0200] [ka]

[0201] (Me represents a methyl group. The same applies below. In the above formula (E3), part of X may be a hydroxyl group.) [Production Example 2: Decamethylcyclopentasiloxane solution of cross-linked organosilicon resin] Manufacturing method for cross-linked organosilicon resin / decamethylcyclopentasiloxane 60% solution A reactor was charged with 800 g of a 50% decamethylcyclopentasiloxane solution of a solid hydrosilyl group-containing organosilicon resin (weight average molecular weight 5,940, hydrogen gas generation rate: 8.3 mL / g) represented by the average composition formula (E21) below, 67.9 g of an organopolysiloxane having vinyl groups at both ends represented by the formula (E22) below, 221.3 g of an organopolysiloxane having vinyl groups at both ends represented by the formula (E23) below, 800 g of 2-propanol, and 0.7 g of a 0.5% 2-propanol solution of chloroplatinic acid. The mixture was then heated at 105°C for 6 hours to carry out the reaction. The solvent was then distilled off by heating under reduced pressure. 200 g of ethanol was then added, followed by 4.0 g of a 5% aqueous sodium hydroxide solution to hydrolyze the unreacted hydrosilyl groups, and 0.5 g of concentrated hydrochloric acid was then added for neutralization. The reaction mixture was heated under reduced pressure to remove the solvent, and the residue was filtered to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin (60% pure resin content) represented by the following average composition formula (E24):

[0202] The resulting decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was heated to 120-130°C under reduced pressure, and the decamethylcyclopentasiloxane was removed to give a solid product (weight average molecular weight 221,000).

[0203] Formula (E21):(Me3SiO 1 / 2 ) 36.0 (HMe2SiO 1 / 2 ) 2.2 (SiO2) 48.0 Formula (E22):

[0204] [ka]

[0205] Formula (E23):

[0206] [ka]

[0207] Average composition formula (E24): (Me3SiO 1 / 2 ) 36.0 (X 1 / 2 Me2SiO 1 / 2 ) 1.1 (R 4 1 / 2 Me2SiO 1 / 2 ) 1.1 (SiO2) 48.0

[0208] [ka]

[0209] In the above formula (E24), R 4 And a part of X may be a hydroxyl group.

[0210] [Production Example 3: Decamethylcyclopentasiloxane solution of cross-linked organosilicon resin] Manufacturing method for cross-linked organosilicon resin / decamethylcyclopentasiloxane 60% solution A reactor was charged with 1,300 g of a 50% decamethylcyclopentasiloxane solution of a powdered hydrosilyl group-containing organosilicon resin (weight average molecular weight 8,550, hydrogen gas generation rate: 10.0 mL / g) represented by the average composition formula (E25) below, 40.8 g of an organopolysiloxane having vinyl groups at both ends represented by the formula (E26) below, 1,300 g of 2-propanol, and 0.8 g of a 0.5% 2-propanol solution of chloroplatinic acid. The reaction was then carried out by heating at 100°C for 6 hours. Next, 82.7 g of a vinyl-terminated polyoxyalkylene represented by the formula (E27) below was added, and the reaction was continued by heating at 100°C for 6 hours. The solvent was then distilled off by further heating under reduced pressure. 325 g of ethanol was then added, followed by 6.5 g of a 5% aqueous sodium hydroxide solution to hydrolyze the unreacted hydrosilyl groups, and 0.8 g of concentrated hydrochloric acid was added for neutralization. After neutralization, 195 g of 0.01 N hydrochloric acid solution was added to hydrolyze the allyl ether groups of the unreacted polyoxyalkylene, and the mixture was neutralized with 3.3 g of 5% deuterium oxide water. The reaction solution was then transferred to an autoclave, and 50 g of Raney nickel was added. The reaction was carried out at 100 ° C for 3 hours while flowing hydrogen at a hydrogen pressure of 1 MPa. The reaction mixture was heated under reduced pressure to distill off the solvent, and the mixture was filtered to obtain a decamethylcyclopentasiloxane solution of a crosslinked organosilicon resin represented by the following average composition formula (E28):

[0211] Furthermore, the resulting decamethylcyclopentasiloxane solution of the crosslinked organosilicon resin was heated to 120-130°C under reduced pressure to remove the decamethylcyclopentasiloxane, and the resulting product was a solid powder (weight average molecular weight 63,800).

[0212] Formula (E25):(Me3SiO 1 / 2 ) 52.0 (HMe2SiO 1 / 2 ) 3.8 (SiO2) 68.0 Formula (E26):

[0213] [ka]

[0214] Formula (E27): CH2=CH-CH2-O-(C2H4O)5(C3H6O)2-CH3 Formula (E28):(Me3SiO 1 / 2 ) 52.0 (X 1 / 2 Me2SiO 1 / 2 ) 1.1 (R 2 Me2SiO 1 / 2 ) 2.7 (SiO2) 68.0

[0215] [ka]

[0216] R 2 =-CH2-CH2-CH2-O-(C2H4O)5(C3H6O)2-CH3 In the above formula (E28), R 2 And a part of X may be a hydroxyl group.

[0217] [Production Example 4: Solution of cross-linked organosilicon resin in isododecane] Manufacturing method for 60% solution of cross-linked organosilicon resin / isododecane solution A reactor was charged with 1,000 g of a 50% isododecane solution of a powdered hydrosilyl group-containing organosilicon resin (weight average molecular weight 4,430, hydrogen gas generation rate: 9.1 mL / g) represented by the average composition formula (E1) below, 98.6 g of an organopolysiloxane having vinyl groups at both ends represented by the formula (E2) below, 1,000 g of 2-propanol, and 0.6 g of a 0.5% 2-propanol solution of chloroplatinic acid. The reaction was carried out by heating at 80°C for 6 hours. The solvent was then distilled off by heating under reduced pressure. 250 g of ethanol was then added, followed by 5 g of a 5% aqueous sodium hydroxide solution to hydrolyze unreacted hydrosilyl groups, and 0.63 g of concentrated hydrochloric acid was added for neutralization. The reaction mixture was heated under reduced pressure to distill off the solvent, and the mixture was filtered, yielding an isododecane solution of a crosslinked organosilicon resin (60% resin purity).

[0218] Furthermore, when the resulting solution of the crosslinked organosilicon resin in isododecane was heated to 120 to 130° C. under reduced pressure and the isododecane was removed, the product obtained was a solid powder. Formula (E1): (MeSiO 1 / 2 ) 26.5 (HMe2SiO 1 / 2 ) 1.8 (SiO2) 36.0 Formula (E2):

[0219] [ka]

[0220] Formula (E3): (MeSiO 1 / 2 ) 26.5 (X 1 / 2 Me2SiO 1 / 2 ) 1.8 (SiO2) 36

[0221] [ka]

[0222] In the above formula (E3), part of X may be a hydroxyl group.

[0223] [Production Example 5: Theanine-treated zinc oxide] A solution of 0.5 g of theanine (Taiyo Kagaku Co., Ltd.), a surface treatment agent, dissolved in 70 g of water was added to 49.5 g of fine particle zinc oxide (MZ-500: manufactured by Teika Corporation), mixed, air-dried, and pulverized in a pulverizer to obtain 1.0% treated zinc oxide.

[0224] [Production Example 6: Theanine-treated hydroxyapatite] A solution of 0.5 g of theanine (Taiyo Kagaku Co., Ltd.), a surface treatment agent, dissolved in 70 g of water was added to 49.5 g of hydroxyapatite (FL-HAP: manufactured by Taihei Chemical Industry Co., Ltd.), mixed, air-dried, and pulverized in a pulverizer to obtain 1.0% treated hydroxyapatite.

[0225] (Manufacturing method) A. Ingredients 1 to 27 were mixed uniformly. Components 28 to 49 were added to BA and mixed uniformly. The solution of ingredients 50 to 52 was added to CB and emulsified. The DC was degassed to obtain a water-in-oil base cosmetic.

[0226] (Evaluation method) 1. Evaluation of powder redispersibility in liquid The water-in-oil emulsion cosmetic product prepared by the prescribed method was filled into a glass bottle containing a stainless steel ball and left to stand in a thermostatic bath at 50°C. After one month, the state of settling of the fine particle metal oxide or hydroxyapatite was observed by shaking up and down and visually inspecting the bottle. Twenty expert evaluators evaluated the product on a four-point scale according to the following criteria. After shaking 5 times, the mixture becomes uniformly dispersed: 4 After 10 shakes, the mixture becomes uniformly dispersed: 3 After shaking 20 times, the mixture becomes uniformly dispersed: 2 Solidified at the bottom of the container and the stainless steel ball does not move even when shaken: 1 <Judgment criteria> (Judgment): (Average score) ◎: 3.5 points or more ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 1.0 points.

[0227] 2. Evaluation of secondary adhesion prevention under high temperature and humidity Twenty expert evaluators took an appropriate amount of water-in-oil emulsion cosmetics prepared using a prescribed method and spread it over their faces with their fingers. They then spent 10 hours in two rooms, one at room temperature of 33°C and humidity of 60%, and the other at room temperature of 25°C and humidity of 90%. They then observed the transfer of the cosmetic film when the cosmetics were wiped off with tissue under the same conditions. Each evaluator rated each item on a 5-point scale using the absolute evaluation method shown below, and the average score was calculated from the total scores of all panelists for each sample. At a room temperature of approximately 25°C and humidity of approximately 60%, the conditions inside the mask (N=5) were 31-33°C and 80-90%, so the above temperature and humidity settings simulated the conditions inside the mask.

[0228] <Evaluation criteria> (Score): (Evaluation result) 5 points: Very little makeup transfer to tissue 4 points: Makeup transfer to tissue is minimal 3 points: Average 2 points: Makeup transfers frequently to tissues 1 point: Makeup transfers to tissues a lot <Judgment criteria> (Judgment): (Average score) ◎: 4.0 points or more ○: 3.0 points or more and less than 4.0 points ×: Less than 3.0 points.

[0229] 3.Viscosity The viscosity was measured at 30°C using a B-type rotational viscometer, rotor No. 2, 6 rpm, and average value measurement for 1 minute.

[0230] 4. Sensory evaluation test method Twenty expert evaluators took an appropriate amount of the water-in-oil emulsion cosmetic and spread it over their faces with their fingers. Each evaluator rated and scored each evaluation item on a 5-point scale using the absolute evaluation method below. The average score was calculated from the total scores of all panelists for each sample, and the results were judged according to the following criteria.

[0231] (Evaluation items): (Evaluation criteria) Duration of pore covering effect: Whether or not the pores on the skin remain inconspicuous No dryness: Does the skin feel dry or any other unpleasant sensation after application? <Evaluation criteria> (Score): (Evaluation result) 5 points: Good 4 points: Fairly good 3 points: Average 2 points: slightly poor 1 point: Defective <Judgment criteria> (Judgment): (Average score) ◎: 4.0 points or more ○: 3.0 points or more and less than 4.0 points ×: Less than 3.0 points

[0232] [Table 1-1]

[0233] [Table 1-2]

[0234] [Table 1-3]

[0235] *1: MTY-100SAS (manufactured by Teika) *2: MZ-500 (manufactured by Teika Co., Ltd.) with surface treatment *3: MZY-505M (manufactured by Teika Co., Ltd.) *4: FL-HAP (manufactured by Taihei Chemical Industry Co., Ltd.) *5: MIYOSTAY Z20S-150 (manufactured by Miyoshi Kasei Co., Ltd.) *6: MZ-500FT (manufactured by Teika) *7: KP-578 (Shin-Etsu Chemical Co., Ltd.) *8: Salakos HS-6C (manufactured by Nisshin Oillio Group) *9: BELSIL DM 1 PLUS (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) *10: Silicon KF-96A (6CS) (Shin-Etsu Chemical Co., Ltd.) *11: Suntheanine CG100 (Taiyo Kagaku Co., Ltd.) *12: L-serine (manufactured by Nippon Rika Pharmaceuticals) *13: L-Threonine (manufactured by Junsei Chemical Co., Ltd.) *14: Glycine (manufactured by Thanachem) *15: Amino Coat (Asahi Kasei Finechem) *16: Amisoft LS-11 *17:AEROJIL R976S (manufactured by Nippon Aerosil Co., Ltd.) *18: 97% God Ball E-90C (manufactured by Suzuki Oil Industries Co., Ltd.) treated with 20% (dimethicone / vinyl dimethicone) crosspolymer (KSG-15, manufactured by Shin-Etsu Chemical Co., Ltd.) and the volatile oils evaporated. *19: God Ball E-90C (manufactured by Suzuki Oil Industries Co., Ltd.) *20: CELLOBEADS D-30 (manufactured by Daito Kasei Kogyo Co., Ltd.) treated with 2% magnesium stearate *21: MX3000C (manufactured by Soken Chemical & Engineering Co., Ltd.) *22: KSP-102 (Shin-Etsu Chemical Co., Ltd.) *23: Silica Microbead N-1505 (manufactured by JGC Catalysts and Chemicals) *24:CS-400 (manufactured by Negami Kogyo) *25: KSP-101 (Shin-Etsu Chemical Co., Ltd.) *26: Chemisnow MR-5C (manufactured by Soken Chemical Engineering Co., Ltd.) *27: KSP-100 (Shin-Etsu Chemical Co., Ltd.) *28: Tospearl 2000B* (manufactured by Momentive) *29: God Ball E2-824C (manufactured by Suzuki Oil Industries Co., Ltd.) *30: MSP-N050 (manufactured by Nikko Rica Corporation) From the above results, the water-in-oil emulsion cosmetics (sunscreen primers) of Examples 1 to 48 were excellent in all of the following: "powder redispersibility in liquid," "secondary adhesion prevention effect under high temperature conditions," "secondary adhesion prevention effect under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." On the other hand, Comparative Example 1, which did not contain component (A), was significantly inferior in terms of secondary adhesion prevention effect and absence of dryness; Comparative Example 2, which did not contain component (B), was significantly inferior in terms of powder redispersibility, secondary adhesion prevention effect, and absence of dryness; Comparative Example 3, which contained the film-forming agent trimethylsiloxysilicate instead of component (C), was significantly inferior in terms of secondary adhesion prevention effect, pore-covering effect, and absence of dryness; and Comparative Example 4, which did not contain component (D), was significantly inferior in terms of powder redispersibility and pore-covering effect.

[0236] Example 49: Water-in-oil emulsion shaking foundation A water-in-oil type shaking foundation was prepared using the composition and manufacturing method shown below. (composition) (mass%) (1) Isododecane 15.0 (2) Dimethylpolysiloxane (25°C kinematic viscosity 2cS) 10.0 (3) Cetyl PEG / PPG-10 / 1 Dimethicone*31 1.2 (4) Theanine (ingredient (B)) *11 0.3 (5) Neopentyl glycol diethylhexanoate 10.0 (6) 2-Ethylhexyl paramethoxycinnamate 5.0 (7) 2-(4-diethylamino-2-hydroxybenzoyl) Benzoic acid hexyl ester 2.0 (8) Crosslinked organosilicon resin of Production Example 1 Decamethylcyclopentasiloxane solution (resin purity 60%) (component (C)) 5.0 (9) Zinc oxide treated with 3% dimethylpolysiloxane (average particle size 25 nm) (ingredient (A)) 9.0 (10) Triethoxycaprylylsilane 2% treated black iron oxide 0.3 (11) Yellow iron oxide treated with 2% triethoxycaprylylsilane 1.8 (12) Triethoxycaprylylsilane 2% treated red iron oxide 0.6 (13) Triethoxycaprylylsilane 2% treated talc 1.0 (14) Spherical silica (average particle size 30 μm) *19 (component (D)) 5.0 (15) Remaining purified water (16) Ethanol 5.0 (17) Tripropylene glycol 10.0 (18) PEG / PPG / Polybutylene Glycol-8 / 5 / 3 Glycerin *32 1.0 *31 ABIL EM-90 (Evonik) *32 WILBRIDE S-753D (NOF Corporation) (Manufacturing method) A: Components (1) to (7) were heated to 80°C and mixed uniformly to dissolve. B: Components (8) to (14) were added to A and mixed and dispersed uniformly using a roll mill. C: Components (15) to (18) were mixed uniformly. D: C was added to B, and emulsified using a disper mixer at 2000 rpm at room temperature for 5 minutes. E:D was filled into a container to obtain a water-in-oil emulsion shaking foundation.

[0237] The water-in-oil emulsion shaking foundation of Example 49 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the water-in-oil emulsion shaking foundation of Example 49 at 30°C was 10,000 mPa s or less.

[0238] Example 50: Water-in-oil emulsion BB cream A water-in-oil emulsion BB cream was prepared using the composition and manufacturing method shown below. (composition) (%) (1) Isododecane 15.0 (2) Dimethylpolysiloxane (25°C kinematic viscosity 2cS) 10.0 (3) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone*40 0.8 (4) PEG-9 Polydimethylsiloxyethyl Dimethicone*41 0.4 (5) Sorbitan sesquiisostearate 0.6 (6) Neopentyl glycol diethylhexanoate 10.0 (7) 2-(4-diethylamino-2-hydroxybenzoyl) Benzoic acid hexyl ester 2.0 (8) Spherical cellulose powder (average particle size 30 μm) (ingredient (D)) *42 3.0 (9) Isododecane solution of the crosslinked organosilicon resin of Production Example 4 (Resin purity 60%) (Component (C)) 10.0 (10) Hydroxyapatite treated with 3% dimethylpolysiloxane (Average particle size 20nm) (Component (A)) 9.0 (11) Triethoxycaprylylsilane 2% treated black iron oxide 0.3 (12) Yellow iron oxide treated with 2% triethoxycaprylylsilane 1.8 (13) Triethoxycaprylylsilane 2% treated red iron oxide 0.6 (14) Triethoxycaprylylsilane 2% treated talc 1.0 (15) Dimethyl distearyl ammonium hectorite 1.5 (16) Benzyl dimethyl stearyl ammonium hectorite 0.6 (17) Serine*12 (ingredient (B)) 0.5 (18) Remaining purified water (19) Ethanol 5.0 (20) Dipropylene glycol 10.0 *40: KF-6038 (Shin-Etsu Chemical Co., Ltd.) *41: KF-6028 (Shin-Etsu Chemical Co., Ltd.) *42: CELLOBEADS D-30 (manufactured by Daito Kasei Kogyo Co., Ltd.) (Manufacturing method) A: Components (3) to (7) were heated to 80°C and mixed uniformly to dissolve. B: Components (10) to (16) were added to A and mixed and dispersed uniformly using a roll mill. C: Components (17) to (20) were mixed uniformly. D: Components (1), (2), (8), and (9) were added to B and dispersed, and C was added and emulsified at 2000 rpm at room temperature for 5 minutes using a disper mixer. E: D was filled into a container to obtain a water-in-oil emulsion BB cream.

[0239] The water-in-oil emulsion BB cream of Example 50 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the water-in-oil emulsion BB cream of Example 50 was 20,000 mPa·s at 30°C.

[0240] Example 51: Water-in-oil emulsion sunscreen (liquid) (composition) (%) 1. 3% dimethylpolysiloxane treated fine particle titanium dioxide (Average particle size 35nm) (Component (A)) 2.0 2. Fine particle zinc oxide treated with 5% dimethylpolysiloxane (average particle diameter 25 nm) (Component (A)) *3 10.0 3. (Acrylates / Ethylhexyl Acrylate / Dimethicone Methacrylate ) Copolymer *7 2.0 4. Dimethylpolysiloxane (25°C kinematic viscosity 1.1 cS) *9 15.0 5. Dimethylpolysiloxane (25°C kinematic viscosity 6cS) *10 10.0 6. Isododecane 3.0 7. Triethylhexanoin 2.0 8. Serine*12 (ingredient (B)) 1.0 9. Crosslinked organosilicon resin of Production Example 2 Decamethylcyclopentasiloxane solution (resin purity 60%) (component (C)) 5.0 10. Propylene glycol dicaprate 4.0 11. 2-Ethylhexyl para-methoxycinnamate 7.0 12. Diethylaminohydroxybenzoylhexyl benzoate 2.5 13. Bis-ethylhexyloxyphenol methoxyphenyl triazine 1.5 14. (Alkyl acrylate / vinyl acetate) copolymer Non-aqueous solvent dispersion*50 3.3 15. Polylactic acid (average particle size 18.5 μm) *51 (component (D)) 1.0 16. Dimethylpolysiloxane 3% treated spherical silica (average particle size 30 μm) (Component (D))*52 0.5 17. Phenoxyethanol 0.1 18. Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone*40 3.0 19. PEG-9 Polydimethylsiloxyethyl Dimethicone*41 1.0 20. 1,3-Butylene Glycol 3.0 21. Ethanol 5.0 22. Polyquaternium-104 0.5 23. Tremella fuciformis extract 0.1 24. Glycerin 1.0 25. Remaining purified water *50: Nissetsu U-3712A (Nippon Carbide Industries Co., Ltd.) *51: LUSMAPOL (registered trademark) AL120R (manufactured by LX Hausys) *52: 48.5g of spherical silica (*19) was mixed with 1.5g of surface treatment agent dimethylpolysiloxane (KF-96 10CS manufactured by Shin-Etsu Chemical Co., Ltd.) and 100g of isopropanol, and then dried under reduced pressure to obtain 3% dimethylpolysiloxane-treated spherical silica. (Manufacturing method) A: Components (1) to (9) were uniformly mixed and dispersed using a roll mill. B: A and components (10) to (19) were mixed and dispersed using a homomixer. C: Components 20 to 25 were mixed and dissolved uniformly. D: C was added to B and emulsified to obtain a sunscreen.

[0241] The sunscreen of Example 51 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the sunscreen of Example 51 at 30°C was 10,000 mPa s or less.

[0242] Example 52: Water-in-oil emulsion sunscreen (liquid) (composition) (%) 1. 2-Ethylhexyl paramethoxycinnamate 5.0 2. Theanine*11 (ingredient (B)) 2.0 3. Dimethylpolysiloxane (25°C kinematic viscosity 2cS) 5.0 4. Isododecane 10.0 5. Isododecane solution of the crosslinked organosilicon resin of Production Example 4 (resin pure content 60%) (Component (C)) 3.0 6. PEG-9 Polydimethylsiloxyethyl Dimethicone*41 2.0 7. PEG-9 Dimethicone 2.5 8. Diethylaminohydroxybenzoylhexyl benzoate 1.0 9. Dimethylpolysiloxane-treated zinc oxide particles (average particle size 25 nm) (Component (A)) 5.0 10. Dimethylpolysiloxane-treated titanium dioxide fine particles (average particle diameter 35 nm) (Component (A)) 5.0 11. Stearalkonium Hectorite 0.5 12. Dimethyl distearyl ammonium hectorite 0.5 13. Dimethylpolysiloxane 5% treated silica (average particle size 12±3μm) (Component (D))*61 2.0 14. Corn starch octenyl succinate aluminum (average particle size 15 μm) (Component (D))*59 1.0 15. Mica 5.0 16. Remaining purified water 17. Ethanol 5.0 18. Glycerin 1.0 19. Polyacrylamide mixture *60 0.5 20.Fragrance (appropriate amount) *59: DRY-FLO PURE (manufactured by Nouryon Japan Co., Ltd.) *60: Sepigel 501 (manufactured by SEPPIC) *61: 95g of spherical silica (Silica Microbead P-1505 manufactured by JGC Catalysts and Chemicals Co., Ltd.) was mixed with 5g of a surface treatment agent, dimethylpolysiloxane (KF-96 100CS manufactured by Shin-Etsu Chemical Co., Ltd.) and 50g of isopropanol, and then dried under reduced pressure to obtain 5% dimethylpolysiloxane-treated spherical silica. (Manufacturing method) A: Components (1) to (12) were uniformly mixed and dispersed using a roll mill. B: A and components (13) to (15) were mixed and dispersed uniformly using a homomixer. C: Components (16) to (20) were mixed uniformly. D: B and C were emulsified and filled into a container to obtain a sunscreen cosmetic.

[0243] The sunscreen of Example 52 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the sunscreen of Example 52 at 30°C was 10,000 mPa s or less.

[0244] Example 53: Aerosol foundation (composition) (%) 1. Fine particle titanium dioxide (average particle diameter 35 nm) (ingredient (A)) 3.0 2. Fine particle zinc oxide (average particle diameter 25 nm) (ingredient (A)) 6.0 3. Hydrophobic treated titanium dioxide (average particle size 0.25 μm) 10.0 4. Iron Oxide 3.0 5. (Acrylates / Ethylhexyl acrylate / Dimethicone methacrylate) Copolymer*7 2.0 6. Dimethylpolysiloxane (25°C kinematic viscosity 10cS) 10.0 7. Dimethylpolysiloxane (25°C kinematic viscosity 2cS) 3.0 8. Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone 1.0 9. Decamethylcyclopentasiloxane solution of crosslinked organosilicon resin of Production Example 1 (Resin purity 60%) (Component (C)) 5.0 10. 2-Ethylhexyl para-methoxycinnamate 7.0 11. Diethylaminohydroxybenzoylhexyl benzoate 2.5 12. Bis-ethylhexyloxyphenol methoxyphenyl triazine 1.5 13. Theanine *11 (ingredient (B)) 0.5 14. Threonine*13 (ingredient (B)) 1.0 15. Methyl methacrylate crosspolymer (average particle size 30 μm) *21 (Component (D)) 1.0 16. Trifluoropropyldimethyltrimethylsiloxysilicate 5.0 17. (Dimethicone / vinyl dimethicone) crosspolymer *27 (ingredient (D)) 2.0 18. Tripropylene Glycol 3.0 19. Remaining purified water (Manufacturing method) A. Components (1) to (6) were uniformly mixed and dispersed using a roller mill. B: A and components (7) to (17) were mixed in a homomixer and dispersed uniformly. C: Components (18) and (19) were mixed and added to B, and emulsified at room temperature using a homomixer to obtain a stock solution. D: 9 g of the concentrate obtained in C was poured into an aluminum pressure vessel, and the valve was then attached. 10 g of 0.15 LPG and 2 g of dimethyl ether were poured into the vessel through the valve to obtain an aerosol foundation.

[0245] The aerosol foundation of Example 53 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the concentrate of the aerosol foundation of Example 53 was 10,000 mPa s or less at 30°C.

[0246] Example 54: Water-in-oil emulsion BB cream A water-in-oil emulsion BB cream was prepared using the composition and manufacturing method shown below. (composition) (%) (1) Isododecane 15.0 (2) Dimethylpolysiloxane (25°C kinematic viscosity 2cS) 10.0 (3) Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone*40 0.8 (4) PEG-9 Polydimethylsiloxyethyl Dimethicone*41 0.4 (5) Sorbitan sesquiisostearate 0.6 (6) Neopentyl glycol diethylhexanoate 10.0 (7) 2-(4-diethylamino-2-hydroxybenzoyl) Benzoic acid hexyl ester 2.0 (8) Spherical cellulose powder (average particle size 30 μm) (ingredient (D)) *42 3.0 (9) Isododecane solution of the crosslinked organosilicon resin of Production Example 4 (Resin purity 60%) (Component (C)) 10.0 (10) Dimethylpolysiloxane 10% Triethoxycaprylylsilane 3% treated zinc oxide (average particle size 25 nm) *62 (ingredient (A)) 9.0 (11) 2% dimethylpolysiloxane treated black iron oxide 0.3 (12) Dimethylpolysiloxane 2% treated yellow iron oxide 1.8 (13) 2% dimethylpolysiloxane treated red iron oxide 0.6 (14) Dimethylpolysiloxane 2% treated talc 1.0 (15) Dimethyl distearyl ammonium hectorite 1.5 (16) Benzyl dimethyl stearyl ammonium hectorite 0.6 (17) Serine*12 (ingredient (B)) 0.5 (18) Remaining purified water (19) Ethanol 5.0 (20) Dipropylene glycol 10.0 *62: SALT-MZ-500 (13%) (Miyoshi Chemicals Co., Ltd.) (Manufacturing method) A: Components (3) to (7) were heated to 80°C and mixed uniformly to dissolve. B: Components (10) to (16) were added to A and mixed and dispersed uniformly using a roll mill. C: Components (17) to (20) were mixed uniformly. D: Components (1), (2), (8), and (9) were added to B and dispersed, and C was added, followed by emulsification in a disper mixer at 2000 rpm at room temperature for 5 minutes. E:D was filled into a container to obtain a water-in-oil emulsion BB cream.

[0247] The water-in-oil emulsion BB cream of Example 54 obtained in this manner was excellent in all of the following: "powder redispersibility in liquid," "effectiveness in preventing secondary adhesion under high temperature conditions," "effectiveness in preventing secondary adhesion under high humidity conditions," "sustained pore-covering effect," and "absence of dryness." The viscosity of the water-in-oil emulsion BB cream of Example 54 was 23,000 mPa·s at 30°C.

[0248] This application is based on Japanese Patent Application No. 2022-194315, filed on December 5, 2022, the disclosure of which is hereby incorporated by reference in its entirety.

Claims

1. The following components (A) to (D): (A) At least one selected from the group consisting of fine particle metal oxides, hydroxyapatite, and composite powders containing metal oxides and hydroxyapatite (B) at least one selected from the group consisting of amino acids and amino acid salts (C) A crosslinked organosilicon resin represented by the following average composition formula (1): 【Chemistry 1】 [In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, and R ２ are each independently a polyoxyalkylene-containing group, a polyglycerin-containing group, or R １ and each R ２ ３ SiO １／２ At least one R in the unit ２ is a polyoxyalkylene-containing group or a polyglycerin-containing group, and R ３ are each independently an organopolysiloxane-containing group, or R １ and each R ３ ３ SiO １／２ At least one R in the unit ３ is an organopolysiloxane-containing group, and X is a divalent group represented by the following general formula (2), where (R １ ３－ｐ (X １／２ ) ｐ SiO １／２ ) may be a plurality of different structural units, optionally R ２ , R ３ and a part of X may be a hydroxyl group; 【Chemistry 2】 (In the formula, R ４ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, e is an integer of 0≦e≦500, and k is an integer of 0≦k≦5. a1, a2, a3, a4, b, c, and d are numbers that satisfy the following conditions: 0<a1≦400, 0≦a2≦200, 0≦a3≦400, 0<a4≦10, 0≦b≦320, 0≦c≦320, 0<d≦1,000, 0.5≦(a1+a2+a3+a4) / d≦1.5, and p is 1. (D) Spherical powder with an average particle size of 5 to 50 μm Contains The content of the component (A) in the cosmetic is 3% by mass or more, The water-in-oil emulsion cosmetic, wherein the component (D) is at least one selected from the group consisting of silicone resin powder, urethane, nylon, cellulose acetate, cellulose, starch, polylactic acid, acrylic resin powder, and silica.

2. The following components (A) to (D): (A) At least one selected from the group consisting of fine particle metal oxides, hydroxyapatite, and composite powders containing metal oxides and hydroxyapatite (however, when component (A) has been surface-treated with component (B), N-acylamino acid treatment is excluded). (B) at least one selected from the group consisting of amino acids and amino acid salts (C) A crosslinked organosilicon resin represented by the following average composition formula (1): 【Chemistry 1】 [In the formula, R １ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, and R ２ are each independently a polyoxyalkylene-containing group, a polyglycerin-containing group, or R １ and each R ２ ３ SiO １／２ At least one R in the unit ２ is a polyoxyalkylene-containing group or a polyglycerin-containing group, and R ３ are each independently an organopolysiloxane-containing group, or R １ and each R ３ ３ SiO １／２ At least one R in the unit ３ is an organopolysiloxane-containing group, and X is a divalent group represented by the following general formula (2), where (R １ ３－ｐ (X １／２ ) ｐ SiO １／２ ) may be a plurality of different structural units, optionally R ２ , R ３ and a part of X may be a hydroxyl group; 【Chemistry 2】 (In the formula, R ４ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms and no aliphatic unsaturated bonds, e is an integer of 0≦e≦500, and k is an integer of 0≦k≦5. a1, a2, a3, a4, b, c, and d are numbers that satisfy the following conditions: 0<a1≦400, 0≦a2≦200, 0≦a3≦400, 0<a4≦10, 0≦b≦320, 0≦c≦320, 0<d≦1,000, 0.5≦(a1+a2+a3+a4) / d≦1.5, and p is 1. (D) Spherical powder with an average particle size of 5 to 50 μm Contains A water-in-oil emulsion cosmetic, wherein the content of the component (A) in the cosmetic is 3% by mass or more.

3. 3. The water-in-oil emulsion cosmetic according to claim 2, wherein the component (D) is at least one selected from the group consisting of silicone-based resin powder, urethane, nylon, cellulose acetate, cellulose, starch, polylactic acid, acrylic resin powder, and silica.

4. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the component (A) comprises at least one selected from the group consisting of zinc oxide, hydroxyapatite, and a composite powder containing a metal oxide and hydroxyapatite.

5. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the component (B) is at least one selected from the group consisting of an amino acid (salt) having a hydroxyl group and an amino acid (salt) having an amide bond.

6. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the weight-average molecular weight of component (C) is 1,000 to 1,000,000.

7. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the content of component (B) in the cosmetic is 0.1 to 1% by mass.

8. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the content of component (C) in the cosmetic is 0.1 to 20% by mass.

9. 3. The water-in-oil emulsion cosmetic according to claim 1, wherein the content of the component (D) in the cosmetic is 0.1 to 20% by mass.

10. 3. The water-in-oil emulsion cosmetic according to claim 1, which has a viscosity of 10,000 mPa·s or less at 30°C.

11. A water-in-oil emulsion cosmetic according to claim 1 or 2, wherein component (B) is at least one selected from neutral amino acids.

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