Organopolysiloxane and cosmetic containing same

Abstract

An organopolysiloxane that is represented by formula (1), has a small particle size of a water-in-oil emulsion, has a narrow distribution width, and is excellent in the production of a water-in-oil emulsion having excellent stability over time. [In the formula, R1 are each independently a group selected from C1-20 alkyl groups, C6-20 aryl groups, and C7-20 aralkyl groups.　R2 are each independently a group selected from formulae (2)-(7) (where x4 is an integer of 3-10; y1 is the average of the degrees of polymerization of glycerol groups and is 1-5; and the proportion of groups having the degree of polymerization with the highest content among the glycerol group degrees of polymerization 1-5 to all groups represented by (6) is 90% or more).]

Description

Organopolysiloxanes and cosmetics containing the same

[0001] This invention relates to organopolysiloxanes and cosmetics containing them. In this invention, compositions for cosmetic use may be referred to simply as "cosmetics."

[0002] Conventionally, silicone-based surfactants have been widely used as emulsifiers for emulsifying silicones. Among these, polyglycerin-modified silicones possess the skin-adherence properties of polyglycerin and the light feel characteristic of silicones, and are widely used in emulsified cosmetics and the like. However, it is known that these polyglycerin-modified silicones tend to cause a sticky feeling (Patent Document 1). Furthermore, compared to polyethylene oxide, a widely used hydrophilic group modifier, they have low surface activity, and the particle size distribution of emulsified cosmetics using them is wide, resulting in poor emulsification stability, which is a problem.

[0003] A common method for producing polyglycerin-modified silicones involves reacting allyl glycidyl ether with glycidol. However, this method often results in the formation of branched or cyclic byproducts, and it is difficult to control the composition due to the wide range of polymerization degrees. While formulations to reduce unreacted glycidol and byproduct polyglycerin have been investigated, there is no mention of the distribution of polyglycerin groups in the modified silicone (Patent Document 2).

[0004] While there are past examples of controlling the degree of polymerization of polyglycerin, there is no mention of its emulsifying power when used as a silicone modifier (Patent Document 3). Furthermore, there are reports of improved emulsification stability when a highly pure glycerin modifier with low ionic impurity content is used to modify silicone, but there is no mention of particle size distribution (Patent Document 4).

[0005] Japanese Patent Publication No. 2002-3334, Japanese Patent Publication No. 2004-277548, Japanese Patent Publication No. 2007-063210, International Publication No. 2014 / 104255

[0006] This invention has been made in view of the above circumstances, and aims to provide an organopolysiloxane that is excellent for producing water-in-oil emulsions with small particle size, narrow distribution width, and excellent temporal stability. In addition, it aims to provide cosmetics that have excellent effects such as temporal stability and feel depending on the dosage form.

[0007] As a result of diligent research to achieve the above objective, the inventors of the present invention have found that organopolysiloxanes modified with high-purity or glycerin-modifying agents with a narrow degree of polymerization distribution are excellent for producing water-in-oil emulsions with small particle size, narrow distribution width, and excellent long-term stability. Furthermore, they have discovered cosmetics with excellent long-term stability and, depending on the dosage form, excellent effects such as usability, leading to the present invention.

[0008] Accordingly, the present invention provides the following: 1. An organopolysiloxane represented by the following formula (1). [In the formula, R 1 R is independently selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. 2 These are independently selected from the following formulas (2) to (7), (In the formula, x1 is an integer between 3 and 10.) (In the formula, x² is an integer between 3 and 10.) (In the formula, x3 is an integer between 3 and 10.) (In the formula, x4 is an integer from 3 to 10, y1 is the average degree of polymerization of the glycerol group, which is from 1 to 5, and the proportion of groups with the highest degree of polymerization among 1 to 5 is 90% or more of the total number of groups shown in (6).) (In the formula, x5 is an integer from 3 to 10, y2 and y3 are the average values ​​of the degree of polymerization, each from 0 to 2, and y2 + y3 is from 0 to 2. Among those where y2 + y3 is 0, 1, and 2, the proportion of the group with the highest degree of polymerization accounts for 90% or more of the total groups shown in (7).) R 3 These are independently organopolysiloxane-containing groups, with one or more R groups per molecule. 3is an organopolysiloxane-containing group. a, b1, b2, b3, c, and d are respectively 1 ≦ a ≦ 20, 0 ≦ b1 ≦ 300, 0 < b2 ≦ 80, 0 ≦ b3 ≦ 20, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, and 10 ≦ b1 + b2 + b3 ≦ 400. The bonding order of each siloxane unit may be block or random. 2. The organopolysiloxane according to 1, wherein c = d = 0 in the formula (1). 3. The organopolysiloxane according to 1 or 2, wherein b3 > 0 in the formula (1). 4. In the organopolysiloxane, R 2 is a group represented by the formula (6), and the proportion of the group having the highest content among the degrees of polymerization of 1 to 5 of the glycerin group is 95% or more based on the total groups represented by (6). The organopolysiloxane according to any one of 1 to 3. 5. In the organopolysiloxane, R 2 is a group represented by the formula (7), and the proportion of the group having the highest content among the degrees of polymerization of 0, 1, and 2 for y2 + y3 is 95% or more based on the total groups represented by (7). The organopolysiloxane according to any one of 1 to 3. 6. In R 3 of the formula (1), the organopolysiloxane-containing group is represented by the following formulas (8) to (11) (where k is an integer of 0 ≦ k ≦ 5. R 4 is independently a group selected from an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, i is an integer of 0 ≦ i ≦ 500, and j1, j2, and j3 are each an integer of 0 to 2.) The organopolysiloxane according to any one of 1 to 5, which is an organopolysiloxane-containing group selected from the groups represented by the formula. 7. The organopolysiloxane according to any one of 1 to 6, having an HLB of 0.1 to 8.0. 8. A cosmetic containing the organopolysiloxane according to any one of 1 to 7. 9. An oil-in-water emulsion containing the organopolysiloxane according to any one of 1 to 7. 10. A cosmetic containing the oil-in-water emulsion according to 9. 11. The particle diameter of the oil-in-water emulsion is represented by the following formula (D. 90 - D 10 ) / D 50 (D10 , D 50 , D 90 The cosmetic composition according to claim 10, wherein the cumulative volume frequency calculated from the smallest particle size of the emulsion is 10%, 50%, and 90%, respectively.) The particle size distribution width shown is 2.5 or less. 12. Particle size D of the water-in-oil emulsion 50 A cosmetic composition according to 10 or 11, wherein the particle size D of the water-in-oil emulsion is 10 μm or less. 13. Particle size D of the water-in-oil emulsion 50 A cosmetic composition according to 10 or 11, wherein the particle size is 5 μm or less.

[0009] According to the present invention, it is possible to provide an organopolysiloxane that is excellent for producing water-in-oil emulsions with small particle size, a narrow particle size distribution, and excellent temporal stability. When this organopolysiloxane is used as an emulsifier, it is possible to provide cosmetics that have excellent temporal stability and, depending on the dosage form, have excellent effects such as a pleasant feel.

[0010] The present invention will be described in detail below, but is not limited to these descriptions. The present invention will be described in detail below in the case of use in cosmetics, but is not particularly limited to its use. In the present invention, ingredient names may be described as cosmetic names or International Nomenclature of Cosmetic Ingredient (INCI). If the cosmetic name and the INCI correspond, the cosmetic name or English description may be omitted.

[0011] [Component (A)] The present invention is an organopolysiloxane represented by the following formula (1), having an alkyl group or alkoxyalkyl group substituted with one or more hydroxyl groups in one molecule. [In the formula, R 1 R is independently selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. 2 R is independently a group selected from alkyl and alkoxyalkyl groups that is substituted with one or more hydroxyl groups, and there is one or more R in one molecule. 2 R is an alkyl group or alkoxyalkyl group substituted with the aforementioned hydroxyl group. 3is independently an organopolysiloxane-containing group, and one or more R in one molecule 3 is an organopolysiloxane-containing group. a, b1, b2, b3, c, d are respectively 1 ≦ a ≦ 20, 0 ≦ b1 ≦ 300, 0 < b2 ≦ 80, 0 ≦ b3 ≦ 20, 0 ≦ c ≦ 10, 0 ≦ d ≦ 10, and 10 ≦ b1 + b2 + b3 ≦ 400. The bonding order of each siloxane unit may be block or random.

[0012] In the above formula (1), R 1 is independently a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having C6 to 20 carbon atoms, and an aralkyl group having C7 to 20 carbon atoms. Among them, an alkyl group, an aryl group, an aralkyl group, and a fluoroalkyl group having 1 to 10 carbon atoms are preferable. More specifically, 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, etc., a trifluoropropyl group, etc. can be mentioned. An alkyl group having 1 to 5 carbon atoms, a phenyl group, or a trifluoropropyl group is more preferable.

[0013] R 2 is independently a group selected from the following formulas (2) to (7). (In the formula, x1 is an integer of 3 to 10.) (In the formula, x2 is an integer of 3 to 10.) (In the formula, x3 is an integer of 3 to 10.) (In the formula, x_{4} is an integer of 3 to 10, y_{_{1}} is the average value of the degree of polymerization of the glycerin group and is 1 to 5, and the proportion of the group having the highest content among the degrees of polymerization of 1 to 5 of the glycerin group is 90% or more with respect to the whole group represented by (6).) (In the formula, x_{5} is an integer of 3 to 10, y_{2}, y_{3} are the average values of the degree of polymerization and are respectively 0 to 2, and y_{2}+y_{3} is 0 to 2. Among those where y_{2}+y_{3} is 0, 1, and 2, the proportion of the group having the highest content among the degrees of polymerization is 90% or more with respect to the whole group represented by (7).)

[0014] In formula (2) above, x1 is an integer between 3 and 10, and preferably between 3 and 8. This range is preferred from the viewpoint of raw material availability. By setting x1 to 10 or less, the hydrophobicity does not become too high, and the emulsification stability is further improved.

[0015] In formula (3) above, x² is an integer between 3 and 10, and preferably between 3 and 8. This range is preferable from the viewpoint of raw material availability. By setting x² to 10 or less, the hydrophobicity does not become too high, and the emulsification stability is further improved.

[0016] In formula (4) above, x3 is an integer between 3 and 10, and preferably between 3 and 8. This range is preferable from the viewpoint of raw material availability. By setting x3 to 10 or less, the hydrophobicity does not become too high, and the emulsification stability is further improved.

[0017] In the above formula (6), x4 is an integer from 3 to 10, preferably from 3 to 8. This range is preferred from the viewpoint of raw material availability. Setting x4 to 10 or less prevents excessive hydrophobicity and further improves emulsion stability. y1 is the average degree of polymerization of the glycerin group, and is from 1 to 5, preferably from 2 to 3 from the viewpoint of emulsion stability. Setting y1 to 5 or less widens the distribution of glycerin, resulting in larger emulsion particle size. y1 is an average value and is one or more types of glycerin units with different degrees of polymerization. Here, glycerin units refer to the repeating units derived from glycerin enclosed by y1 in the above formula (6).

[0018] R 2When is the group represented by formula (6), y1 is an average value and consists of one or more types of groups with different degrees of polymerization of glycerin units, preferably a mixture of groups with degrees of polymerization of glycerin units from 1 to 5. Groups with a degree of polymerization of 6 or higher may also be included, but their content is preferably less than 1% (mol%, hereinafter the same) of the total groups represented by (6). The proportion of the group having the highest degree of polymerization among the groups with a degree of polymerization of glycerin units from 1 to 5 is preferably 90% or more, or 95% or more, of the total groups represented by (6). It is preferable that the component with a degree of polymerization of 2 or 3 each accounts for 90% or more individually, and more preferably 95% or more. Within this range, the emulsion particle size becomes finer, the particle size distribution becomes narrower, and the emulsifying properties are further improved.

[0019] In the case of the group represented by formula (7) above, x5 is an integer from 3 to 10, preferably from 3 to 8. y2 and y3 are average values ​​of the degree of polymerization, each being from 0 to 2, and y2 + y3 being from 0 to 2. A mixture may also be used in which the sum of the degrees of polymerization of the glycerin units grouped by y2 and the glycerin units grouped by y3 is from 0 to 2. Furthermore, a mixture may be included in which the sum of the degrees of polymerization of the glycerin units is 3 or more, but its content is preferably less than 1% (mol%, hereinafter the same) of the total group represented by (7), and it is more preferable that y2 + y3 consists of groups where 0, 1, and 2. Among the groups where y2 + y3 is 0, 1, and 2, the proportion of the group with the highest content of the degree of polymerization is 90% or more of the total group represented by (7), preferably 95% or more. Within this range, the emulsion particle size becomes finer, the particle size distribution becomes narrower, and the emulsification properties are further improved.

[0020] The method for synthesizing polyglycerin compounds having alkenyl groups at the terminal end, with a main component content of 90% or more, is not particularly limited, but it is preferable to refer to a method for synthesizing high-purity polyglycerin with a narrow distribution, such as those described in Japanese Patent Publication No. 5036989 and Japanese Patent Publication No. 3700250. On the other hand, synthesizing an epoxy compound and a compound having a hydroxyl group using a ring-opening reaction of the epoxy group in the presence of an alkaline catalyst is undesirable because the degree of polymerization of glycerin varies depending on the composition of the raw materials, and there is a high possibility that the main component content will be less than 90%.

[0021] The alkyl or alkoxyalkyl groups substituted with one or more hydroxyl groups listed above are not particularly limited, but formulas (4) to (7) are preferred because having multiple hydroxyl groups in a single modifying group increases hydrophilicity. Furthermore, formula (6) or formula (7) is preferred from the viewpoint of stability of the water-in-oil emulsion prepared using organopolysiloxane as an emulsifier.

[0022] In the above formula (1), R 3 These are independently organopolysiloxane-containing groups, for example, the groups represented by the following formulas (8) to (11). 3 3SiO 1 / 2 One or more R in each unit 3 R is an organopolysiloxane-containing group. 3 Some of these may be hydroxyl groups. (In the formula, k is an integer between 0 and 5. 4 (Each is independently selected from alkenyl groups having 2 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms, where i is an integer between 0 and 500, and j1, j2, and j3 are integers between 0 and 2.)

[0023] k is an integer between 0 and 5, preferably 0 and 2. i is an integer between 0 and 500, preferably 1 and 100, and more preferably 1 and 50. If i is greater than 500, the hydrophobicity is too high, which may lead to a lack of emulsification stability. j1 to j3 are integers between 0 and 2, inclusive.

[0024] a, b1, b2, b3, c, and d are within the following ranges: 1 ≤ a ≤ 20, preferably 1 ≤ a ≤ 10, and more preferably 1 ≤ a ≤ 5. When c = d = 0, a = 0 is preferred. 0 ≤ b1 ≤ 300, preferably 10 ≤ b1 ≤ 200, and more preferably 20 ≤ b1 ≤ 150. 0 < b2 ≤ 80, preferably 1 ≤ b2 ≤ 40, and more preferably 2 ≤ b2 ≤ 25. From the viewpoint of increasing hydrophilicity by increasing the amount of alkyl or alkoxyalkyl groups substituted with one or more hydroxyl groups, b2 is more preferably 3 or higher. 0 ≤ b3 ≤ 20, preferably 0 ≤ b3 ≤ 15, and more preferably 0 ≤ b3 ≤ 10. From the viewpoint of increasing emulsifying properties by increasing the amount of organopolysiloxane-containing groups, b3 > 0, and more preferably 1 or higher. Furthermore, from the viewpoint of emulsification, 10 ≤ b1 + b2 + b3 ≤ 400, preferably 20 ≤ b1 + b2 + b3 ≤ 200, and more preferably 30 ≤ b1 + b2 + b3 ≤ 150. 0 ≤ c ≤ 10, preferably 0 ≤ c ≤ 5, and more preferably 0 ≤ c ≤ 2. 0 ≤ d ≤ 10, preferably 0 ≤ d ≤ 5, and more preferably 0 ≤ d ≤ 2. Among these, linear organopolysiloxanes with c = d = 0 are also a preferred embodiment.

[0025] [Organopolysiloxane] R2 imparts hydrophilicity, and R imparts hydrophobicity. 3 The hydrophilicity of the organopolysiloxane can be controlled by changing the ratio of these components. The HLB calculated by the Griffin method is preferably 0.1 to 15, and among these, 0.1 to 8.0 is preferred, 0.1 to 6.0 is more preferred, and 0.5 to 4.5 is even more preferred for use as a water-in-oil type emulsifier. The Griffin method is defined as HLB value = 20 × (sum of molecular weights of hydrophilic components / total molecular weight). The HLB value is a numerical value that represents the affinity of the surfactant for water and oil.

[0026] The organopolysiloxane of the present invention preferably has a weight-average molecular weight in the range of 1,000 to 50,000, more preferably 1,000 to 10,000, even more preferably 2,000 to 10,000, and particularly preferably 3,000 to 10,000. Being within the above range is more preferable in terms of performance and workability such as filtration. If the weight-average molecular weight of the organopolysiloxane is 1,000 or more, when used as an emulsifier, molecular movement of the emulsifier at the interface can be suppressed, thus improving emulsification stability. Furthermore, if the weight-average molecular weight is 50,000 or less, emulsion formation is more sufficient. Organopolysiloxanes with a weight-average molecular weight of 3,000 to 10,000 are preferable because they can be used as water-in-oil emulsifiers not only with silicone oils but also when oils other than silicone oils are used in the oil phase. In this 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 under the following conditions (the same applies hereinafter).

[0027] [Measurement Conditions] Developing solvent: Tetrahydrofuran (THF) Flow rate: 0.6 mL / min Detector: Differential refractive index detector (RI) Detector temperature: 40°C Column: TSK Guardcolumn SuperH-H, TSKgel SuperHM-N (6.0 mm I.D. × 15 cm × 1), TSKgel SuperH2500 (6.0 mm I.D. × 15 cm × 1) (both manufactured by Tosoh Corporation) Column temperature: 40°C Sample injection volume: 50 μL (0.3 mass% THF solution)

[0028] [Manufacturing Method] The method for synthesizing the organopolysiloxane of the present invention is not particularly limited, but it can be obtained by an addition reaction between an organohydrogenpolysiloxane having a hydrosilyl group and a compound having an alkenyl group.

[0029] More specifically, the organopolysiloxane represented by formula (1) above can be obtained by hydrosilylation reacting the organohydrogenpolysiloxane represented by formula (12) below with one or more terminal alkenyl group-containing compounds represented by formulas (13), (14), (15), (16), (17), (18), (19), (20), (21), or (22) below (provided that at least one of the groups represented by formulas (13) to (18) below is included). This hydrosilylation reaction may also be carried out in the presence of a platinum catalyst or a rhodium catalyst. (In the formula, R 1 (a, b1, b2, b3, c, and d are as described above.) (In the formula, x1 is as described above.) (In the formula, x² is as described above.) (In the formula, x3 is as described above.) (In the equation, x4 and y1 are as described above.) (In the formula, x5, y2, and y3 are as described above.) (In the formula, k, R 4 i, j1, and j2 are the same as above.

[0030] The organohydrogenpolysiloxane represented by the above average composition formula (12) is M unit (R 1 3SiO 1 / 2 ), D unit ((R 1 2SiO 2 / 2 ) and (R 1 HSiO 2 / 2 )) is an essential component, and T units (R 1 SiO 3 / 2 ), Q unit (SiO 4 / 2 It consists of constituent components, with the following being optional components. Its weight-average molecular weight is preferably in the range of 1,000 to 50,000, and more preferably in the range of 1,000 to 20,000, from the viewpoint of performance and workability such as filtration.

[0031] The method for producing a crosslinked organosilicon resin by the above hydrosilylation reaction will be described in detail below. In the hydrosilylation reaction step between the organohydrogenpolysiloxane represented by formula (12) and the terminal unsaturated group-containing compound represented by formulas (13), (14), (15), (16), (17), (18), (19), (20), (21), or (22), the molar ratio of hydrosilyl group to terminal unsaturated group is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2.

[0032] The hydrosilylation reaction is preferably carried out in the presence of a platinum catalyst or a rhodium catalyst. For example, chlorplatinic acid, alcohol-modified chlorplatinic acid, chlorplatinic acid-vinylsiloxane complex, etc. are preferred. Furthermore, since excessive use of the catalyst will cause the reactant to become discolored, the amount of platinum or rhodium used is preferably 50 ppm or less, and particularly preferably 20 ppm or less.

[0033] Furthermore, the above addition reaction may be carried out in the presence of an organic solvent as needed. 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; aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane; monohydric 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, and 1-decanol; and dihydric aliphatic alcohols such as ethylene glycol and 1,2-propylene glycol. Ethanol, 1-propanol, and 2-propanol are particularly preferred from the viewpoint of reactivity.

[0034] The amount of organic solvent used is preferably 1 to 80% by mass of the total reaction solution (system), and more preferably 5 to 50% by mass. Within this range, the reaction system is kept uniform, and the reaction proceeds efficiently.

[0035] 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.

[0036] The process may also include a step to remove the rhodium or platinum catalyst used after the addition reaction using activated carbon. The amount of activated carbon used is preferably 0.001 to 5.0% by mass of the total system, and more preferably 0.01 to 1.0% by mass. Using this range further suppresses discoloration of the reactants.

[0037] Unreacted hydrosilyl groups may be present in the organopolysiloxane after the addition reaction. Furthermore, if the organic solvent used during the addition reaction is an aliphatic alcohol, a dehydrogenation reaction will proceed, and alkoxy groups may remain.

[0038] After the addition reaction, the process may include a step of substituting any remaining hydrosilyl groups with hydroxysilyl groups, if necessary. In particular, when used in cosmetics and the like, the hydrosilyl groups may become inactive over time due to dehydrogenation reactions, potentially generating hydrogen gas, which poses a safety risk. Therefore, it is preferable to include a step of substituting hydrosilyl groups with hydroxysilyl groups.

[0039] One method for substituting hydrosilyl groups with hydroxysilyl groups involves adding a basic catalyst such as an alkali metal carbonate, alkali metal bicarbonate, or alkali metal hydroxide to hydrolyze the unreacted hydrosilyl groups, followed by neutralization with an acidic catalyst equal to the molar equivalent of the basic catalyst. Specific examples of basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, and barium hydroxide as examples of strong basic catalysts, and sodium carbonate, calcium carbonate, and sodium bicarbonate as examples of weak basic catalysts. A strong basic catalyst is particularly preferable in terms of promoting the dehydrogenation reaction, and sodium hydroxide is specifically preferred. Specific examples of acidic catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid; sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, citric acid, and oxalic acid. In general, it is preferable to use acids or bases in combination with water and heat them at a temperature below the boiling point of water, rather than using them alone. Through this process, hydrosilyl groups (SiH groups) are replaced with hydroxysilyl groups (SiOH groups).

[0040] After the addition reaction, a deodorization process to reduce the odor may be included as needed. In particular, when used in cosmetics and the like, it is preferable to include a deodorization process because odor develops over time. The odor development mechanism of typical polyether-modified silicones is explained as follows: When an addition reaction is carried out between an allyl ether-modified polyether and a hydrogen polyorganosiloxane in the presence of a platinum catalyst, the allyl group undergoes internal transition as a side reaction, producing a propenyl ether-modified polyether. Since this propenyl ether-modified polyether does not have addition reactivity with the hydrogen polyorganosiloxane, it remains in the system as an impurity. When water reacts with this propenyl ether-modified polyether, it is thought that the propenyl ether is hydrolyzed, generating propionaldehyde, which is the cause of the malodor. Furthermore, it is known that the above hydrolysis reaction is further accelerated in the presence of an acid catalyst, and when polyether-modified silicone is used in water-based cosmetics, the oxidative degradation of the polyether causes the solution to become acidic over time, which accelerates the hydrolysis reaction mentioned above and causes odor development.

[0041] Two typical formulations can be cited as examples of deodorization processes. The first formulation 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 Publication No. 2137062).

[0042] Specific examples of acidic catalysts used in the first formulation include inorganic acids such as hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, and phosphoric acid; sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; and carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, benzoic acid, oxalic 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 one with a low boiling point, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Furthermore, from the viewpoint of processing efficiency, it is preferable to use strong acids such as hydrochloric acid or trifluoroacetic acid, but when using cyclic organopolysiloxane as a solvent, there is a risk of ring opening under strong acid conditions, so it is preferable to use a weak acid such as citric acid or acetic acid.

[0043] The processing temperature is preferably 80°C or lower to prevent oxidation of the hydrophilic groups. The amount of acidic aqueous solution added is preferably 0.1 to 100% by mass relative to the organic group-modified organosilicon resin, and more preferably 5 to 30% by mass.

[0044] From a productivity standpoint, a preferred method involves adding an aqueous solution to the reaction solution to bring the pH down to 7 or below, followed by heating, stirring, and then strip purification. The above strip purification can be carried out at room temperature or under reduced pressure, but the temperature is preferably 120°C or below. To efficiently perform strip purification under these temperature conditions, it is preferable to carry it out under reduced pressure, or, in the case of atmospheric pressure, under the flow of an inert gas such as nitrogen or argon.

[0045] The second formulation involves adding hydrogen to the solution after the addition reaction to alkylate the unsaturated double bond (a so-called hydrogenation reaction), thereby stably controlling the generation of propionaldehyde over time (U.S. Patent No. 5,225,509, Japanese Patent Publication No. 7-330907).

[0046] Hydrogenation reactions can be carried out using hydrogen or metal hydrides, and further categorized into homogeneous and heterogeneous reactions. These can be carried out individually or in combination. However, considering the advantage that no catalyst remains in the product, heterogeneous catalytic hydrogenation using a solid catalyst is the most preferred method.

[0047] Examples of solid catalysts include elements or compounds of nickel, palladium, platinum, rhodium, cobalt, chromium, copper, and iron. In this case, a catalyst support is not necessary, but if one is used, activated carbon, silica, silica-alumina, alumina, zeolite, etc., can be used. These catalysts can be used individually or in combination. The most preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is usually used by developing it in an alkali, it is especially important to carefully measure the pH of the reaction solution. Also, since the reaction system becomes weakly alkaline, hydrolysis reactions with acidic aqueous solutions are particularly effective for deodorization.

[0048] Hydrogenation reactions are generally preferably carried out at a pressure of 1 to 100 MPa and a temperature of 50 to 200°C. The hydrogenation reaction can be either palindromic or continuous. In the case of palindromic reactions, the reaction time depends on the amount of catalyst and temperature, but is generally 3 to 12 hours. The hydrogen pressure can be adjusted to a constant pressure as appropriate, but the endpoint of the hydrogenation reaction is the point at which the hydrogen pressure stops changing, which can be determined by carefully observing the pressure gauge.

[0049] The amount of aldehyde contained in the cross-linked organosilicon resin purified by such acid treatment or hydrogenation reaction can be reduced to 70 ppm or less, 20 ppm or less, and even 10 ppm or less.

[0050] Furthermore, it is possible to combine the two types of deodorization treatment processes mentioned above. While acid treatment can decompose and remove aldehyde compounds, there are limitations to completely removing unsaturated double bonds, and therefore it is not possible to completely suppress the generation of aldehydes, which are the cause of the odor. Hydrogenation treatment can reduce the amount of aldehyde compounds generated by eliminating unsaturated double bonds, but aldehyde condensates formed by the condensation of some aldehydes remain in the system even after the above treatment and are difficult to remove by strip purification. Therefore, complete deodorization is possible by applying a hydrogenation reaction to the solution after the addition reaction to alkylate the remaining unsaturated double bonds, and then adding an acid catalyst to decompose the aldehyde condensates in the system (International Publication No. 2002 / 05588).

[0051] [Water-in-oil emulsion] When the organopolysiloxane of the present invention is used as an emulsifier in a water-in-oil emulsion, the particle size distribution of the emulsion is narrowed, and the average particle size D 50 The particle size becomes smaller. Therefore, while maintaining high emulsification stability, the emulsion is less likely to break down when applied to the skin, making the oil phase feel more noticeable and resulting in a richer texture. When conventional polyglycerin-modified silicones are used, the average particle size tends to be large and the emulsion tends to have a wide particle size distribution. Emulsions with large particle sizes are known to coalesce easily and be unstable, but the emulsion obtained above can exist in a relatively stable state. Furthermore, it provides good applicability and a rich feel when applied to the skin, while also reducing the stickiness characteristic of surfactants and providing excellent moisture retention. In particular, creams (water-in-oil emulsions) have excellent applicability, richness, and long-term stability, and sunscreen milks have excellent applicability, richness, and suppression of white cast and whitening. In formulations containing titanium dioxide or zinc oxide, such as sunscreens, it exhibits effects such as suppression of white cast and whitening. Sunscreen creams have excellent long-term stability.

[0052] When the organopolysiloxane of the present invention is used as an emulsifier, the particle size of the water-in-oil emulsion is given by the following formula (D 90 -D 10 ) / D 50 (D10 , D 50 , D 90 The particle size distribution width shown by (where the cumulative volume frequencies calculated from the smallest particle size of the emulsion are 10%, 50%, and 90%, respectively) is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. When it is below the above upper limit, the particle size distribution of the emulsion becomes a differential film, and the emulsification stability is further improved. In this invention, the particle size of the emulsion refers to the volume-average particle size measured by a laser diffraction / scattering particle size distribution analyzer (for example, a laser diffraction / scattering particle size distribution analyzer LS 13 320 (manufactured by Beckman Coulter)). 10 , D 50 , D 90 This means that the cumulative volume frequencies calculated from the smallest particle size in the emulsion are 10%, 50%, and 90%, respectively.

[0053] In the present invention, the particle size D of the emulsion 50 From the viewpoint of refining the emulsion to improve its feel and emulsion stability, the particle size is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. By making the particle size 10 μm or less, coalescence between emulsion particles is prevented, and the emulsion becomes more stable.

[0054] [Cosmetics] The organopolysiloxane of the present invention can be incorporated into cosmetics in various ways. For example, it can be mixed in the oil phase, aqueous phase, or both and used as an emulsifier, texture modifier, thickener, compatibilizer, or insolubilizer, or used as a powder dispersant. The organopolysiloxane (A) of the present invention or the above-mentioned water-in-oil emulsion can be used for various purposes, but is particularly applicable as a raw material for all cosmetics applied externally to the skin and hair. In this case, the amount of organopolysiloxane (A) is preferably 0.1 to 20% by mass of the total cosmetic composition, and more preferably 0.1 to 10% by mass. From the viewpoint of sufficient emulsifying performance, 0.1% by mass or more is preferred. Also, from the viewpoint of usability, 20% by mass or less is preferred.

[0055] The cosmetic composition described above may be either an emulsion or a non-aqueous type. When a refreshing feel is desired, an emulsion is selected, and any of the following emulsion forms are acceptable: O / W emulsion, W / O emulsion, O / W / O emulsion, or W / O / W emulsion. From the viewpoint of obtaining the effects of the present invention, an oil-in-water emulsion (O / W emulsion) is preferred. When an oily feel or water resistance is desired, a non-aqueous composition or a powder composition can be selected, and in either case, a good cosmetic composition can be obtained. In this invention, "non-aqueous composition" refers to a composition that does not intentionally contain water.

[0056] The cosmetics of the present invention are not particularly limited, but can be applied to a variety of products, such as serums, lotions, creams, hair care products, foundations, makeup bases, sunscreens, concealers, blushes, lipsticks, lip glosses, balms, mascaras, eyeshadows, eyeliners, body makeup, deodorants, and nail cosmetics. Among these, makeup cosmetics such as lotions, creams, hair care products, and foundations, as well as cosmetics with sunscreen effects, are particularly preferred. The properties of the cosmetics of the present invention can be selected from a variety of forms, such as liquid, cream, solid, paste, gel, mousse, soufflé, clay, powder, and stick.

[0057] The viscosity of the cosmetic is not particularly limited and is selected appropriately depending on the dosage form. For example, in the case of liquid cosmetics, the viscosity is appropriately selected from ranges such as 15.0 to 80.0 mPa·s and 15.0 to 50.0 mPa·s. Among these, 15.0 to 30.0 mPa·s is preferred, and 15.0 to 25.0 mPa·s is more preferred. Setting it above the lower limit prevents the particles from coalescing and makes it more stable. Setting it below the upper limit improves the applicability. The viscosity of the cosmetic is the value at 25°C measured with a B-type viscometer, for example, a rotational viscometer (Toki Sangyo, VISCOMETER TVB-10M).

[0058] [Other Ingredients] The cosmetic composition of the present invention may contain various ingredients commonly used in cosmetics as other ingredients. Other ingredients may include, for example, (B) aqueous components, (C) oils, (D) powders, (E) surfactants, (F) cross-linked organopolysiloxanes, (G) film-forming agents, (I) other additives. These can be used individually or in appropriate combinations of two or more. These ingredients can be appropriately selected and used depending on the type of cosmetic composition, and their amounts can be known amounts depending on the type of cosmetic composition.

[0059] (B) Aqueous component The aqueous component is not particularly limited as long as it is an aqueous component that can be normally incorporated into cosmetics. Specifically, examples include water, lower alcohols such as ethanol (INCI: Alcohol), sugar alcohols such as erythritol, maltitol, xylitol, and sorbitol (INCI), and humectants such as polyhydric alcohols such as BG (INCI: Butylene Glycol), glycerin, PG (INCI: Propylene Glycol), DPG (INCI: Dipropylene Glycol), and pentylene glycol (INCI). These can be used individually or in appropriate combinations of two or more. When incorporating this component, the amount incorporated is preferably 0.1 to 90% by mass in the cosmetic.

[0060] (C) Oils The cosmetic composition of the present invention may contain oils. The oils may be volatile or non-volatile, and may be solid, semi-solid, or liquid at room temperature (25°C). Examples include silicone oils, natural animal and vegetable oils and fats and semi-synthetic oils, hydrocarbon oils, higher alcohols, fatty acids, ester oils, fluorinated oils, and ultraviolet absorbers. When oils are included, the amount of oil is not particularly limited, but is preferably 1 to 95% by mass of the total cosmetic composition, and more preferably 15 to 40% by mass.

[0061] ・Silicone oils include, for example, dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-96L-1cs, KF-96L-1.5cs, KF-96L-2cs, etc.), cyclotetrasiloxane (INCI), cyclopentasiloxane (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-995), cyclohexasiloxane (INCI), methyl trimethicone (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: TMF-1.5), caprylyl methicone (INCI), phenyl trimethicone (INCI), diphenyl dimethicone (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-54, KF-54HV), and diphenylsiloxy phenyl trimethicone (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-56 A) Examples include low-viscosity to high-viscosity linear or branched organopolysiloxanes such as methylhexylpolysiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane / methylphenylsiloxane copolymers; silicone rubbers such as amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxanes, pyrrolidone carboxylic acid-modified organopolysiloxanes; high-polymerization gum-like dimethicone (INCI); gum-like amino-modified organopolysiloxanes; and gum-like dimethylsiloxane / methylphenylsiloxane copolymers; as well as cyclic organopolysiloxane solutions of silicone gum and rubber, amino acid-modified silicones, fluorine-modified silicones, silicone resins, and silicone resin solutions.

[0062] - Solid Oily Components In the present invention, if it is desired to solidify the cosmetic composition, it is preferable to incorporate an oily component that is solid at 25°C. The oily component that is solid at 25°C preferably has a melting point of 40°C or higher, more preferably 60 to 110°C, and can include waxes, hydrocarbons, esters, higher alcohols, and higher fatty acids. It is not particularly limited as long as it is a raw material that can be normally incorporated into cosmetics. Specifically, carnauba wax (INCI: Copernicia Cerifera (Carnauba) Wax), sugarcane wax, candelilla wax (INCI: Euphorbia Cerifera (Candelilla) Wax), refined candelilla wax, rice wax, wood wax, jojoba wax, kapok wax, rice bran wax, white bayberry fruit wax, shea butter, cocoa butter, Japanese wax (INCI: Rhus Succedanea Fruit Wax), montan wax (INCI: Montan Wax), hydrogenated castor oil isostearate and other vegetable waxes, beeswax, beef tallow, beef bone tallow, lard (INCI: Lard), horse tallow (INCI: Horse) Examples include animal waxes such as fat, sheep fat, lanolin (INCI: Lanolin), oak tallow, shellac wax, and whale wax; semi-synthetic waxes such as lanolin esters, lanolin fatty acid esters, and beeswax acid esters; hydrogenated oils such as hydrogenated castor oil and hydrogenated coconut oil; hydrocarbon waxes such as solid paraffin, polyethylene, ceresin, ozokerite, and microcrystalline wax; wax esters such as synthetic beeswax; amino acids such as dioctyldodecyl lauroyl glutamate; higher alcohols such as stearyl alcohol, behenyl alcohol, and cetanol; fatty acids such as stearic acid and behenic acid; and silicone waxes such as acrylic silicone resins of acrylic-silicone graft or block copolymer (Shin-Etsu Chemical Co., Ltd.: acrylic-silicone graft copolymer: KP-561P, KP-562P, etc.), or derivatives thereof. Preferably, one or more selected from these are used.

[0063] ・Natural animal and vegetable oils and semi-synthetic oils, natural animal and vegetable oils and semi-synthetic oils, としては, アボガド oil (indicated name (INCI:Persea Gratissima (Avocado) Oil), アマニoil (indicated name (INCI: Linum) Usitatissimum (Linseed) Seed Oil)), アーモンド oil (indicated name (INCI: Prunus AmｽggallsDulces (Sweet Almond) Oil), Egoma Oil (representing name), Olive Oil (representing name (INCI: Olea Europaea (Oliv) Fruit Oil)), America Gaya Oil (representing name (INCI: Torreya Californica (California Nutmeg) Oil)), Kousi Gaya Oil (representing name (INCI: Cymbopogon Nardus (Citronella) Oil)), Kaya Seed Oil (representing name (INCI: Torreya Nucifera Seed)) Oil), Kyonin Oil (INCI: Kyonin Yu), Goma Oil (INCI: Sesamum Indicum (Sesame) Seed Oil), Komenuka Oil (INCI: Oryza Sativa (Rice) Bran Oil), Sazanka Oil (INCI: Camellia Kissi Seed Oil), Saflawo Oil (INCI: Carthamus Tinctorius (Saflawoer)) Seeded Oil), Daizu Oil (INCI: Glycine Soja (Soybean) Oil), Chami Oil (INCI: Camellia Sinensis Seeded Oil), Tsubaki Oil (INCI: Camellia Japan Seeded Oil), Evening Primrose Oil (INCI: Oenothera Biennis (Evening Primrose)) Oil), Natane Oil (name), Tomorokoshi Germ Oil (name (INCI: Zea Mays (Corn) Germ Oil)), Kome Germ Oil (name (INCI: Oryza Sativa (Rice) Germ Oil)),Combi germ oil (INCI: Triticum Vulgare (Wheat) Germ Oil) and other germ oils, paschic oil (INCI: Elaeis Guineensis (Palm) Oil), paschic kernel oil (INCI: Elaeis Guineensis (Palm) Kernel Oil), himashi oil (INCI: Ricinus Communis (Castor) Seeed) Helianthus Annuus (Sunflower) Seed Oil), Himawari Seed Oil (INCI: Helianthus Annuus (Sunflower) Seed Oil), Boodu Seed Oil (INCI: Vitis Vinifera (Grape) Seed Oil), Hohoba Seed Oil (INCI: Simmondsia Chinese (Jojoba) Seed Oil), Macadamia Seed Oil (INCI: Macadamia Ternifolia Seed Oil) Oil), Medow Floam Oil (INCI: Limnanthes Alba (Meadowfoam) Seeed Oil), Cotton Oil (INCI: Gossypium Herbaceum (Cotton) Seeed Oil), Yashi Oil (INCI: Cocos Nucifera (Coconut) Oil), Pearnut Oil (INCI: Arachis Hypogaea (Pearnut)) Natural plant oils such as Salmon liver oil (INCI: Shark Liver Oil), Salmon liver oil (INCI: Cod Liver Oil), Cod liver oil (INCI: Fish Liver Oil), Turtle oil (INCI: Tortle Oil), Mink oil (INCI: Mink Oil), Egg oil (INCI: Egg Oil), etc., and natural animal oils such as Hydrogenated Coconut oil (INCI: Hydrogenated Coconut ... Oil)), liquid ラノリン (indicated name (INCI: Lanolin Oll)) and other semi-synthetic oils and greases. ,

[0064] Liquid oily components include hydrocarbon oils, higher fatty acids, higher alcohols, esters, silicone oils, and fluorinated oils.

[0065] Hydrocarbon oils include, for example, linear or branched hydrocarbon oils, and may be volatile or non-volatile hydrocarbon oils. Specifically, examples include olefin oligomers (INCI), isoparaffins such as (C13,14) isoparaffins (INCI), isododecane (INCI), undecane (INCI), tridecane (INCI), dodecane (INCI), isohexadecane (INCI), hydrogenated polyisobutene (indication name (INCI): Hydrogenated Polyisobutene)), mineral oil (INCI), coconut alkanes (INCI), alkanes such as (C13-15) alkanes (INCI), etc.

[0066] • Higher fatty acids include oleic acid (INCI: Oleic Acid), linoleic acid (INCI: Linoleic Acid), linolenic acid (INCI: Linolenic Acid), arachidonic acid (INCI: Arachidonic Acid), eicosapentaenoic acid (EPA) (INCI: Eicosapentaenoic Acid), docosahexaenoic acid (DHA) (INCI: Docosahexaenoic Acid), isostearic acid (INCI: Isostearic Acid), and hydroxystearic acid (INCI: Hydroxystearic Acid). Examples include Acid.

[0067] • Higher alcohols: For example, alcohols with six or more carbon atoms are preferred as higher alcohols. Specific examples of higher alcohols include oleyl alcohol, isostearyl alcohol, 2-decyltetradecinol, cholesterol, phytosterol, polyoxyethylene cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (cerakyl alcohol), etc.

[0068] Esters are liquid oils in which a fatty acid having 1 to 20 carbon atoms is condensed with an alcohol having 1 to 20 carbon atoms, and include polyesters such as monoesters, diesters, and triesters. Specifically, alkyl glycol monoisostearate such as diisobutyl adipate (indication name (INCI): Diisobutyl Adipate)), dihexyldecyl adipate (indication name), diheptylundecyl adipate (indication name (INCI): Diheptylundecyl Adipate)), isostearyl isostearate (indication name (INCI): Isostearyl Isostearate)), isocetyl isostearate (indication name (INCI): Isocetyl Isostearate)), trimethylolpropane triisostearate (indication name (INCI): Trimethylolpropane Triisostearate)), and glycol diethylhexanoate (indication name (INCI): Glycol (Diethylhexanoate), Cetyl Ethylhexanoate (Indication Name (INCI): Cetyl Ethylhexanoate), Triethylhexanoin (Indication Name (INCI): Triethylhexanoin), Trimethylolpropane Triethylhexanoate (Indication Name (INCI): Trimethylolpropane Triethylhexanoate), Pentaerythrityl Tetraethylhexanoate (Indication Name (INCI): Pentaerythrityl Tetraethylhexanoate), Octyldodecyl Stearoyl Oxystearate (Indication Name (INCI): Octyldodecyl Stearoyl Octyldodecyl esters such as Stearate, oleyl oleate (indication name (INCI: Oleyl Oleate)), octyldodecyl oleate (indication name (INCI: Octyldodecyl Oleate)), decyl oleate (indication name (INCI: Decyl Oleate)), neopentyl glycol dioctanoate (indication name (INCI: Neopentyl Glycol Diethylhexanoate)), neopentyl glycol dicaprate (indication name (INCI: Neopentyl Glycol Dicaprate)),Triethyl citrate (INCI: Triethyl Citrate), Diethylhexyl succinate (INCI: Diethylhexyl Succinate), Amyl acetate (INCI: Amyl Acetate), Ethyl acetate (INCI: Ethyl Acetate), Butyl acetate (INCI: Butyl Acetate), Isocetyl stearate (INCI: Isocetyl Stearate), Butyl stearate (INCI: Butyl Stearate), Diisopropyl sebacate (INCI: Diisopropyl Sebacate), Diethylhexyl Sebacate (Indication name (INCI): Diethylhexyl Sebacate), Cetyl Lactate (Indication name (INCI): Cetyl Lactate), Myristyl Lactate (Indication name (INCI): Myristyl Lactate), Isononyl Isononanoate (Indication name (INCI): Isononyl Isononanoate), Isotridecyl Isononanoate (Indication name (INCI): Isotridecyl Isononanoate), Isopropyl Palmitate (Indication name (INCI): Isopropyl Palmitate), Ethylhexyl Palmitate (Indication name (INCI): Ethylhexyl Palmitic acid esters such as isopalmitate, hexyldecyl palmitate (indication name (INCI): Isocetyl Palmitate, Hexyldecyl Palmitate), myristic acid esters such as cholesteryl hydroxystearate (indication name (INCI): Cholesteryl Hydroxystearate), isopropyl myristate (indication name (INCI): Isopropyl Myristate), octyldodecyl myristate (indication name (INCI): Octyldodecyl Myristate), myristyl myristate (indication name (INCI): Myristyl Myristate)), ethylhexyl laurate (indication name (INCI): Ethylhexyl Laurate), hexyl laurate (indication name (INCI: Hexyl Laurate)),Examples of glyceride oils include dioctyldodecyl lauroyl glutamate (INCI: Dioctyldodecyl Lauroyl Glutamate), isopropyl lauroyl sarcosinate (INCI: Isopropyl Lauroyl Sarcosinate), diisostearyl malate (INCI: Diisostearyl Malate), glyceryl acetate (INCI: Glyceryl Acetate), and glyceryl stearate (INCI: Glyceryl Stearate).

[0069] Fluorine-based oils Examples of fluorine-based oils include perfluoropolyethers such as polyperfluoromethylisopropyl ether (INCI: Polyperfluoromethylisopropyl Ether), perfluorocarbons such as perfluorodecalin (INCI: Perfluorodecalin), and perfluorohexane (INCI: Perfluorohexane).

[0070] UV absorbers include homosalate (INCI), octocrylene (INCI), t-butyl methoxydibenzoylmethane (INCI: Butyl Methoxydibenzoylmethane), ethylhexyl salicylate (INCI: Ethylhexyl Salicylate), and diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate), oxybenzone-6 (Indication name (INCI: Benzophenone-6)), oxybenzone-9 (Indication name (INCI: Benzophenone-9)), oxybenzone-1 (Indication name (INCI: Benzophenone-1)), polysilicone-15 (INCI), dimethoxybenzylidene dioxoimidazolidinepropionate octyl (Indication name (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidinepropionate)), oxybenzone-2 (Indication name (INCI: Benzophenone-2)), terephthalylidene dicamphor sulfonic acid (Indication name (INCI: Terephthalylidene Diamphor Sulfonic Acid), Ethylhexyl Triazone (INCI), Methylbis(trimethylsiloxy)silylisopentyl Trimethoxycinnamate (INCI: Isopentyl Trimethoxyl Trisiloxane), Drometrizole Trisiloxane (INCI), Ethylhexyl Dimethyl PABA (INCI: Ethylhexyl Dimethyl PABA), Isopropyl Paramethoxycinnamate (INCI: Isopropyl Methoxyl Methoxinnamate), Ethylhexyl Methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate), bis-ethylhexyloxyphenol methoxyphenyl triazine (Indication name (INCI: Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine)),Oxybenzone-3 (Indication name (INCI: Benzophenone-3)), Oxybenzone-4 (Indication name (INCI: Benzophenone-4)), Oxybenzone-5 (Indication name (INCI: Benzophenone-5)), Phenylbenzimidazole sulfonic acid (Indication name (INCI: Phenylbenzimidazole Sulfonic Acid)), Methylene bis-benzotriazolyltetramethylbutylphenol (Indication name (INCI: Methylene Bis-Benzotriazolyl Tetramethylbutylphenol)), Glyceryl dimethoxycinnamate ethylhexanoate (Indication name (INCI: Glyceryl Ethylhexanoate) Examples include Dimethoxycinnamate, Glyceryl PABA (INCI: Glyceryl PABA), Methyl Diisopropylcinnamate (INCI: Diisopropyl Methyl Cinnamate), Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate (INCI: Ethylhexyl Dimethoxybenzylidene Dioxoimidazolidine Propionate), etc. Furthermore, it is possible to use UVA absorbers (e.g., diethylamino hydroxybenzoyl hexyl benzoate (INCI: Diethylamino Hydroxybenzoyl Hexyl Benzoate)) and UVB absorbers (e.g., ethylhexyl methoxycinnamate (INCI: Ethylhexyl Methoxycinnamate)) in combination, and it is also possible to combine them in any desired way.

[0071] Furthermore, with respect to the oil (C), it is preferable to select an oil with high compatibility with component (A) of the present invention in order to easily incorporate component (A) of the present invention into cosmetics. Even oils with poor compatibility can be incorporated by limited formulation or in combination with other compatibilizers.

[0072] (D) Powder The powder is not particularly limited as long as it is a raw material that can be normally incorporated into cosmetics, but examples include pigments, silicone spherical powders, etc. When incorporating powder, the amount of powder is not particularly limited, but it is desirable to incorporate it in an amount of 0.1 to 90% by mass of the total cosmetic, and more preferably 1 to 35% by mass.

[0073] - Coloring pigments: Any of the following can be used as coloring pigments: red iron oxide, yellow iron oxide, white titanium oxide, black iron oxide, red iron oxide, ultramarine, conch, manganese violet, cobalt violet, chromium hydroxide, chromium oxide, cobalt oxide, cobalt titanate, iron oxide-doped titanium oxide, iron titanate, (titanium / titanium oxide) calcined products, (lithium / cobalt) titanate, titanium nitride, iron hydroxide, γ-iron oxide and other inorganic brown pigments, inorganic yellow pigments such as yellow ochre, lake-formed tar dyes, lake-formed natural pigments and other colored pigments.

[0074] Furthermore, the shape of the pigment according to the present invention may be spherical, substantially spherical, rod-shaped, spindle-shaped, petal-shaped, strip-shaped, irregularly shaped, etc., and there are no particular limitations on its geometric form as long as it can impart color to cosmetics. Also, from the viewpoint of opacity, pigments with a particle size, i.e., a volume-average particle size, in the range of 150 to 600 nm are preferred. The volume-average particle size can be measured by TEM or the like. If it is less than 150 nm, the opacity is low, which may result in low coloring efficiency of cosmetics, and if it is greater than 600 nm, the feel of use may deteriorate.

[0075] Furthermore, the pigments according to the present invention may be partially or completely surface-treated with inorganic compounds such as alumina, aluminum hydroxide, silica, or hydrated silica.

[0076] The hydrophobic treatment of a colored pigment according to the present invention refers to surface treatment of the colored pigment with a hydrophobic treatment agent. The surface hydrophobic treatment agent for the colored pigment according to the present invention is not particularly limited as long as it can impart hydrophobicity, and examples include silicone treatment agents, waxes, paraffins, organofluorine compounds such as perfluoroalkyls and phosphates, surfactants, amino acids such as N-acyl glutamic acid, and metal soaps such as aluminum stearate and magnesium myristate.

[0077] More preferably, silicone treatment agents include silanes or silylation agents such as caprylsilane (Shin-Etsu Chemical Co., Ltd.: AES-3083) or trimethoxysilyldimethicone, silicone oils such as dimethyl silicone (Shin-Etsu Chemical Co., Ltd.: KF-96A series), methylhydrogen-type polysiloxane (Shin-Etsu Chemical Co., Ltd.: KF-99P, KF-9901, etc.), silicone branched silicone treatment agents (Shin-Etsu Chemical Co., Ltd.: KF-9908, KF-9909, etc.), and silicone compounds such as acrylic silicone (Shin-Etsu Chemical Co., Ltd.: KP-574, KP-541). In particular, the silicone powder treatment agent described in Japanese Patent Publication No. 3912961 is preferably used, and among them, triethoxysilylethylpolydimethylsiloxyethylhexyldimethicone (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-9909), which is a dimethylpolysiloxane having triethoxysilyl groups, polydimethylsiloxyethyl groups, and hexyl groups in its side chains, is effectively used because it exhibits high affinity even when the dispersion medium for dispersing the highly hydrophobic treated colored pigment according to the present invention is a mixed composition of silicone and hydrocarbons.

[0078] Furthermore, the above-mentioned surface hydrophobic treatment agents may be used individually or in combination of two or more types.

[0079] In the present invention, there are no particular limitations on the manufacturing method for surface-treating the colored pigment using a hydrophobic treatment agent, and it can be carried out by known methods. Surface treatment methods can be broadly classified into dry methods and wet methods. As a dry method, for example, the treatment can be carried out by mixing / contacting the colored pigment and the hydrophobic treatment agent used in the present invention using any agitator, pulverizer, mixer, disperser, etc., such as a Henschel mixer, ball mill, jet mill, kneader, planetary mixer, sand mill, attritor, ribbon blender, disper mixer, homo mixer, etc. In this case, the treatment may be carried out while applying energy such as heating, mechanochemical mechanical force, or superheated steam. Alternatively, after thoroughly mixing / contacting the colored pigment and the hydrophobic treatment agent, the treatment may be carried out by separately applying energy such as heating, mechanochemical mechanical force, or superheated steam. Alternatively, when mixing / contacting the hydrophobic agent with the colored pigment, to improve the dispersion efficiency of the hydrophobic agent, the hydrophobic agent may be pre-dissolved or dispersed in an arbitrary amount of water, solvent, or supercritical fluid, and then sprayed onto the colored pigment. In a wet method, the colored pigment and hydrophobic agent are dispersed in water, solvent, or supercritical fluid, mixed / contacted, and then the solvent is evaporated. Furthermore, it is possible to apply energy such as heating, mechanochemical force, or superheated steam to carry out the treatment.

[0080] Specific examples of colored pigments that have undergone hydrophobic surface treatment include the KTP-09 series, particularly KTP-09W, KTP-09R, KTP-09Y, KTP-09B, etc. (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0081] Inorganic powders include fine particles made from zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, cleaved talc, mica, kaolin, sericite, muscovite, synthetic mica, phlogopite, rose mica, biotite, lithium mica, silicic acid, silicon dioxide, fumed silica, hydrated silicon dioxide, aluminum silicate, magnesium silicate, aluminum magnesium silicate, calcium silicate, barium silicate, strontium silicate, metal tungstate salts, hydroxyapatite, vermiculite, hydylite, bentonite, montmorillonite, hectorite, zeolite, ceramics, dicalcium phosphate, alumina, aluminum hydroxide, boron nitride, glass, etc. Furthermore, examples of inorganic colored pearl pigments include titanium dioxide-coated mica, bismuth oxychloride, titanium dioxide-coated bismuth oxychloride, titanium dioxide-coated talc, fish scale foil, and titanium dioxide-coated colored mica. The fine particle metal oxide is one or more selected from fine particle titanium dioxide (INCI), fine particle iron-containing titanium dioxide, fine particle zinc oxide (INCI), fine particle cerium oxide (INCI), and composites thereof. These metal oxides may also be composite powders with other powders. The average primary particle diameter is preferably 200 nm or less, and more preferably 120 nm or less. If the particle diameter is larger than this, the ultraviolet protection function will decrease, and white residue will remain. The average primary particle diameter can be measured by transmission electron microscopy or the like.

[0082] The above-mentioned fine metal oxide particles are not particularly limited, being either untreated or having undergone known surface treatments used in the aforementioned cosmetics. Furthermore, they may be dispersions pre-dispersed with volatile oils or ester oils. Specific examples of dispersions include the SPD series, particularly SPD-T5, SPD-T5L, SPD-T6, SPD-T7, SPD-Z5, SPD-Z5L, etc. (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0083] Examples of metal powders include fine metal particles made of aluminum, copper, stainless steel, silver, etc.

[0084] Examples of organic powders include silicone, polyamide, polyacrylic acid / acrylic acid ester, polyester, polyethylene, polypropylene, polystyrene, styrene-acrylic acid copolymer, divinylbenzene-styrene copolymer, polyurethane, vinyl resin, urea resin, melamine resin, benzoguanamine, polymethylbenzoguanamine, tetrafluoroethylene, polymethyl methacrylate (e.g., polymethyl methacrylate), cellulose, silk, nylon, phenolic resin, epoxy resin, and polycarbonate. In particular, examples of silicones include silicone resin particles (specific examples include those manufactured by Shin-Etsu Chemical Co., Ltd.: KMP-590, KMP-591, KMP-592, etc.) and silicone resin-coated silicone rubber powder (specific examples include those manufactured by Shin-Etsu Chemical Co., Ltd.: KSP-100, KSP-101, KSP-102, KSP-105, KSP-300, KSP-411, KSP-441, etc.), which may be pre-dispersed in water or oil. Other examples include metal soaps, and specific examples include powders consisting of zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, magnesium myristate, zinc cetyl phosphate, calcium cetyl phosphate, and sodium zinc cetyl phosphate. Furthermore, organic dyes are also included, with specific examples including tar dyes such as Red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, as well as natural dyes such as carminic acid, laccaic acid, calsamine, brazilin, and crocin.

[0085] - Inorganic-organic composite powders: Examples of inorganic-organic composite powders include composite powders in which the surface of an inorganic powder is coated with an organic powder by a known or publicly used method.

[0086] Furthermore, the aforementioned powders may also be those with treated particle surfaces. The surface treatment agent is preferably one that can impart hydrophobicity from the viewpoint of water resistance of the cosmetic. The hydrophobic treatment agent is not particularly limited and can include silicone treatment agents, waxes, paraffins, organofluorine compounds such as perfluoroalkyl group modified phosphates, surfactants, amino acids such as N-acyl glutamic acid, aluminum stearate, and metal soaps such as magnesium myristate. More preferably, silicone treatment agents include silanes or silylation agents such as triethoxycaprylylsilane (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: AES-3083) or trimethoxysilyldimethicone (INCI), dimethyl silicone (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-96A series), methylhydrogen-type polysiloxanes such as hydrogen dimethicone (INCI) (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-99P, KF-9901, etc.), silicone oils such as silicone-branched silicone treatment agents (manufactured by Shin-Etsu Chemical Co., Ltd.: KF-9908, KF-9909, etc.), and acrylic silicones (manufactured by Shin-Etsu Chemical Co., Ltd.: KP-574, KP-541). Furthermore, the above surface hydrophobic treatment agents may be used alone or in combination of two or more types.

[0087] (E) Surfactants As surfactants, there are nonionic, anionic, cationic and amphoteric surfactants, and as long as they do not impair the effects of the present invention, those commonly used in cosmetics can be used. Among these surfactants, partially crosslinked polyether-modified silicones, partially crosslinked polyglycerin-modified silicones, linear or branched polyoxyethylene-modified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-modified organopolysiloxanes, linear or branched polyoxyethylene-alkyl-comodified organopolysiloxanes, linear or branched polyoxyethylene-polyoxypropylene-alkyl-comodified organopolysiloxanes, linear or branched polyglycerin-modified organopolysiloxanes, linear or branched polyglycerin-alkyl-comodified organopolysiloxanes, and linear or branched pyrrolidone-modified organopolysiloxanes are preferred. In these surfactants, it is preferable that the content of hydrophilic polyoxyethylene groups, polyoxyethylene polyoxypropylene groups, or polyglycerin residues accounts for 10 to 70% by mass of the molecule. Furthermore, when using partially crosslinked polyether-modified silicone or partially crosslinked polyglycerin-modified silicone, in a composition consisting of the crosslinked organopolysiloxane and a liquid oil at room temperature, it is preferable that the crosslinked organopolysiloxane swells by absorbing more than its own weight of the liquid oil relative to the liquid oil. As the liquid oil, liquid silicone, hydrocarbon oil, ester oil, natural animal and vegetable oil, semi-synthetic oil, or fluorine-based oil can be used in any component of the oil, for example, with a kinematic viscosity of 0.65 to 100 mm at 25°C. 2Examples of low viscosity silicones (1 / s), liquid paraffin, hydrocarbon oils such as squalane, isododecane, and isohexadecane, glyceride oils such as triethylhexanoin, ester oils such as isotridecyl isononanoate, and natural animal and vegetable oils such as jojoba oil. Specific examples of cross-linked organopolysiloxanes include those manufactured by Shin-Etsu Chemical Co., Ltd.: KSG-210, KSG-240, KSG-310, KSG-320, KSG-330, KSG-340, KSG-320Z, KSG-350Z, KSG-710, KSG-810, KSG-820, KSG-830, KSG-840, KSG-820Z, KSG-850Z, etc. Specific examples of non-crosslinked organopolysiloxanes include KF-6011, KF-6013, KF-6043, KF-6017, KF-6028, KF-6038, KF-6048, KF-6100, KF-6104, KF-6105, KF-6106, etc., manufactured by Shin-Etsu Chemical Co., Ltd. In any case, the amount of surfactant blended is preferably 0.1 to 20% by mass of the total cosmetic composition, and one or more types of crosslinked organopolysiloxanes, non-crosslinked organopolysiloxanes, or both can be appropriately selected within a range that does not impair the effects of the present invention.

[0088] (F) Crosslinked organopolysiloxane The crosslinked organopolysiloxane is not particularly limited as long as it is commonly used in cosmetics, and can be used alone or in appropriate combination of two or more types. Unlike the silicone powder described in (D) above, this crosslinked organopolysiloxane does not have a spherical shape. Also, unlike the surfactants (E) above, it is a compound that does not have a polyether or polyglycerin structure in its molecular structure. It is an elastomer that has structural viscosity when swollen with the oils (B) above. Specific examples include (dimethicone / vinyl dimethicone) crosspolymer, (dimethicone / phenyl vinyl dimethicone) crosspolymer, (vinyl dimethicone / lauryl dimethicone) crosspolymer, (lauryl polydimethylsiloxyethyl dimethicone / bis-vinyl dimethicone) crosspolymer, etc., as defined in cosmetic labeling names. These are commercially available as swollen products containing liquid oil at room temperature. Specific examples include KSG-15, KSG-1510, KSG-16, KSG-1610, KSG-18A, KSG-19, KSG-41A, KSG-42A, KSG-43, KSG-44, KSG-042Z, KSG-045Z, and KSG-048Z, all manufactured by Shin-Etsu Chemical Co., Ltd. When incorporating this component, the amount used is preferably 0.01 to 30% by mass as solid content in the cosmetic composition.

[0089] (G) Film-forming agents The film-forming agents are not particularly limited as long as they are raw materials that can be incorporated into cosmetics as usual, but specifically, latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate, and alkyl polyacrylates, dextrin, cellulose derivatives such as alkylcellulose and nitrocellulose, siliconeized polysaccharide compounds such as tri(trimethylsiloxy)silylpropylcarbamate pullulan, acrylic-silicone graft copolymers such as (alkyl acrylate / dimethicone) copolymers, silicone resins such as trimethylsiloxysilicate, silicone-based resins such as silicone-modified polynorbornene and fluorine-modified silicone resins, fluororesins, aromatic hydrocarbon resins, polymer emulsion resins, terpene resins, polybutene, polyisoprene, alkyd resins, polyvinylpyrrolidone-modified polymers, rosin-modified resins, polyurethanes, etc. are used.

[0090] Among these, silicone-based coating agents are particularly preferred, and among them, tri(trimethylsiloxy)silylpropylcarbamate pullulan (commercially available as a solvent-soluble product, manufactured by Shin-Etsu Chemical Co., Ltd.: TSPL-30-D5, ID), (alkyl acrylate / dimethicone) copolymer (commercially available as a solvent-soluble product, manufactured by Shin-Etsu Chemical Co., Ltd.: KP-543, KP-545, KP-549, KP-550, KP-545L, etc.), trimethylsiloxysilicate (commercially available as a solvent-soluble product, manufactured by Shin-Etsu Chemical Co., Ltd.: KF-7312J, X-21-5250, etc.), silicone-modified polynorbornene (commercially available as a solvent-soluble product, manufactured by Shin-Etsu Chemical Co., Ltd.: NBN-30-ID, etc.), and organosiloxane grafted polyvinyl alcohol polymers can be used, but are not limited to these. One or more types of film-forming agents can be used. When these ingredients are included, the amount is preferably 0.1 to 20% by mass in the cosmetic composition.

[0091] (I) Other additives Other additives include oil-soluble gelling agents, water-soluble thickeners, antiperspirants, preservatives and disinfectants, fragrances, salts, antioxidants, pH adjusters, chelating agents, cooling agents, anti-inflammatory agents, skin beautifying ingredients (whitening agents, cell activators, skin roughness improvers, blood circulation promoters, skin astringents, anti-seborrheic agents, etc.), vitamins, amino acids, water-soluble polymer compounds, fibers, inclusion compounds, etc.

[0092] Oil-soluble gelling agents include metal soaps such as aluminum stearate, magnesium stearate, and zinc myristate; amino acid derivatives such as N-lauroyl-L-glutamic acid and α,γ-di-n-butylamine; dextrin fatty acid esters such as dextrin palmitate, dextrin stearate, and dextrin 2-ethylhexanoate palmitate; sucrose fatty acid esters such as sucrose palmitate and sucrose stearate; fructooligosaccharide fatty acid esters such as fructooligosaccharide stearate and fructooligosaccharide 2-ethylhexanoate; benzylidene derivatives of sorbitol such as monobenzylidene sorbitol and dibenzylidene sorbitol; and organically modified clay minerals such as disteardimonium hectorite, stearalkonium hectorite, and hectorite.

[0093] • Water-soluble thickeners: As water-soluble thickeners, plant-derived polymers such as gum arabic, tragacanth, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), starch (rice, corn, potato, wheat, etc.), algae colloid, trant gum, locust bean gum, etc.; microbial polymers such as xanthan gum, dextran, succinoglucan, pullulan, etc.; animal-derived polymers such as collagen, casein, albumin, gelatin, etc.; starch-derived polymers such as carboxymethyl starch, methylhydroxypropyl starch, etc.; methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, nitrocellulose, sodium cellulose sulfate Examples include cellulose-based polymers such as sodium carboxymethylcellulose, crystalline cellulose, cationized cellulose, and cellulose powder; alginate-based polymers such as sodium alginate and propylene glycol alginate; vinyl-based polymers such as polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene-based polymers and polyoxyethylene polyoxypropylene copolymer polymers; acrylic-based polymers such as sodium polyacrylate, polyethyl acrylate, polyacrylamide, and acryloyldimethyl taurate salt copolymer; other synthetic water-soluble polymers such as polyethyleneimine and cationic polymer; and inorganic water-soluble polymers such as bentonite, aluminum magnesium silicate, montmorillonite, bydelite, nontronite, saponite, hectorite, and anhydrous silicic acid.

[0094] In particular, one or more water-soluble thickeners selected from plant-derived polymers, microbial polymers, animal-derived polymers, starch-derived polymers, cellulose-derived polymers, alginate-derived polymers, polyoxyethylene polyoxypropylene copolymer polymers, acrylic polymers, and inorganic water-soluble polymers are preferably used.

[0095] Examples of antiperspirants include aluminum hydroxyhalides such as chlorohydroxyaluminum, aluminum halides such as aluminum chloride, aluminum allantoin salts, tannic acid, persimmon tannin, sulfuric acid (aluminum / potassium), zinc oxide, zinc paraphenolsulfonate, calcined alum, tetrachloro(al / zirconium) hydrate, and trichlorohydrate glycine (al / zirconium). Particularly preferred as components that exhibit high efficacy are aluminum hydroxyhalides, aluminum halides, and complexes or mixtures thereof with oxyzirconyl oxyhalides and hydroxyzirconyl hydroxyhalides (e.g., tetrachloro(al / zirconium) hydrate, trichlorohydrate glycine (al / zirconium)).

[0096] Examples of preservatives and disinfectants include alkyl parahydroxybenzoates, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, imidazolidinyl urea, salicylic acid, isopropylmethylphenol, carbolic acid, parachlormethacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, iodide propynyl butylcarbamate, polylysine, photosensitizer, silver, and plant extracts.

[0097] Fragrances include natural and synthetic fragrances. Natural fragrances include plant-derived fragrances isolated from flowers, leaves, wood, and fruit peels, as well as animal-derived fragrances such as musk and civet. Synthetic fragrances include hydrocarbons such as monoterpenes, alcohols such as aliphatic alcohols and aromatic alcohols, aldehydes such as terpene aldehydes and aromatic aldehydes, ketones such as alicyclic ketones, esters such as terpene esters, lactones, phenols, oxides, nitrogen-containing compounds, and acetals.

[0098] Salts include inorganic salts, organic acid salts, amine salts, and amino acid salts. Examples of inorganic salts include sodium salts, potassium salts, magnesium salts, calcium salts, aluminum salts, zirconium salts, and zinc salts of inorganic acids such as hydrochloric acid, sulfuric acid, carbonic acid, and nitric acid. Examples of organic acid salts include salts of organic acids such as acetic acid, dehydroacetic acid, citric acid, malic acid, succinic acid, ascorbic acid, and stearic acid. Examples of amine salts and amino acid salts include salts of amines such as triethanolamine and salts of amino acids such as glutamic acid. In addition, salts of hyaluronic acid, chondroitin sulfate, etc., and even acid-alkali neutralization salts used in pharmaceutical formulations can be used.

[0099] Antioxidants: While not particularly limited, examples of antioxidants include carotenoids, ascorbic acid and its salts, ascorbyl stearate, tocopherol, tocopheryl acetate, tocopherol, p-t-butylphenol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, ferulic acid, thiotaurine, hypotaurine, sulfites, erythorbic acid and its salts, chlorogenic acid, epicatechin, epigallocatechin, epigallocatechin gallate, apigenin, campherol, myricetin, quercetin, and the like.

[0100] pH adjusters Examples of pH adjusters include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium bicarbonate, and ammonium bicarbonate.

[0101] Chelating agents include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, and phosphoric acid.

[0102] Cooling agents include L-menthol, camphor, and menthyl lactate.

[0103] Anti-inflammatory agents include allantoin, glycyrrhizic acid and its salts, glycyrrhetinic acid and stearyl glycyrrhetinate, tranexamic acid, and azulene.

[0104] • Skin beautifying ingredients include whitening agents such as arbutin, hydroquinone, tranexamic acid, ascorbic acid derivatives, glutathione, and saxifrage extract; cell activators such as royal jelly, photosensitizers, cholesterol derivatives, and calf blood extract; skin roughness improving agents; nonylic acid vanenylamide, benzyl nicotinate, β-butoxyethyl nicotinate, capsaicin, gingerol, cantharis tincture, ichthammol, caffeine, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine, trazoline, acetylcholine, verapamil, cepharanthine, and γ-oryzanol; skin astringents; and anti-seborrheic agents such as sulfur and thianthol.

[0105] Vitamins include vitamin A derivatives such as vitamin A oil, retinol, retinyl acetate, and retinyl palmitate; vitamin B2 derivatives such as riboflavin, riboflavin butyrate, and flavin adenine nucleotide; vitamin B6 derivatives such as pyridoxine hydrochloride, pyridoxine dioctanoate, and pyridoxine tripalmitate; vitamin B derivatives such as vitamin B12 and its derivatives; vitamin B15 and its derivatives; L-ascorbic acid, L-ascorbic acid dipalmitate, L-ascorbic acid-2-sulfate sodium, and L-ascorbic acid phosphate dicate. Examples include vitamin C compounds such as lium, vitamin D compounds such as ergocalciferol and cholecalciferol, vitamin E compounds such as α-tocopherol, β-tocopherol, γ-tocopherol, dl-α-tocopherol acetate, dl-α-tocopherol nicotinate, and dl-α-tocopherol succinate; nicotinic acid compounds such as nicotinic acid, benzyl nicotinate, and nicotinamide; vitamin H, vitamin P, calcium pantothenate, D-pantothenyl alcohol, pantothenyl ethyl ether, acetylpantothenyl ethyl ether, and other pantothenic acid compounds, as well as biotin.

[0106] Examples of amino acids include glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, aspartic acid, glutamic acid, cystine, cysteine, methionine, and tryptophan.

[0107] Nucleic acids include deoxyribonucleic acid, among others.

[0108] Examples of hormones include estradiol and ethenylestradiol.

[0109] Examples of inclusion compounds include cyclodextrins.

[0110] The cosmetic composition described above may be either an emulsion or a non-aqueous form. When a refreshing feel is desired, an emulsion form is selected. The emulsion form may be any of the following: O / W emulsion, W / O emulsion, O / W / O emulsion, or W / O / W emulsion. When an oily feel or water resistance is desired, a non-aqueous composition or a powder composition can be selected. In either case, a good cosmetic composition can be obtained. In this invention, "non-aqueous composition" refers to a composition that does not intentionally contain water. Among these, a non-aqueous composition that can be expected to have particularly high oil resistance is preferred.

[0111] The present invention will be described in more detail below with reference to production examples, examples, and comparative examples, but the present invention is not limited to the production examples and examples described below. Unless otherwise specified, "%" in the composition refers to mass %. In the formulas showing the structures below, the wavy lines of substituents indicate the parts that are bonded to the silicon atoms of the siloxane unit, and the bonding order of those having multiple types of repeating units may be in blocks or random. Organopolysiloxanes are used as production examples, and cosmetic examples are used as examples and comparative examples. The amounts indicated are those of the described formulations.

[0112] Table 1 below details the raw materials used in the manufacturing example. Polyglycerin containing a terminal alkenyl group, represented by formula (17).

[0113]

[0114] Alkenyl group-containing polyglycerin represented by formula (18)

[0115]

[0116] [Manufacturing Example 1] 100 g of organohydrogenpolysiloxane represented by formula (6) below average composition formula (E1) (weight average molecular weight 3,660, hydrosilyl group amount: 2.46 mmol / g), 25.3 g of 3-allyloxy-1,2-propanediol represented by formula (E2) below (vinyl group amount: 7.6 mmol / g), 125.3 g of 2-propanol, and 0.13 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 41.8 g of organopolysiloxane having a vinyl group at one end, represented by formula (E3) below, was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 10.0 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.17 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 6,120) represented by the following formula (E4). The HLB of the obtained organopolysiloxane was 3.0.

[0117]

[0118] [Manufacturing Example 2] 100 g of organohydrogenpolysiloxane represented by formula (3) below average composition formula (E5) (weight average molecular weight 4,210, hydrosilyl group amount: 2.85 mmol / g), 21.8 g of allyl glycol represented by formula (E6) below (vinyl group amount: 9.8 mmol / g), 97.5 g of 2-propanol, and 0.15 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 91.5 g of organopolysiloxane having a vinyl group at one end, represented by formula (E7) below, was added and the mixture was heated at 80°C for 3 hours. Subsequently, 7.3 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.12 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 8,980) represented by the following formula (E8). The HLB of the obtained organopolysiloxane was 2.0.

[0119]

[0120] [Manufacturing Example 3] 100 g of organohydrogenpolysiloxane represented by formula (2) below average composition formula (E9) (weight average molecular weight 3,450, hydrosilyl group amount: 2.32 mmol / g), 22.3 g of 7-octenyl alcohol represented by formula (E10) below (vinyl group amount: 7.8 mmol / g), 110.0 g of 2-propanol, and 0.07 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 44.4 g of organopolysiloxane having a vinyl group at one end, represented by formula (E11) below, was added and the reaction was carried out by heating at 80°C for 3 hours. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E12) (weight-average molecular weight 5,760). The HLB of the obtained organopolysiloxane was 2.7.

[0121]

[0122] [Manufacturing Example 4] 100 g of organohydrogenpolysiloxane represented by formula (4) below average composition formula (E13) (weight average molecular weight 3,170, hydrosilyl group amount: 2.21 mmol / g), 24.7 g of trimethylolpropane monoallyl ether represented by formula (E14) below (vinyl group amount: 5.7 mmol / g), 124.7 g of 2-propanol, and 0.12 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 60.4 g of organopolysiloxane having a vinyl group at one end, represented by formula (E15) below, was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 8.1 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.14 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E16) (weight-average molecular weight 5,870). The HLB of the obtained organopolysiloxane was 2.7.

[0123]

[0124] [Manufacturing Example 5] 100 g of organohydrogenpolysiloxane represented by formula (5) below average composition formula (E17) (weight average molecular weight 4,460, hydrosilyl group amount: 2.24 mmol / g), 28.7 g of 7-octene-1,2,3-triol represented by formula (E18) below (vinyl group amount: 6.2 mmol / g), 103.0 g of 2-propanol, and 0.13 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 41.0 g of organopolysiloxane having a vinyl group at one end, represented by formula (E19) below, was added and the mixture was heated at 80°C for 3 hours. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E20) (weight-average molecular weight 7,570). The HLB of the obtained organopolysiloxane was 3.4.

[0125]

[0126] [Manufacturing Example 6] 100 g of organohydrogenpolysiloxane represented by formula (7) below average composition formula (E21) (weight average molecular weight 3,750, hydrosilyl group amount: 2.13 mmol / g), 37.4 g of raw material K from Table 1 shown below formula (E22) (vinyl group amount: 3.6 mmol / g), 123.6 g of 2-propanol, and 0.14 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 102.7 g of organopolysiloxane having a vinyl group at one end shown below formula (E23) was added and heated at 80°C for 3 hours. Subsequently, 11.0 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.18 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 9,000) represented by the following formula (E24). The HLB of the obtained organopolysiloxane was 3.1.

[0127]

[0128] [Manufacturing Example 7] Method for producing organopolysiloxane of formula (6) 100 g of organohydrogenpolysiloxane represented by the following average composition formula (E25) (weight average molecular weight 2,890, hydrosilyl group amount: 2.08 mmol / g), 25.0 g of raw material A from Table 1 represented by the following formula (E26) (vinyl group amount: 4.8 mmol / g), 93.7 g of 2-propanol, and 0.07 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 66.3 g of organopolysiloxane having a vinyl group at one end, represented by the following formula (E27), was added and heated at 80°C for 3 hours. Subsequently, 10.0 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.17 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 5,530) represented by the following formula (E28). The HLB of the obtained organopolysiloxane was 2.6.

[0129]

[0130] [Manufacturing Example 8] 100 g of organohydrogenpolysiloxane represented by formula (6) (E29) below (weight-average molecular weight 3,600, hydrosilyl group amount: 2.22 mmol / g), 42.2 g of raw material B from Table 1 shown by formula (E30) below (vinyl group amount: 3.6 mmol / g), 128.0 g of 2-propanol, and 0.17 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 63.4 g of organopolysiloxane having a vinyl group at one end, shown by formula (E31) below, was added and the reaction was carried out by heating at 80°C for 3 hours. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E32) (weight-average molecular weight 7,400). The HLB of the obtained organopolysiloxane was 4.1.

[0131]

[0132] [Manufacturing Example 9] 100 g of organohydrogenpolysiloxane represented by formula (6) (E33) below (weight-average molecular weight 3,130, hydrosilyl group amount: 3.19 mmol / g), 52.7 g of raw material C from Table 1 shown in formula (E34) below (vinyl group amount: 4.8 mmol / g), 129.8 g of 2-propanol, and 0.15 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 82.0 g of organopolysiloxane having a vinyl group at one end, shown in formula (E35) below, was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 15.3 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.26 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 7,350) represented by the following formula (E36). The HLB of the obtained organopolysiloxane was 4.5.

[0133]

[0134] [Manufacturing Example 10] 100 g of organohydrogenpolysiloxane represented by formula (6) (E37) below (weight-average molecular weight 3,300, hydrosilyl group amount: 1.66 mmol / g), 18.7 g of raw material D from Table 1 shown by formula (E38) below (vinyl group amount: 4.8 mmol / g), 83.1 g of 2-propanol, and 0.09 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 97.2 g of organopolysiloxane having a vinyl group at one end shown by formula (E39) below was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 10.7 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.18 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 7,130) represented by the following formula (E40). The HLB of the obtained organopolysiloxane was 1.7.

[0135]

[0136] [Manufacturing Example 11] 100 g of organohydrogenpolysiloxane represented by formula (6) below average composition formula (E41) (weight average molecular weight 6,790, hydrosilyl group amount: 2.65 mmol / g), 6.4 g of raw material E3 from Table 1 shown below formula (E42) (vinyl group amount: 4.8 mmol / g), 116.0 g of 2-propanol, and 0.14 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 67.7 g of organopolysiloxane having a vinyl group at one end shown below formula (E43) was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 13.6 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.23 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E44) (weight-average molecular weight 13,860). The HLB of the obtained organopolysiloxane was 3.6.

[0137]

[0138] [Manufacturing Example 12] 100 g of organohydrogenpolysiloxane represented by formula (6) (E45) below (weight-average molecular weight 9,950, hydrosilyl group amount: 2.76 mmol / g), 27.9 g of 3-allyloxy-1,2-propanediol represented by formula (E46) below (vinyl group amount: 7.6 mmol / g), 127.9 g of 2-propanol, and 0.13 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 69.4 g of organopolysiloxane having a vinyl group at one end, represented by formula (E47) below, was added and the mixture was heated at 80°C for 3 hours. Subsequently, 9.0 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.15 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E48) (weight-average molecular weight 19,630). The HLB of the obtained organopolysiloxane was 2.8.

[0139]

[0140] [Comparative Example 1 of Manufacturing] Method for producing organopolysiloxane 100 g of organohydrogenpolysiloxane (weight-average molecular weight 4,030, hydrosilyl group amount: 2.23 mmol / g) represented by the following average composition formula (E49), 30.7 g of raw material F from Table 1 shown in the following formula (E50) (vinyl group amount: 4.8 mmol / g), 104.6 g of 2-propanol, and 0.13 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirmation of the reaction, 57.0 g of organopolysiloxane having a vinyl group at one end, shown in the following formula (E51), was added and heated at 80°C for 3 hours. Subsequently, 10.5 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.18 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 7,570) represented by the following formula (E52). The HLB of the obtained organopolysiloxane was 3.3.

[0141]

[0142] [Comparative Example 2 of Manufacturing] 100 g of organohydrogenpolysiloxane represented by the following average composition formula (E53) (weight-average molecular weight 3,480, hydrosilyl group amount: 2.44 mmol / g), 40.1 g of raw material G from Table 1 represented by the following formula (E54) (vinyl group amount: 3.6 mmol / g), 105.1 g of 2-propanol, and 0.11 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 91.8 g of organopolysiloxane having a vinyl group at one end, represented by the following formula (E55), was added and the mixture was heated at 80°C for 3 hours. Subsequently, 11.2 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.19 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 8,080) represented by the following formula (E56). The HLB of the obtained organopolysiloxane was 3.5.

[0143]

[0144] [Comparative Example 3] 100 g of organohydrogenpolysiloxane represented by the following average composition formula (E57) (weight-average molecular weight 3,490, hydrosilyl group amount: 3.16 mmol / g), 60.1 g of raw material H from Table 1 represented by the following formula (E58) (vinyl group amount: 3.6 mmol / g), 160.1 g of 2-propanol, and 0.16 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 106.6 g of organopolysiloxane having a vinyl group at one end, represented by the following formula (E59), was added and the reaction was carried out by heating at 80°C for 3 hours. Subsequently, 14.4 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.24 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E60) (weight-average molecular weight 9,300). The HLB of the obtained organopolysiloxane was 4.5.

[0145]

[0146] [Comparative Example 4] 100 g of organohydrogenpolysiloxane represented by the following average composition formula (E61) (weight-average molecular weight 3,480, hydrosilyl group amount: 2.44 mmol / g), 35.4 g of raw material I from Table 1 represented by the following formula (E62) (vinyl group amount: 2.8 mmol / g), 108.3 g of 2-propanol, and 0.11 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 131.2 g of organopolysiloxane having a vinyl group at one end, represented by the following formula (E63), was added and the mixture was heated at 80°C for 3 hours. Subsequently, 13.5 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.23 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 9,290) represented by the following formula (E64). The HLB of the obtained organopolysiloxane was 2.7.

[0147]

[0148] [Comparative Example 5] 100 g of organohydrogenpolysiloxane represented by the following average composition formula (E65) (weight-average molecular weight 3,570, hydrosilyl group amount: 2.10 mmol / g), 31.3 g of raw material J from Table 1 represented by the following formula (E66) (vinyl group amount: 3.6 mmol / g), 105.0 g of 2-propanol, and 0.13 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 75.1 g of organopolysiloxane having a vinyl group at one end, represented by the following formula (E67), was added and the mixture was heated at 80°C for 3 hours. Subsequently, 10.5 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.18 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane represented by the following formula (E68) (weight-average molecular weight 7,370). The HLB of the obtained organopolysiloxane was 3.0.

[0149]

[0150] [Comparative Example 6] Method for producing organopolysiloxane 100 g of organohydrogenpolysiloxane (weight-average molecular weight 4,770, hydrosilyl group amount: 1.90 mmol / g) represented by the following average composition formula (E69), 36.9 g of raw material L from Table 1 shown in the following formula (E70) (vinyl group amount: 3.1 mmol / g), 136.9 g of 2-propanol, and 0.11 g of 0.5% platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex / ethanol solution were charged into a reactor and the reaction was carried out by heating at 80°C for 3 hours. After confirming the reaction, 67.0 g of organopolysiloxane having a vinyl group at one end, shown in the following formula (E71), was added and heated at 80°C for 3 hours. Subsequently, 11.0 g of 0.01 N hydrochloric acid solution was added and heated at 80°C for 3 hours to hydrolyze the remaining propenyl ether, and the mixture was neutralized with 0.18 g of 5% sodium bicarbonate solution. The reaction mixture was heated under reduced pressure to remove the solvent, and the mixture was filtered to obtain an organopolysiloxane (weight-average molecular weight 9,730) represented by the following formula (E72). The HLB of the obtained organopolysiloxane was 3.6.

[0151]

[0152] [Examples 1-12, Comparative Examples 1-6] Creams (water-in-oil emulsions) with the compositions shown in the table below were prepared. (Manufacturing Method) Components 1 and 2 were mixed until uniform. Components 3-5 were then gently added after uniform mixing and stirred to form an emulsion. This was filled into a designated container to obtain a water-in-oil emulsion, or cream. The obtained creams were evaluated as follows. The results are shown in the table.

[0153] [Particle Size and Particle Size Distribution Measurement] The volume-based median diameter D of particles from the prepared water-in-oil emulsion of organopolysiloxane was measured using a laser diffraction / scattering particle size distribution analyzer (Microtrac MT3300EX2, Microtrac-Bell). 50 This is the value. Furthermore, the above device allows for the particle size distribution (D 90 -D 10 ) / D 50 The result was calculated.

[0154] [Evaluation of Usability] Ten expert panelists evaluated the obtained cream (water-in-oil emulsion) based on the following criteria for application (ease of spreading) and richness (thick feel). The results were judged based on the average of the ten panelists' scores, according to the following criteria: 5 points: Good 4 points: Fairly good 3 points: Average 2 points: Fairly bad 1 point: Bad

[0155] <Judgment Criteria> ◎◎: Average score of 4.5 or higher ◎: Average score of 4.0 or higher but less than 4.5 ○: Average score of 3.0 or higher but less than 4.0 △: Average score of 2.0 or higher but less than 3.0 ×: Average score less than 2.0

[0156] [Stability over Time] The initial viscosity of the obtained cream (water-in-oil emulsion) and the viscosity after storage in a constant temperature bath at 50°C for one month were compared and evaluated based on the change from the initial viscosity. ◎◎: ±0% or more and less than ±5% ◎: ±5% or more and less than ±10% ○: ±10% or more and less than ±15% △: ±15% or more and less than ±20% ×: ±20% or more Initial viscosity: The viscosity of the obtained cream (water-in-oil emulsion) at 25°C after one week was measured using a rotational viscometer (Toki Sangyo, VISCOMETER TVB-10M) with spindle No. 23 at a rotation speed of 6 rpm. The viscosity after storage was also measured in the same manner at a temperature of 25°C. Viscosity change rate (%) = 100 - (viscosity after storage at 50°C for 1 month / initial viscosity) × 100

[0157]

[0158]

[0159] Compared to Comparative Examples 1 to 6, the cream (water-in-oil emulsion) of the present invention had a smaller average particle size and a narrower particle size distribution, resulting in superior applicability, richness, and long-term stability.

[0160] [Example 13, Comparative Examples 7 and 8] Sunscreen milk (water-in-oil emulsion) with the composition shown in the table below was prepared. (Manufacturing method) Components 1 to 6 were mixed until uniform. Components 9 to 12 were then gently added after uniform mixing and stirred to form an emulsion. Components 7 and 8 were then added to the emulsion and mixed. This was filled into a designated container to obtain sunscreen milk. The obtained sunscreen milk was evaluated as follows.

[0161] [Evaluation of Usability] Ten expert panelists evaluated the obtained sunscreen milk based on the following criteria: applicability (ease of spreading), richness (thick feel), white cast (resistance to whitening when applied), and whitening (resistance to whitening when wet after application and drying). The results were judged based on the average values ​​of the ten panelists, according to the following criteria. The same method was used for evaluating applicability and richness.

[0162] - When the same amount of whitening was applied, a score was given as follows: 5 points for very high transparency after application, 4 points for high transparency, 3 points for a slightly white finish, 2 points for whitening, and 1 point for very whitening. ◎: Average score of 4.0 points or higher ○: Average score of 3.0 points or higher but less than 4.0 points △: Average score of 2.0 points or higher but less than 3.0 points ×: Average score less than 2.0 points

[0163] Sunscreen cosmetics were applied to a 1 mm thick whitened quartz glass plate using a bar coater (KOSP-CN-05M, manufactured by Cortec Co., Ltd.), dried at 50°C for 2 hours, immersed in purified water for 10 minutes, and then the water was removed before measurement. A spectrophotometer (U-3310) manufactured by Hitachi High-Tech Science was used for measurement, and the transmittance at 410 nm was evaluated. ◎: 90% or more ○: 85% or more to less than 90% △: 80% or more to less than 85% ×: Less than 80%

[0164] (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 25% (Dimethicone / Polyglycerin-3) crosspolymer (indication name (INCII: Dimethicone / Polyglycerin-3 crosspolymer)) and 75% dimethicone (indication name (INCI: DIMETHICONE)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 7% (Dimethicone / Vinyl Dimethicone) crosspolymer (indication name (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer)) and 93% cyclopentasiloxane (indication name (INCI: Cyclopentasiloxane)) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 polydimethylsiloxyethyl dimethicone (Indication name (INCI: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone)) (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Dimethicone (Indication name (INCI: DIMETHICONE)) (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd.: Titanium dioxide (Indication name (INCI: Titanium Dioxide) 40% dispersion) (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd.: Zinc oxide (Indication name (INCI: Zinc Oxide) 60% dispersion)

[0165] The sunscreen milk of the present invention was superior to Comparative Examples 7 and 8 in terms of application, richness, white cast, and whitening.

[0166] The following are examples of cosmetic formulations. The following were evaluated using the same criteria as above. [Example 15] W / O Cream Composition % 1. KSG-310 (Note 1) 3 2. KSG-44 (Note 2) 1 3. Composition of Manufacturing Example 5 0.2 4. Squalane 10.8 5. BG 6 6. Ethanol 5 7. Glycerin 2 8. Sodium Citrate 0.2 9. Sodium Chloride 0.5 10. Phenoxyethanol 0.2 11. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 30% (PEG-15 / Lauryl Dimethicone) crosspolymer (indication name (INCII: PEG-15 / Lauryl Dimethicone Crosspolymer)) and 70% mineral oil (indication name (INCI: Mineral Oil)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 30% (Vinyl Dimethicone / Lauryl Dimethicone) crosspolymer (indication name (INCI: Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer)) and 70% squalane (indication name (INCI: Squalane)) <Preparation of cosmetic> A: Components 1 to 4 were mixed uniformly. B: Components 5 to 11 were uniformly mixed. C: The mixture obtained in B was added to the mixture obtained in A and emulsified to obtain a W / O cream. The obtained W / O cream had excellent applicability and richness, was moist, and had good stability over time.

[0167] [Example 16] W / O Cream Composition % 1. Organopolysiloxane from Manufacturing Example 8 4 2. KSG-18A (Note 1) 1 3. KF-6104 (Note 2) 3 4. KF-96A-6cs 13 5. BG 8 6. Ethanol 5 7. Sorbitol 2 8. Sodium citrate 0.2 9. Sodium chloride 0.5 10. Methylparaben 0.1 11. Dipotassium glycyrrhizate 0.2 12. Arbutin 3 13. Sodium pyrosulfite 0.02 14. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) (Indication name (INCI): Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) and 85% diphenylsiloxy phenyl trimethicone (Indication name (INCI): Diphenylsiloxy) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI): Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone) <Preparation of cosmetic> A: Components 1 to 4 were uniformly mixed. B: Components 5 to 14 were uniformly mixed. The mixture obtained in C:B was added to the mixture obtained in A and emulsified to obtain a W / O cream. The obtained W / O cream had excellent applicability and richness, was moist, and had good stability over time.

[0168] [Example 17] W / O Cream Composition % 1. KSG-840 (Note 1) 3 2. KSG-44 (Note 2) 3 3. Organopolysiloxane from Manufacturing Example 8 0.5 4. Squalane 6 5. Jojoba Seed Oil 14 6. KSP-100 (Note 3) 1 7. BG 5 8. Glycerin 3 9. Sodium Hyaluronate (1% aqueous solution) 1.5 10. Sodium Citrate 0.2 11. Sodium Chloride 0.5 12. Ethylhexylglycerin 0.1 13. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 30% (Lauryl Dimethicone / Polyglycerin-3 Crosspolymer (Indication name (INCI): Lauryl Dimethicone / Polyglycerin-3 Crosspolymer) and 70% Squalane (Indication name (INCI): Squalane) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 30% (Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer (Indication name (INCI): Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer) and 70% Squalane (Indication name (INCI): Squalane) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Vinyl Dimethicone / Methicone Silsesquioxane) Crosspolymer (Indication name (INCI: Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer)) <Preparation of cosmetic> A: Components 1 to 6 were mixed uniformly. B: Components 7 to 13 were mixed uniformly. C: The mixture obtained in B was added to the mixture obtained in A and emulsified to obtain a W / O cream.The resulting W / O cream exhibited excellent applicability, a rich texture, and good moisture retention and stability over time.

[0169] [Example 18] Concealer composition % 1. KSP-101 (Note 1) 18 2. KSP-300 (Note 2) 4 3. KSG-19 (Note 3) 6 4. Organopolysiloxane from Manufacturing Example 7 0.5 5. KF-56A 7 6. KF-96A-6cs Remaining amount 7. KF-96L-2cs 18 8. Silicone-treated fine particle zinc oxide 59. Titanium dioxide 0.3 Total 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Vinyl dimethicone / methicone silsesquioxane) crosspolymer (Indication name (INCI: Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Diphenyl dimethicone / vinyl diphenyl dimethicone / silsesquioxane) crosspolymer (Indication name (INCI: Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane Crosspolymer)) (Note 3) Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Vinyl Dimethicone) Crosspolymer (Indication name (INCI): Dimethicone / Vinyl Dimethicone Crosspolymer) and 85% Dimethicone (Indication name (INCI): Dimethicone) <Preparation of Cosmetic> Components 1 to 9 were uniformly mixed to obtain a concealer. The obtained concealer had excellent applicability and richness, was fresh, and had good stability over time.

[0170] [Example 19] O / W Cream Composition % 1. KSG-048Z (Note 1) 5 2. KSG-19 (Note 2) 10 3. Organopolysiloxane from Manufacturing Example 11 0.5 4. KF-96A-6cs 10 5. Polysorbate 60 1 6. BG 5 7. Pentylene glycol 2 8. Xylitol 2 9. SIMULGEL NS (Note 3) 1 10. Carboxyvinyl polymer 0.2 11. Sodium hydroxide Appropriate amount 12. Phenoxyethanol 0.3 13. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 20% (Lauryl polydimethylsiloxyethyl dimethicone / bis-vinyl dimethicone) crosspolymer (indication name (Lauryl olimethylsiloxyethyl Dimethicone / Bis-Vinyldimethicone Crosspolymer)) and 80% dimethicone (indication name (INCI: Dimethicone)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Dimethicone / vinyl dimethicone) crosspolymer (indication name (INCI: Dimethicone / Vinyl Dimethicone) A mixture of 15% Crosspolymer and 85% Dimethicone (Indication name (INCI: Dimethicone)) (Note 3) (Hydroxyethyl acrylate / sodium acryloyldimethyl taurate copolymer composition manufactured by SEPPIC) <Preparation of cosmetic> A: Components 1 to 4 were mixed uniformly. B: Components 5 to 13 were mixed uniformly. C: The mixture obtained in A was added to the mixture obtained in B and emulsified to obtain an O / W cream. The obtained O / W cream had excellent applicability and richness, was fresh, and had good stability over time.

[0171] [Example 20] O / W Sunscreen Cream Composition % 1. Xanthan Gum 0.2 2. BG 8 3. Caprylhydroxamic Acid 0.1 4. SEPIGEL 305 (Note 1) 2 5. Polyoxyethylene (60) Hydrogenated Castor Oil 1 6. KF-6043 (Note 2) 0.5 7. Allantoin 0.2 8. Purified Water Remainder 9. Organopolysiloxane from Manufacturing Example 12 0.3 10. KF-56A 3 11. KSG-016F (Note 3) 1.5 12. Cetanol 2 13. Ethylhexyl Methoxycinnamate 5 14. Alkylsilane-treated Zinc Oxide Microparticles 2 15. Ethanol 10 Total 100.0 (Note 1) Manufactured by SEPPIC (Polyacrylamide composition) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Indication name (INCI: PEG-10 Dimethicone)) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 25% (Dimethicone / Vinyl Dimethicone) Crosspolymer (Indication name (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer) and 75% Dimethicone (Indication name (INCI: Dimethicone)) <Preparation of cosmetic> A: Components 1 to 8 were heated to 80°C and mixed uniformly. B: Components 9 to 14 were heated to 80°C and mixed uniformly. The mixture obtained in C:B was added to the mixture obtained in A, emulsified, and then slowly cooled. Component 15 was added and mixed uniformly to obtain a sunscreen. The resulting O / W sunscreen cream had excellent applicability and richness, was moisturizing, and had good stability over time.

[0172] [Example 21] W / O Sunscreen Cream Composition % 1. Organopolysiloxane from Manufacturing Example 1 2 2. KSG-18A (Note 1) 2 3. KF-6048 (Note 2) 1.5 4. Dicaprylyl carbonate 8 5. Isononyl isononanoate 3 6. Disteardimonium hecto 0.8 7. Stearyl glycyrrhetinate 0.2 8. Ethylhexyl methoxycinnamate 7 9. Diethylamino hydroxybenzoyl hexyl benzoate 2 10. Cetyl ethylhexanoate 5 11. KSP-300 (Note 3) 2 12. SPD-T7 (Note 4) 12 13. SPD-Z5 (Note 5) 12 14. Pentylene glycol 2 15. Ethanol 6 16. Sodium citrate 0.2 17. Sodium chloride 0.5 18. Total water remaining 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) (Indication name (INCI): Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) and 85% diphenylsiloxy phenyl trimethicone (Indication name (INCI): Diphenylsiloxy) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Cetyl PEG / PPG-10 / 1 Dimethicone (Indication name (INCI): Cetyl PEG / PPG-10 / 1 Dimethicone)(Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane) Crosspolymer (Indication name (INCI: Diphenyl Dimethicone / Vinyl Diphenyl Dimethicone / Silsesquioxane Crosspolymer)) (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Titanium dioxide (Indication name (INCI: Titanium Dioxide) 40% dispersion) (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd.: Zinc oxide (Indication name (INCI: Zinc Oxide) 60% dispersion) <Preparation of cosmetic> A: Components 1 to 11 were uniformly mixed. B: Components 14 to 18 were uniformly mixed. The mixture obtained in C:B was added to the mixture obtained in A and emulsified, and components 12-13 were added and mixed uniformly to obtain a W / O sunscreen cream. The obtained W / O sunscreen cream had excellent applicability and richness, was refreshing, and had good stability over time.

[0173] [Example 22] W / O Shaking Sunscreen Composition % 1. Organopolysiloxane from Manufacturing Example 7 0.5 2. KSG-18A (Note 1) 3 3. KF-6038 (Note 2) 2 4. (Caprylic / Capric Acid) Coconut Alkyl 5.5 5. Triethylhexanoin 5 6. Homosalate 5 7. Ethylhexyl Salicylate 5 8. Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 2.5 9. Octocrylene 2 10. KMP-590 (Note 3) 0.5 11. KF-96L-2cs 27 12. KF-6105 (Note 4) 1.5 13. Metal Soap Treated Fine Particle Titanium Dioxide 4.5 14. Alkyl Silane Treated Fine Particle Zinc Oxide 12 15. BG 3 16. Ethanol 6 17. Tranexamic acid 2 18. Glyceryl caprylate 0.1 19. Sodium citrate 0.2 20. Sodium chloride 0.5 21. Total water remaining 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Phenyl Vinyl Dimethicone) crosspolymer (indication name (INCI): Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) and 85% diphenylsiloxy phenyl trimethicone (indication name (INCI): Diphenylsiloxy)(Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone)) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Polymethylsilsesquioxane (Indication name (INCI: Polymethylsilsesquioxane)) (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI: Lauryl Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone)) <Preparation of Cosmetics> A: Components 11-14 were dispersed in a homomixer, then components 1-10 were added and mixed uniformly. B: Components 15-21 were mixed uniformly. C: The mixture obtained in B was added to the mixture obtained in A and emulsified to obtain a W / O shaking sunscreen. The obtained W / O shaking sunscreen had excellent applicability and richness, and good stability over time.

[0174] [Example 23] Shakin' Foundation Composition % 1. Organopolysiloxane from Manufacturing Example 3 0.5 2. KSG-18A (Note 1) 3 3. KF-6038 (Note 2) 2 4. KSP-441 (Note 3) 8 5. KP-550 (Note 4) 1.5 6. Disteardimonium hecto 1.5 7. Dimethylsilylated silica 1.6 8. Ethylhexyl methoxycinnamate 5 9. Triethylhexanoin 6 10. Isododecane 10 11. KF-96L-2cs Remaining amount 12. KF-96A-6cs 6 13. KF-6106 (Note 5) 0.75 14. Metal soap treated fine particle titanium dioxide 3 15. KTP-09W (Note 6) 8.5 16. KTP-09Y (Note 7) 0.9 17. KTP-09R (Note 7) 0.5 18. KTP-09B (Note 7) 0.119. Ethanol 6 Total 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) (Indication name (INCI): Dimethicone / Phenyl Vinyl Dimethicone Crosspolymer) and 85% diphenylsiloxyphenyl trimethicone (Indication name (INCI): Diphenylsiloxy) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI): Lauryl PEG-9 Polydimethylsiloxyethyl Dimethicone)(Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Polysilicone-22 (Indication name (INCI: Polysilicone-22)) (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Acrylates / Dimethicone) Copolymer (Indication name (INCI: Acrylates / Dimethicone Copolymer)) (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd.: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI: Polyglyceryl-3 Polydimethylsiloxyethyl Dimethicone)) (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl Polydimethylsiloxyethylhexyl Dimethicone (Indication name (INCI: Triethoxysilyl Titanium dioxide treated with Polydimethylsiloxyethylhexyl Dimethicone (Note 7) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (Indication name (INCI): Triethoxysilyl Polydimethylsiloxyethyl Hexyl Dimethicone) Iron oxide <Preparation of cosmetic> A: Components 12 to 18 were dispersed using a three-roller machine. B: Components 1 to 11 were mixed uniformly. C: The mixture obtained in A was added to the mixture obtained in B and mixed uniformly to obtain a shaking foundation. The obtained shaking foundation had excellent applicability and richness, and good stability over time.

[0175] [Example 24] W / O Liquid Foundation Composition % 1. Organopolysiloxane from Manufacturing Example 10 2 2. KSG-15 (Note 1) 2 3. KF-6017 (Note 2) 2 4. KF-56A (Note 3) 5 5. Disteardimonium hecto 1 6. KF-995 17.1 7. KF-96A-6cs 5 8. KSP-100 (Note 4) 2 9. Ethylhexyl palmitate 5 10. KP-578 (Note 5) 0.2 11. KTP-09W (Note 6) 15 12. KTP-09Y (Note 7) 0.9 13. KTP-09R (Note 7) 0.5 14. KTP-09B (Note 7) 0.1 15. BG 5 16. Sodium citrate 0.2 17. Sodium chloride 0.5 18. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 7% (Dimethicone / Vinyl Dimethicone Crosspolymer) (Indication name (INCI): Dimethicone / Vinyl Dimethicone Crosspolymer) and 93% Cyclopentasiloxane (Indication name (INCI): Cyclopentasiloxane) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Indication name (INCI): PEG-10 Dimethicone) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxy Phenyl Trimethicone (Indication name (INCI): Diphenylsiloxy Phenyl Trimethicone)(Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Vinyl Dimethicone / Methicone Silsesquioxane) Crosspolymer (Indication name (INCI: Vinyl Dimethicone / Methicone Silsesquioxane Crosspolymer)) (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Acrylates / Ethylhexyl Acrylate / Dimethicone Methacrylate) Copolymer (Indication name (INCI: Acrylates / Ethylhexyl Acrylate / Dimethicone Methacrylate Copolymer)) (Note 6) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl Polydimethylsiloxyethylhexyl Dimethicone (Indication name (INCI: Triethoxysilyl Titanium dioxide treated with Polydimethylsiloxyethylhexyl Dimethicone (Note 7) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (Indication name (INCI): Triethoxysilyl Polydimethylsiloxyethyl Hexyl Dimethicone) Iron oxide <Preparation of cosmetic> A: Components 9 to 14 were dispersed using a three-roller machine. B: Components 1 to 8 were mixed uniformly. C: Components 15 to 18 were mixed uniformly. D: The mixture obtained in C was added to the mixture obtained in B and emulsified, A was added and mixed uniformly to obtain a W / O liquid foundation. The resulting W / O liquid foundation exhibited excellent applicability, richness, and good stability over time.

[0176] [Example 25] W / O Liquid Foundation Composition % 1. KSG-360Z (Note 1) 3 2. KSG-19 (Note 2) 5 3. KF-6028 (Note 3) 3 4. KF-96L-2cs 24.8 5. Disteardimonium hecto 1.2 6. Dicaprate PG 5 7. KF-7312L (Note 4) 1.5 8. Cetyl ethylhexanoate 6 9. Organopolysiloxane from Manufacturing Example 3 0.5 10. Metal soap treated fine particle titanium dioxide 5 11. KF-9901 (Note 5) treated titanium dioxide 8.5 12. KF-9901 (Note 5) treated yellow iron oxide 0.9 13. KF-9901 (Note 5) treated red iron oxide 0.5 14. KF-9901 (Note 5) treated black iron oxide 0.1 15. DPG 5 16. Sodium citrate 0.2 17. Sodium chloride 18. Total remaining water: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 35% (PEG-15 / Lauryl Polydimethylsiloxyethyl Dimethicone) Crosspolymer (Indication name (INCI: PEG-15 / Lauryl Polydimethylsiloxyethyl Dimethicone Crosspolymer) and 93% Dimethicone (Indication name (INCI: Dimethicone)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Vinyl Dimethicone) Crosspolymer (Indication name (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer) and 85% Dimethicone (Indication name (INCI: Dimethicone))(Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: PEG-9 Polydimethylsiloxyethyl Dimethicone (Indication name (INCI: PEG-9 Polydimethylsiloxyethyl Dimethicone)) (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Trimethylsiloxysilicate (Indication name (INCI: Trimethylsiloxysilicate)) (Note 5) Manufactured by Shin-Etsu Chemical Co., Ltd.: Hydrogen Dimethicone (Indication name (INCI: Hydrogen Dimethicone)) <Preparation of Cosmetics> A: Components 8 to 14 were dispersed using a three-roller machine. B: Components 1 to 7 were mixed uniformly. C: Components 15 to 18 were mixed uniformly. The mixture obtained in D:B was emulsified by adding the mixture obtained in C, and then A was added and mixed uniformly to obtain a W / O liquid foundation. The obtained W / O liquid foundation had excellent applicability and richness, and good stability over time.

[0177] [Example 26] BB Cream Composition % 1. Organopolysiloxane from Manufacturing Example 3 3 2. KSG-42A (Note 1) 5 3. KF-6048 (Note 2) 3 4. Disteardimonium hecto 1 5. Isododecane 12 6. Hexyl laurate 5 7. t-Butyl methoxydibenzoylmethane 3 8. Homosalate 8 9. Octocrylene 5 10. Ethylhexyl salicylate 5 11. Bis-ethylhexyloxyphenol methoxyphenyl triazine 1.5 12. Isotridecyl isononanoate 2 13. KF-6105 0.2 14. AES-3083 (Note 3) treated titanium dioxide 6 15. AES-3083 (Note 3) treated yellow iron oxide 0.8 16. AES-3083 (Note 3) treated red iron oxide 0.4 17. AES-3083 (Note 3) treated black iron oxide 0.1 18. BG 5 19. Sodium citrate 0.2 20. Sodium chloride 12 11. Total remaining water 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 20% (vinyl dimethicone / lauryl dimethicone) crosspolymer (indication name (INCI): Vinyl Dimethicone / Lauryl Dimethicone Crosspolymer) and 80% isododecane (indication name (INCI): Isododecane)(Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Cetyl PEG / PPG-10 / 1 Dimethicone (Indication name (INCI: Cetyl PEG / PPG-10 / 1 Dimethicone)) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxycaprylylsilane (Indication name (INCI: Triethoxycaprylylsilane)) <Preparation of cosmetic> A: Components 12 to 17 were dispersed using a three-roller machine. B: Components 1 to 11 were mixed uniformly. C: Components 18 to 21 were mixed uniformly. D: The mixture obtained in B was emulsified by adding the mixture obtained in C, and A was added and mixed uniformly to obtain BB cream. The obtained BB cream had excellent applicability and richness, and good stability over time.

[0178] [Example 27] Composition of poured foundation % 1. KSG-240 (Note 1) 3 2. Organopolysiloxane from Manufacturing Example 3 0.3 3. Ethylhexyl methoxycinnamate 7.5 4. Octocrylene 2 5. Diethylamino hydroxybenzoyl hexyl benzoate 2.5 6. KF-56A (Note 2) 6 7. KF-6105 0.3 8. Alkylsilane-treated fine particle zinc oxide 4 9. KTP-09W (Note 3) 5 10. KTP-09Y (Note 4) 0.6 11. KTP-09R (Note 4) 0.3 12. KTP-09B (Note 4) 0.1 13. Ceresin 2.4 14. Phenoxyethanol 0.2 15. PCA-Na 1 16. Glycerin 4 17. BG 8 18. Sodium citrate 0.2 19. Sodium chloride 120. Total remaining water 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 20% (Dimethicone / (PEG-10 / 15)) crosspolymer (indication name (INCII: Dimethicone / (PEG-10 / 15) crosspolymer) and 80% cyclopentasiloxane (indication name (INCI: Cyclopentasiloxane)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Diphenylsiloxyphenyl trimethicone (indication name (INCI: Diphenylsiloxy Phenyl Trimethicone))(Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone (Indication name (INCI): Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone) treated titanium dioxide (Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl polydimethylsiloxyethyl hexyl dimethicone (Indication name (INCI): Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone) treated iron oxide <Preparation of cosmetic> A: After dispersing components 1 to 12 in a homomixer, component 13 was added and heated to 95°C. B: Components 14-20 were uniformly mixed at 85°C. C: The mixture obtained in B was emulsified by adding the mixture obtained in A, filled into a container, and cooled to obtain a pourable foundation. The obtained pourable foundation had excellent applicability and richness, was moist, and had good stability over time.

[0179] [Example 28] Mascara composition % 1. TSPL-30-ID (Note 1) 10 2. Isododecane residue 3. Disteardimonium hecto 5 4. KP-574 (Note 2) treated black iron oxide 5 5. KP-574 (Note 2) treated talc 5 6. KMP-590 5 7. Organopolysiloxane from Manufacturing Example 10 1.2 8. Propylene carbonate 1.6 9. Phenoxyethanol 0.2 10. Dextrin palmitate 2 11. Synthetic wax 6 12. Paraffin wax 6 Total 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Tri(trimethylsiloxy)silylpropylcarbamate pullulan (Indication name (INCI): Trimethylsiloxysilylcarbamate Pullulan)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Acrylates / Tridecyl acrylate / Triethoxysilylpropyl methacrylate / Dimethicone methacrylate) copolymer (Indication name (INCI): Acrylates / Tridecyl acrylate / Triethoxysilylpropyl methacrylate / Dimethicone methacrylate copolymer)) <Preparation of cosmetics> A: Components 1-9 were dispersed using a disperser, then components 10-12 were added and the mixture was heated to 95°C. B: The mixture obtained in A was cooled to obtain mascara. The resulting mascara had excellent applicability, richness, and good oil resistance.

[0180] [Example 29] Lipstick composition % 1. Polyethylene 7 2. Microcrystalline wax 3 3. KP-561P (Note 1) 10.5 4. Triethylhexanoin 14 5. Neopentyl glycol diethylhexanoate 14 6. Neopentyl glycol dicaprate 8 7. Hydrogenated polyisobutene remainder 8. KF-54HV (Note 2) 7.5 9. Sericite 0.7 10. Appropriate amount of Red No. 201 11. Appropriate amount of Red No. 202 12. Appropriate amount of Yellow No. 4 13. KTP-09W (Note 3) 2.7 14. Appropriate amount of KTP-09B (Note 4) 15. Appropriate amount of KTP-09R (Note 4) 16. Polyglyceryl-2 triisostearate 4 17. Mica 618. Organopolysiloxane of Manufacturing Example 11 Total 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: (Acrylates / Stearyl Acrylate / Dimethicone Methacrylate) Copolymer (Indication name (INCI): Acrylates / Stearyl Acrylate / Dimethicone Methacrylate Copolymer) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: Diphenyl Dimethicone (Indication name (INCI): Diphenyl Dimethicone) (Note 3) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl Polydimethylsiloxyethylhexyl Dimethicone (Indication name (INCI): Triethoxysilylethyl Polydimethylsiloxyethylhexyl Hexyl Dimethicone-treated titanium oxide(Note 4) Manufactured by Shin-Etsu Chemical Co., Ltd.: Triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (Indication name (INCI): Triethoxysilylethyl Polydimethylsiloxyethyl Hexyl Dimethicone) treated iron oxide <Preparation of cosmetic> A: Components 9 to 16 were dispersed in a roll mill. B: Components 1 to 8 were heated to 95°C and mixed uniformly. C: The mixture obtained in A, the mixture obtained in B, and components 17 to 18 were mixed uniformly and heated to 85°C. D: The mixture obtained in C was filled into a stick container to obtain a lipstick. The obtained lipstick had excellent applicability and richness, and good adhesion resistance.

[0181] [Example 30] Out-of-bath hair treatment composition % 1. Organopolysiloxane from Manufacturing Example 3 3 2. KSG-19 (Note 2) 1 3. KF-6017 (Note 3) 0.2 4. KF-96A-6cs 8.5 5. Fragrance (appropriate amount) 6. Dipropylene glycol 8 7. Ethanol 5 8. Methyl parahydroxybenzoate 0.1 9. Sodium citrate 0.2 10. Sodium chloride 0.5 11. Total amount of purified water remaining: 100.0 (Note 1) Manufactured by Shin-Etsu Chemical Co., Ltd.: A mixture of 15% (Dimethicone / Vinyl Dimethicone Crosspolymer) (Indication name (INCI: Dimethicone / Vinyl Dimethicone Crosspolymer) and 85% Dimethicone (Indication name (INCI: Dimethicone)) (Note 2) Manufactured by Shin-Etsu Chemical Co., Ltd.: PEG-10 Dimethicone (Indication name (INCI: PEG-10 Dimethicone)) <Preparation of cosmetic> A: Components 1 to 4 were mixed uniformly. B: Components 6 to 11 were mixed uniformly. C: The mixture obtained in B was added to the mixture obtained in A and emulsified, and component 5 was added to obtain an out-of-bath treatment. The resulting leave-in hair treatment had excellent manageability, was moisturizing, and exhibited good stability over time.

Claims

1. An organopolysiloxane represented by the following formula (1). [In the formula, R 1 R is independently selected from alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms. 2 These are independently selected from the following formulas (2) to (7), (In the formula, x1 is an integer between 3 and 10.) (In the formula, x² is an integer between 3 and 10.) (In the formula, x3 is an integer between 3 and 10.) (In the formula, x4 is an integer from 3 to 10, y1 is the average degree of polymerization of the glycerol group, which is from 1 to 5, and the proportion of groups with the highest degree of polymerization among 1 to 5 is 90% or more of the total number of groups shown in (6).) (In the formula, x5 is an integer from 3 to 10, y2 and y3 are the average values ​​of the degree of polymerization, each from 0 to 2, and y2 + y3 is from 0 to 2. Among those where y2 + y3 is 0, 1, and 2, the proportion of the group with the highest degree of polymerization accounts for 90% or more of the total groups shown in (7).) R 3 These are independently organopolysiloxane-containing groups, with one or more R groups per molecule. 3 is an organopolysiloxane-containing group. a, b1, b2, b3, c, and d satisfy the following conditions: 1 ≤ a ≤ 20, 0 ≤ b1 ≤ 300, 0 < b2 ≤ 80, 0 ≤ b3 ≤ 20, 0 ≤ c ≤ 10, 0 ≤ d ≤ 10, and 10 ≤ b1 + b2 + b3 ≤ 400, respectively. Note that the bonding order of each siloxane unit may be in blocks or random.

2. The organopolysiloxane according to claim 1, wherein c = d = 0 in formula (1).

3. The organopolysiloxane according to claim 1, wherein b3 > 0 in formula (1).

4. In the organopolysiloxane, R 2 The organopolysiloxane according to claim 1, wherein is the group represented by formula (6), and the proportion of the group having the highest degree of polymerization of the glycerin group among 1 to 5 is 95% or more of the total number of groups represented by (6).

5. In the organopolysiloxane, R 2 The organopolysiloxane according to claim 1, wherein is the group represented by formula (7), and among those where y2 + y3 is 0, 1, and 2, the proportion of the group having the highest degree of polymerization is 95% or more of the total group represented by (7).

6. R in formula (1) above 3 In this, the organopolysiloxane-containing group is as shown in formulas (8) to (11) below The organopolysiloxane according to claim 1, wherein the organopolysiloxane-containing group is selected from the groups represented by the formula (wherein k is an integer between 0 and 5, R4 is independently selected from an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, i is an integer between 0 and 500, and j1, j2, and j3 are each integers between 0 and 2).

7. The organopolysiloxane according to claim 1, wherein the HLB is 0.1 to 8.

0.

8. A cosmetic composition comprising the organopolysiloxane described in claim 1.

9. A water-in-oil emulsion comprising the organopolysiloxane described in claim 1.

10. A cosmetic composition comprising the water-in-oil emulsion according to claim 9.

11. The particle size of the water-in-oil emulsion is such that the particle size distribution width represented by the following formula ((D 90 −D 10 ) / D 50 (D 10 , D 50 , D 90 are the cumulative volume frequencies calculated from the smaller particle sizes of the emulsion and are 10%, 50%, and 90% respectively.) is 2.5 or less. The cosmetic according to claim 10.

12. Particle size D of the water-in-oil emulsion 50 The cosmetic composition according to claim 10, wherein the particle size is 10 μm or less.

13. Particle size D of the water-in-oil emulsion 50 The cosmetic composition according to claim 10, wherein the particle size is 5 μm or less.

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