Carboxylic acid co-modified organopolysiloxane and its uses

Abstract

[Problem] To provide: a novel carboxylic acid-comodified organopolysiloxane which functions superbly as a powder dispersant or the like, and is capable of stably and uniformly dispersing various hydrophobic powders in a water phase; a use of the same as a powder treatment agent; and an external preparation composition containing the same. [Solution] A carboxylic acid-comodified organopolysiloxane represented by structural formula (1) [In the formula, R1 is a hydrocarbon group having a carbon number no greater than 6, or is a hydrogen atom, R2 is a C6-30 monovalent hydrocarbon group, L1 is a specific organic silicon-containing organic group, Rc is a carboxyl group-containing organic group, R' each independently represent a group selected from R1, R2, L1 and Rc, and Rc and L1 must be present in each molecule], and a use therefor.

Description

[Technical Field]

[0001] The present invention relates to a carboxylic acid-co-modified organopolysiloxane that has a specific carboxyl group-containing organic group (hereinafter sometimes referred to as a "carboxylic acid-modified group") and a specific silicon-containing organic group in the molecule and is highly useful as a powder treatment agent, and to uses thereof, particularly an aqueous powder dispersion (slurry). [Background technology]

[0002] Cosmetics containing an aqueous phase as a continuous phase provide a fresh, moist feel when used, and are therefore widely used as, for example, skin care cosmetics such as emulsions, base cosmetics, sunscreens, foundations, eye shadows, and other makeup cosmetics. In particular, oil-in-water emulsion cosmetics containing inorganic UV protection agents, such as hydrophobic titanium oxide fine particles and hydrophobic zinc oxide fine particles, can be designed to have a high SPF (Sun Protection Factor), an index that indicates the degree of effectiveness in blocking UV-B rays (wavelengths of 280 to 315 nm), and are therefore widely used as sunscreen cosmetics such as sunscreens.

[0003] On the other hand, oil-in-water emulsion cosmetics usually suffer from the problem that the cosmetic film obtained by applying the cosmetic has poor water resistance. To impart water resistance to the cosmetic film, Patent Documents 1 and 2 propose the use of carboxylic acid-modified silicones under alkaline conditions to stabilize the cosmetic by well dispersing hydrophobic powders in the aqueous phase, or to prepare aqueous slurries that serve as cosmetic raw materials. Patent Document 2 in particular proposes carboxylic acid-modified silicones that may optionally have a siloxane-modified group and a carboxyl-containing organic group. However, the carboxylic acid-modified silicones specifically proposed in Patent Documents 1 and 2 may not be able to form aqueous slurries that are stable over long periods of time with some hydrophobic powders, such as hydrophobized zinc oxide fine particles, leaving room for improvement in powder dispersibility. Meanwhile, in Patent Document 3, the applicants propose using a neutralized salt of a modified silicone having a carbosiloxane dendrimer structure and a carboxylic acid-modified group in an oil-in-water emulsion cosmetic, but do not disclose a carboxylic acid-co-modified organopolysiloxane that is a linear co-modified siloxane molecule, has an organosilicon-containing organic group such as a carbosiloxane dendrimer structure in the side chain portion, and has a carboxylic acid-modified group within the molecule, and furthermore, does not describe or suggest the use of a neutralized product of the carboxylic acid-co-modified organopolysiloxane as an aqueous dispersant for hydrophobic powders. Similarly, Patent Document 4 discloses a water-repellent cosmetic powder obtained by treating a powder with a metal cation salt of a carboxylic acid-modified organopolysiloxane, but similarly does not disclose the use of a carboxylic acid-co-modified organopolysiloxane that contains a specific organosilicon-containing organic group, and the treated powder is water-repellent but does not have dispersibility in an aqueous phase, making it unable to solve the problems of the present invention. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Patent Publication No. WO2015 / 159773 [Patent Document 2] International Patent Publication No. WO2020 / 036065 [Patent Document 3] International Patent Publication No. WO2009 / 022621 [Patent Document 4] Japanese Patent Application Publication No. 9-59125 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention has been made to solve the above-mentioned problems, and has an object to provide a novel carboxylic acid co-modified organopolysiloxane that is capable of stably and uniformly dispersing a variety of hydrophobic powders in an aqueous phase and has excellent functionality as a powder dispersant, etc. A further object is to provide an aqueous powder composition that uses the carboxylic acid co-modified organopolysiloxane, which has excellent handling properties and is capable of exhibiting sufficient functions such as water repellency, water resistance, and sebum resistance when incorporated into topical preparation compositions such as cosmetics, and a topical preparation composition containing the same. [Means for solving the problem]

[0006] As a result of extensive investigation, the present inventors have found that the compound is liquid at 50°C and has a carboxyl group in the molecule. The present inventors have discovered that the above-mentioned problems can be solved by a linear, carboxylic acid-co-modified organopolysiloxane having the formula (I) and having at least one organosilicon-containing organic group (L1) selected from a silylalkyl group having a carbosiloxidedendron structure and a group having a siloxane macromonomer structure in a specific ratio in its side chain portion, and have arrived at the present invention. The present inventors have also discovered that the above-mentioned problems can be solved by using the co-modified organopolysiloxane as a powder treatment agent, and have arrived at the present invention. Furthermore, the present inventors have discovered that the above-mentioned problems can be solved by using the co-modified organopolysiloxane, a basic substance, a hydrophilic medium, and a powder to form an aqueous powder composition in which the powder is uniformly dispersed in an aqueous phase, and by a topical preparation composition (particularly a cosmetic) containing the same, and a method for producing the same, and have arrived at the present invention. In particular, the above-mentioned problems can be solved extremely effectively when the carboxylic acid-co-modified organopolysiloxane has the specific degree of polymerization, etc., described below, and is liquid at room temperature (25°C). [Effects of the Invention]

[0007] The present invention can provide a novel carboxylic acid co-modified organopolysiloxane that can stably and uniformly disperse a variety of hydrophobic powders in an aqueous phase and has excellent functionality as a powder dispersant, etc. Furthermore, by using this carboxylic acid co-modified organopolysiloxane as a powder treatment agent, it is possible to provide an aqueous powder composition that is easy to handle and that can exhibit sufficient functions such as water repellency, water resistance, and sebum resistance when incorporated into topical preparation compositions such as cosmetics, as well as a topical preparation composition containing the same. DETAILED DESCRIPTION OF THE INVENTION

[0008] The co-modified organopolysiloxane of the present invention and its use as various treatment agents (surfactants or surface treatment agents), particularly its use as a powder treatment agent / powder dispersant and its use as a cosmetic raw material, will be described in detail below.

[0009] The carboxylic acid-co-modified organopolysiloxane of the present invention is a linear polysiloxane that is liquid at 50°C and is represented by structural formula (1) described below. It has, at its side chain, an organosilicon-containing organic group (L1) selected from a silylalkyl group having a carbosiloxidedendron structure and a group having a siloxane macromonomer structure, and also has a specific carboxyl group-containing organic group within the molecule. The carboxyl group-containing organic group in the carboxylic acid-co-modified organopolysiloxane of the present invention may be introduced into a side chain or terminal, with a side chain being particularly preferred. The carboxylic acid-co-modified organopolysiloxane of the present invention may be liquid at 50°C and 1 atmosphere. For example, it may be solid at room temperature (25°C), but a liquid at room temperature (25°C) is particularly preferred.

[0010] The carboxylic acid co-modified organopolysiloxane according to the present invention has the following structural formula (1): [ka] (1) It is expressed as:

[0011] In the formula, R 1 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, and other R 2 , L 1 and does not contain a group corresponding to Rc, and is industrially preferably a methyl group or a phenyl group.

[0012] R 2 is a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, which may be optionally contained in the molecule, and may improve the affinity with non-silicone oils such as hydrocarbon oils (cosmetic raw materials). 2 is an alkyl group having 6 to 30 carbon atoms, and examples thereof include a hexyl group, a heptyl group, an octyl group, a decyl group, a dodecyl group, an undecyl group, and a hexadecyl group, and an alkyl group having 8 to 20 carbon atoms is particularly preferred.

[0013] L1 is a silicon-containing organic group selected from a silylalkyl group having a carbosiloxidedendron structure and a group having a siloxane macromonomer structure, and the carboxylic acid co-modified organopolysiloxane according to the present invention contains a specific carboxyl group-containing organic group Rc and at least one L present in a side chain position within the molecule. 1 By the presence of a certain ratio, excellent powder dispersion performance, particularly in the aqueous phase, is realized. 1 teeth, The following general formula (2) when i=1: [ka] (2) (In the formula, R 1 is the same group as above, and R C is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is a divalent organic group. i represents a generation of a silylalkyl group represented by the formula: i+1 is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. i a silylalkyl group having a siloxane dendron structure represented by the formula: The following general formula (2'): [ka] (2´) (In the formula, R 11 are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and R 11 at least one of which is the monovalent hydrocarbon group, where t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500; and The following general formula (2´´): [ka] (2´´) (In the formula, R 11 and r is as defined above).

[0014] L 1 may be the same or different. For example, a silylalkyl group having a carbosiloxidedendron structure and a group having a siloxane macromonomer structure may be contained in the same molecule, a silylalkyl group may be a combination of organosilicon-containing organic groups with different degrees of branching (generations), and a group having a siloxane macromonomer structure may be a combination of organosilicon-containing organic groups with different degrees of polymerization.

[0015] L 1 The group represented by the formula (I) may be a silylalkyl group having a carbosiloxane dendrimer structure, and is defined as the silylalkyl group represented by the above general formula (2) when i = 1. The silylalkyl group having a carbosiloxane dendrimer structure has a structure in which the carbosiloxane units spread out like a dendrimer, and is therefore a functional group that exhibits higher water repellency than linear or simply branched polysiloxane units. This allows the carboxylic acid-co-modified organopolysiloxane of the present application to achieve high powder dispersibility without impairing the feel derived from the hydrophilic functional group. Furthermore, the silylalkyl group having a carbosiloxane dendrimer structure is a functional group that confers the advantageous property of being chemically stable and therefore capable of being used in combination with a wide range of cosmetic ingredients.

[0016] In general formula (2), R C is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and industrially, is preferably a methyl group or a phenyl group.

[0017] In the general formula (2), i is L 1 represents a generation of a silylalkyl group represented by the formula: i+1is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. In particular, it is preferably a methyl group when i=c.

[0018] The number of classes c is preferably an integer of 1 to 3 from an industrial perspective, and more preferably 1 or 2. In each generation number, the group represented by L1 is represented as follows: and Z are the same groups as defined above.

[0019] When the number of layers c=1, L1 is expressed by the following general formula (2-1). [ka] (2-1)

[0020] When the number of layers c=2, L1 is expressed by the following general formula (2-2). [ka] (2-2)

[0021] In formula (2), each ai is independently a number in the range of 0 to 3, and in the structures represented by formulas (2-1) to (2-3) when the number of generations is 1 to 3, a1, a2, and a3 are independently a number in the range of 0 to 3. These ai are particularly preferably numbers in the range of 0 to 1, and it is particularly preferred that ai is 0.

[0022] In the above formula, each Z is independently a divalent organic group, and specific examples include divalent organic groups formed by addition reaction of a silicon-bonded hydrogen atom with a functional group having an unsaturated hydrocarbon group at its terminal, such as an alkenyl group, an acryloxy group, or a methacryloxy group. However, depending on the method for introducing the silylalkyl group having the carbosiloxane dendrimer structure, Z is not limited to these functional groups and can be appropriately selected. In the present invention, Z is preferably an alkylene group having 2 to 10 carbon atoms, and most preferably an ethylene group.

[0023] L 1 The group represented by L may be a siloxane macromonomer structure-containing group bonded to a silicon atom constituting the main chain via oxygen or an alkylene group, and is a hydrophobic functional group that exhibits a certain degree of water repellency / oleophilicity, achieving a high level of powder dispersibility for the carboxylic acid co-modified organopolysiloxane of the present application without impairing the feel derived from the hydrophilic functional group. Specifically, L 1 The group represented by the formula (2) may be a functional group represented by the formula (2') or (2''). 11 Industrially, particularly preferred examples of R are a methyl group, a phenyl group, or a hydroxyl group. 11 A configuration in which a part of R is a methyl group and a part is a long-chain alkyl group having 8 to 30 carbon atoms is also suitable. 11 At least one of the groups is a monovalent hydrocarbon group such as a methyl group, t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500. From the viewpoint of compatibility with various oils, r is preferably a number in the range of 1 to 100, and particularly preferably a number in the range of 2 to 30.

[0024] Rc is the general formula: -Rc 1 -(ORc 2 )p-(O)w-Rc 3 -COOH(Rc 1 represents a linear or branched alkylene group having 2 to 22 carbon atoms; Rc 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms; Rc 3 represents a bond (-) or a linear or branched alkylene group having 1 to 22 carbon atoms, p represents a number from 0 to 200, and w represents a number of 0 or 1), and the L 1 When present in the molecule together with a specific silicon-containing organic group, in particular, the neutralized salt with a basic substance can realize excellent powder dispersibility in an aqueous phase.

[0025] In the general formula representing the carboxyl group-containing organic group, Rc 1represents a linear or branched alkylene group having 2 to 22 carbon atoms, preferably 2 to 12 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include a decamethylene group.

[0026] Also, Rc 2 Examples of the linear or branched alkylene group having 2 to 4 carbon atoms include ethylene, propylene, trimethylene, and butylene groups.

[0027] Rc 3 may be a bond (-) or a linear or branched alkylene group having 1 to 22 carbon atoms.

[0028] p represents a number from 0 to 200, preferably a number from 0 to 20, and particularly preferably a number from 0 to 10. w represents a number of 0 or 1, preferably 0. When p and w are both 0 and Rc 3 is a bond (-), the carboxyl group-containing organic group has the structural formula -(C n H 2n )-COOH, in which one carboxyl group is bonded to a silicon atom via a linear or branched alkylene group. In the formula, n is preferably a number from 3 to 20, and particularly preferably a number from 3 to 16.

[0029] R' is independently selected from the group R 1 ,R 2 ,L 1 and Rc, and R' is L 1 If R' is Rc, the structure further has a silicon-containing organic group at the molecular chain terminal, and if R' is Rc, the structure has a carboxyl group-containing organic group at the molecular chain terminal, preferably a methyl group. However, when n4, which will be described later, is 0, the carboxylic acid-co-modified organopolysiloxane according to the present invention has an Rc of 1 or more, and therefore at least one of the R's is Rc.

[0030] In structural formula (1), n1 to n4 represent the average degree of polymerization of each diorganosiloxy unit, and (n1 + n2 + n3 + n4) is a number in the range of 1 to 1000, preferably 2 to 50, and particularly preferably 2 to 20. That is, the carboxylic acid co-modified organopolysiloxane according to the present invention is preferably of relatively low polymerization, particularly from the standpoint of powder dispersion performance in an aqueous phase. In particular, when the polymerization is relatively low, it is liquid and has a low viscosity at room temperature (25°C), which is advantageous for preparing an aqueous slurry.

[0031] Furthermore, in structural formula (1), n1 is a number in the range of 0 to 999, more preferably 0 to 49, and most preferably 0 to 5. n2 is a number in the range of 0 to 100, and more preferably 0 to 10. n3 is a number in the range of 1 to 100, and more preferably 1 to 10. n4 is a number in the range of 0 to 100, and more preferably 0 to 10.

[0032] From the viewpoint of the technical effects of the present invention, n1 to n4 are numbers within a range in which the carboxylic acid co-modified organopolysiloxane according to the present invention is liquid at room temperature (25°C), and it is particularly preferable that the viscosity is low. A carboxylic acid co-modified organopolysiloxane that is liquid at room temperature (25°C) and has a low viscosity has advantages such as excellent dispersibility for hydrophobic powders and no heating operation is required when forming an aqueous dispersion composition.

[0033] From the viewpoint of the technical effects of the present invention, it is particularly preferable that the carboxylic acid co-modified organopolysiloxane according to the present invention has, in the above structural formula (1), (n1+n2+n3+n4) is a number in the range of 2 to 20, n3 is a number in the range of 1 to 10, n4 is a number in the range of 1 to 10, and (n1+n2+n3) / n4 is in the range of 0.1 to 5.0. A carboxylic acid co-modified organopolysiloxane having such a structure has L at a certain ratio on its molecular chain side chains. 1and a carboxyl group-containing organic group represented by Rc, the powder treatment effect is excellent, and the uniform dispersion of hydrophobic powders in the aqueous phase is further improved. As a result, when an aqueous dispersion composition containing the carboxylic acid co-modified organopolysiloxane is used as a cosmetic raw material, it has the advantage of being able to effectively achieve functions such as sufficient water repellency, water resistance, and sebum resistance. Another advantage is that the uniform dispersion of the hydrophobic powder in the aqueous phase can be maintained for an extended period of time.

[0034] The carboxylic acid co-modified organopolysiloxane according to the present invention can be produced by a method in which an organopolysiloxane having a reactive functional group such as Si-H is reacted with a compound having an organosilicon-containing organic group having one carbon-carbon double bond at one end of the molecular chain (for example, the above-mentioned silyl alkyl group), followed by an addition reaction with an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid silyl ester, or an allyloxycarboxylic acid silyl ester in the presence of a platinum catalyst, and then saponification or hydrolysis after the reaction to obtain the target product.

[0035] [Uses of carboxylic acid co-modified organopolysiloxane] The novel carboxylic acid co-modified organopolysiloxane according to the present invention has a silicon-containing organic group that exhibits high water repellency and a hydrophilic carboxyl group-containing organic group in the same molecule, and preferably has a low viscosity, which makes it easy to handle, efficient to work with, and stable in blending with various cosmetic raw materials. As a result, it is useful as a variety of treatment agents and cosmetic raw material components, and is particularly useful as a powder surface treatment agent, surfactant, or powder dispersant used in the surface treatment of hydrophobic powders used in cosmetics or for dispersing powders into an aqueous phase.

[0036] [Use as a powder processing agent or powder dispersant] The carboxylic acid-co-modified organopolysiloxane according to the present invention functions as a surface treatment agent or dispersant for powders, particularly hydrophobic powders, and when used in combination with a basic substance, it is possible to form an aqueous powder composition in which the hydrophobic powder is uniformly and stably dispersed in the aqueous phase. In particular, a carboxylic acid-co-modified organopolysiloxane composition containing (A) the carboxylic acid-co-modified organopolysiloxane according to the present invention, (B) a basic compound, and (C) one or more hydrophilic media selected from water, polyhydric alcohols, and lower alcohols forms a carboxylate structure in the hydrophilic medium in which the carboxylic acid residues are partially neutralized, and is therefore particularly useful as a powder surface treatment agent, surfactant, or surface treatment agent, which is a dispersant for hydrophobic powders.

[0037] [Powder composition] The present invention relates to a powder composition containing (A) the carboxylic acid co-modified organopolysiloxane of the present invention, (B) a basic compound, (C) one or more hydrophilic media selected from water, polyhydric alcohols, and lower alcohols, and (D) a powder or colorant. The powder composition preferably contains (D1) a hydrophobic powder or colorant, and has a structure in which component (D1) is dispersed in an aqueous phase. The powder composition containing the carboxylic acid co-modified organopolysiloxane of the present invention can be suitably used in topical preparation compositions, and particularly as cosmetics or cosmetic raw materials.

[0038] The powder composition according to the present invention is preferably an aqueous dispersion composition in which an aqueous phase made of a hydrophilic medium is a continuous phase, and is a composition in which a powder or colorant, particularly a hydrophobic powder or colorant, is dispersed in a hydrophilic medium. Because it generally has fluidity, it is sometimes called an "aqueous slurry." Note that the hydrophilic medium in the present invention refers to an aqueous dispersion medium containing water, one or more alcohols selected from polyhydric alcohols that are uniformly miscible with water, and lower alcohols such as ethyl alcohol, and salts such as basic substances, and it is particularly preferred that the hydrophilic medium is substantially free of oil / oily cosmetic ingredients that are not miscible with water and that can form an independent oil phase.

[0039] The carboxylic acid co-modified organopolysiloxane according to the present invention can be used in the same manner as the carboxylic acid-modified silicones specifically disclosed in Patent Document 1 or Patent Document 2, and is also useful in that it can easily prepare an aqueous slurry that has low viscosity and excellent long-term storage stability, even from inorganic powders such as zinc oxide that cannot be sufficiently treated with these conventionally known carboxylic acid-modified silicones.

[0040] [(B) Basic substance] The powder composition of the present invention preferably contains at least one (B) basic substance. Component (B) can anionize the carboxylic acid-modified moiety of (A) the carboxylic acid co-modified organopolysiloxane of the present invention, thereby improving its function as a surfactant / powder dispersant. In particular, the aqueous dispersion composition of the present invention contains (D) a powder or colorant, preferably (D1) a hydrophobic powder or colorant. The combined use of components (A) and (B) allows component (D) to be dispersed in the aqueous phase more effectively than with component (A) alone, improving the uniform dispersibility and stability of the aqueous dispersion composition and also contributing to the realization of sufficient water repellency, water resistance, and sebum resistance in cosmetics and other products incorporating the aqueous dispersion composition as a cosmetic ingredient.

[0041] The basic substance used in the present invention is not particularly limited as long as it is a compound that exhibits basicity when dissolved in water, and various inorganic and organic compounds can be used. One or more basic substances may be blended.

[0042] Examples of the organic compound include monoethanolamine, triethanolamine, 2-amino-2-methyl-1,3-propanediol, aminomethylpropanol, aminomethylpropanol, 2-amino-2-hydroxymethyl-1,3-propanediol, arginine, and guanidine.

[0043] Examples of inorganic compounds include sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, calcium carbonate, and ammonia, and among these, potassium hydroxide is particularly suitable.

[0044] The amount of the basic compound in the aqueous dispersion composition of the present invention is not particularly limited, but in the case of a monovalent base relative to 1 mole of carboxylic acid groups contained in the (A) carboxylic acid-co-modified organopolysiloxane to be added, the carboxylic acid group / monovalent base (molar ratio) is preferably 1 / 0.5 to 1 / 1.5.

[0045] The pH of the aqueous dispersion composition of the present invention may be acidic or alkaline, but from the standpoint of anionizing the carboxylic acid-modified sites of the carboxylic acid co-modified organopolysiloxane (A) and improving the dispersibility of the powder or colorant, which is component (D), it is preferably weakly acidic to alkaline. Specifically, the pH of the entire composition is preferably in the range of 6.5 to 14.0, may be in the range of 7.1 to 10.0, and more preferably in the range of 7.2 to 9.5.

[0046] [(C) Hydrophilic medium] The hydrophilic medium is the main dispersion medium of the powder composition of the present invention, and is at least one selected from water, polyhydric alcohols, and lower alcohols, forming the aqueous phase of the composition. The powder composition of the present invention is preferably an aqueous dispersion, and in the presence of the above-mentioned components (A) and (B), it preferably forms a structure in which the powder or colorant (component (D)) is stably dispersed in the aqueous phase.

[0047] The hydrophilic medium in the present invention preferably contains water. On the other hand, (A) carboxylic acid co-modified organopolysiloxane has a silicon-containing organic group and a carboxyl group-containing organic group, both of which exhibit high water repellency, in the same molecule, and therefore, unlike conventionally known carboxylic acid-modified silicones, may be able to form an aqueous dispersion composition that exhibits excellent uniform dispersibility and stability of the powder or colorant (component (D)) in the aqueous phase, even when it does not contain one selected from polyhydric alcohols and lower alcohols (particularly ethyl alcohol).

[0048] When the hydrophilic medium of the present invention contains a polyhydric alcohol and a lower alcohol (particularly ethyl alcohol), the powder or colorant (component (D)) can be uniformly dispersed in the aqueous phase and exhibits excellent stability, and when the aqueous dispersion composition of the present invention is used as a cosmetic raw material, the moisturizing feel and usability can be adjusted in some cases. In particular, when used as a raw material for cosmetics, the hydrophilic medium (component (C)) in the powder composition preferably contains water, but component (C) may also be a mixture of (C1) water and one or more selected from (C2) a polyhydric alcohol and a lower alcohol (preferably ethanol).

[0049] Examples of polyhydric alcohols include sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, and polyethylene glycol. These polyhydric alcohols can be used alone or in combination of two or more. On the other hand, typical lower alcohols include methyl alcohol and ethyl alcohol, but from the perspective of use as a cosmetic ingredient, non-toxic ethyl alcohol is particularly preferred. Lower alcohols can be used alone or in combination with the aforementioned polyhydric alcohols. Specifically, ethyl alcohol and the aforementioned polyhydric alcohols can be used alone or mixed in any mass ratio between 100:0 and 0:100 in the present invention, and may or may not further contain water.

[0050] [(D) Powder or colorant] The (D) powder or colorant used in the powder composition (particularly the aqueous slurry) according to the present invention is one commonly used as a component of cosmetics, and includes white and color pigments and extender pigments. White and color pigments are used to color cosmetics, while extender pigments are used to improve the feel of cosmetics. The "powder" used in the present invention can be any white and color pigment or extender pigment commonly used in cosmetics, without any particular limitations. It is preferable to blend one or more types of powder in the present invention. There are no limitations on the shape (spherical, rod-like, needle-like, plate-like, irregular, spindle-like, cocoon-like, etc.), particle size (aerosol-like, fine particles, pigment-grade, etc.), or particle structure (porous, non-porous, etc.) of the powder, but it is preferable that the average primary particle size be in the range of 1 nm to 100 μm. In particular, when these powders or colorants are blended as pigments, it is preferable to blend one or more types selected from inorganic pigment powders, organic pigment powders, and resin powders having an average particle size in the range of 1 nm to 20 μm.

[0051] Examples of powders include inorganic powders, organic powders, surfactant metal salt powders (metal soaps), colored pigments, pearl pigments, and metal powder pigments, and composites of these can also be used. Furthermore, examples include those whose surfaces have been subjected to hydrophobic or water-repellent treatments. In particular, in the present invention, a preferred component (D) is a hydrophobic powder or colorant (D1) that has been hydrophobized. Specific examples of hydrophobic treatments and hydrophobic powders are the same as those of the hydrophobic powders or colorants disclosed by the applicants in paragraphs 0043 to 0054 of the above-mentioned Patent Document 2 (International Publication No. WO2020 / 036065).

[0052] Hydrophobic powders are difficult to disperse in an aqueous phase because their surfaces have been hydrophobized; however, by using the carboxylic acid co-modified organopolysiloxane of the present invention, it is possible to realize a composition (including use as a cosmetic ingredient or topical composition) in which a large amount of hydrophobic powder or colorant is uniformly and stably dispersed in an aqueous phase, and this has the advantage that a low-viscosity aqueous slurry can be prepared even with inorganic powders such as zinc oxide, which cannot be sufficiently dispersed under the same conditions as conventional carboxylic acid-modified silicones.

[0053] The hydrophobic powder used in the present invention is preferably an inorganic powder having ultraviolet absorbing / scattering ability, such as titanium oxide, zinc oxide, iron oxide, cerium oxide, or a composite thereof, the surface of which has been hydrophobized. The composite refers to a surface-treated powder, a powder in which other inorganic particles are dispersed within an inorganic powder, or the like. Particularly preferred is (D1-1) hydrophobized titanium oxide or zinc oxide fine particle having an average particle size in the range of 1 to 200 nm. By using the carboxylic acid-co-modified organopolysiloxane of the present invention, preferably together with the above-mentioned components (B) and (C), a powder composition, particularly an aqueous dispersion composition, in which these powders or colorants are uniformly and stably dispersed in an aqueous phase is formed.

[0054] [Powder composition as a raw material for cosmetics, etc., and its composition] The powder composition of the present invention containing the carboxylic acid co-modified organopolysiloxane and a powder or colorant is preferably an aqueous dispersion composition in which an aqueous phase made of a hydrophilic medium is a continuous phase, and is a composition in which a powder or colorant, particularly a hydrophobic powder or colorant, is dispersed in a hydrophilic medium, and can be used as a raw material for use in compositions such as cosmetics, paints, inks, etc. (hereinafter referred to as "cosmetics, etc.").

[0055] When used as a raw material for cosmetics, etc., the powder composition preferably contains the above-mentioned components (A) to (D) in an amount of 80% by mass or more, more preferably 90% by mass or more, based on the total amount of the composition. Furthermore, the powder composition of the present invention can form a low-viscosity aqueous slurry even when it contains a relatively large amount of powder or colorant. Therefore, it is possible to realize a composition in which the powder or colorant (component (D)), preferably the hydrophobic powder or colorant (D1) is contained in an amount ranging from 10 to 70% by mass, preferably from 15 to 65% by mass, and more preferably from 15 to 60% by mass of the total composition, and in which the powder or colorant is uniformly and stably dispersed in the aqueous phase.

[0056] When used as a raw material for cosmetics, etc., the powder composition preferably contains 5 to 30 parts by mass of component (A) per 100 parts by mass of component (D), particularly (D1) the hydrophobic powder or colorant, and more preferably 10 to 25 parts by mass. If the amount of component (A) is less than the lower limit, the hydrophobic powder or colorant may not be sufficiently dispersed in the aqueous phase, whereas if the amount of component (A) is more than the upper limit, it may not be possible to incorporate a sufficient amount of component (D) into the powder composition, which is an aqueous slurry.

[0057] When used as a raw material for cosmetics, etc., the hydrophilic medium (component (C)) in the powder composition preferably contains water. Specifically, when component (C) consists of (C1) water and (C2) one or more selected from polyhydric alcohols and lower alcohols (preferably ethanol), the content of component (C1) is preferably in the range of 10 to 80% by mass, more preferably 15 to 70% by mass, and particularly preferably 20 to 65% by mass, based on the total mass of the powder composition. Furthermore, the content of component (C2) is preferably in the range of 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, even more preferably 1 to 40% by mass, and particularly preferably 2 to 35% by mass, based on the total mass of the powder composition.

[0058] When used as a raw material for cosmetics, etc., the powder composition of the present invention preferably does not contain components other than the above-mentioned components in a proportion of the total of 20% by mass, and may contain other components in a proportion of 10% by mass or less, as long as the performance of the dispersion is not impaired. However, it is preferable not to add compounds that may impair the stability of the dispersion. In particular, the addition of oils is not recommended.

[0059] Optionally added components include, but are not limited to, preservatives. That is, an aqueous dispersion composition comprising the above components may decay depending on the storage conditions and storage period. To prevent such decay, a preservative may be added. Such preservatives are not particularly limited, and examples include glycol-based preservatives such as propylene glycol, butylene glycol, dipropylene glycol, pentylene glycol, and hexylene glycol; parabenzoic acid esters such as methyl parahydroxybenzoate; piroctone olamine, phenoxyethanol, and caprylic / capric triglyceride polyglyceryl-3. Each of these components can be added within a range that exhibits preservative properties and does not adversely affect the performance of the carboxylic acid-co-modified organopolysiloxane used as a dispersant. Among these, the use of pentylene glycol and 1,3-butylene glycol is particularly preferred. From the viewpoint of the above-mentioned applicability, it is preferable that the amount of components other than the carboxylic acid-co-modified organopolysiloxane, powder or colorant, water, and preservatives according to the present invention be 1% or less. The glycols mentioned above are often used in cosmetics as moisturizing agents, but because they have antibacterial properties, they also act as preservatives.

[0060] These components overlap with part of the above-mentioned component (C), and therefore, by using a polyhydric alcohol as component (C), it may be possible to improve the storage stability and moisturizing function of the powder composition of the present invention, particularly the aqueous slurry, without the need to add a separate preservative, moisturizer, etc.

[0061] The dispersion method for obtaining the powder composition of the present invention, particularly a composition in which a powder or a colorant is dispersed in a hydrophilic medium, is not particularly limited as long as it is a known method that can uniformly disperse each component using mechanical force, and methods using a bead mill, a high-pressure homogenizer, a three-roll mill, etc. are preferred.

[0062] The powder composition obtained by the present invention can also be applied to form a thin film. For example, a zinc oxide coating fixed with silica can be produced by applying a zinc oxide dispersion treated with silicone and then heat-treating it with high heat or plasma. Furthermore, when a dispersant such as polyether or polyether alkyl ether is used as the dispersant for the same zinc oxide dispersion, a silicone-coated zinc oxide coating can be easily produced by heating at a temperature lower than the decomposition temperature of the silicone coating the zinc oxide. Needless to say, coatings can also be formed with other powders.

[0063] [Use of aqueous dispersion composition: cosmetic raw materials, etc.] The aqueous dispersion composition of the present invention can also be incorporated directly into cosmetics, paints, inks, etc. In this case, a cosmetic composition, aqueous paint, or ink composition can be obtained by mixing the dispersion with various components used in cosmetics, paints, inks, etc. In particular, the aqueous dispersion composition of the present invention is suitable as a cosmetic raw material that is directly incorporated into cosmetics.

[0064] The cosmetic thus obtained can disperse hydrophobic powders suitably in the aqueous phase of the aqueous composition or emulsion, thereby enabling cosmetics containing the aqueous dispersion to have sufficient water repellency, water resistance, sebum resistance, and other properties.

[0065] The above-mentioned cosmetics are not particularly limited, and by mixing cosmetic raw materials with the aqueous dispersion composition of the present invention as necessary, it is possible to obtain UV protective cosmetics such as sunscreens, base makeup cosmetics such as foundations, point makeup cosmetics such as lipsticks, etc. In other words, the aqueous dispersion composition of the present invention can be used directly in the production of cosmetics.

[0066] The cosmetic preparations can be in any form, such as oil-based cosmetic preparations, aqueous cosmetic preparations, O / W cosmetic preparations, or W / O cosmetic preparations. In particular, they are particularly suitable for use in sunscreen cosmetic preparations (including sunscreen agents) because they can stably contain a large amount of inorganic UV protection agents.

[0067] The cosmetic preparation may contain any aqueous and oily components that can be used in the cosmetic field. The aqueous and oily components are not particularly limited, and may contain, for example, oils, surfactants, moisturizers, higher alcohols, sequestering agents, natural and synthetic polymers, water-soluble and oil-soluble polymers, UV screening agents, various extracts, coloring agents such as organic dyes, preservatives, antioxidants, pigments, thickeners, pH adjusters, fragrances, cooling agents, antiperspirants, disinfectants, skin activators, various powders, and other ingredients.

[0068] As these components, for example, those specifically disclosed in the above-mentioned Patent Documents 1 and 2 can be used without any restrictions.

[0069] When the aqueous dispersion composition of the present invention is incorporated into a paint, the resin in the paint may be either curable or non-curable. The paint may be a solvent-based paint containing an organic solvent, or a water-based paint in which the resin is dissolved or dispersed in water.

[0070] When the aqueous dispersion composition of the present invention is used as an additive component to a coating composition, it can be used in combination with film-forming resins such as acrylic resins, polyester resins, and epoxy resins; various pigments such as coloring pigments, extender pigments, and luster pigments; curing catalysts, surface conditioners, antifoaming agents, pigment dispersants, plasticizers, film-forming aids, ultraviolet absorbers, and antioxidants.

[0071] The aqueous paint and ink compositions thus obtained are also preferred in that the hydrophobic powder is stably dispersed in the aqueous medium.

[0072] [External preparation composition] As described above, the carboxylic acid-co-modified organopolysiloxane according to the present invention and compositions containing it can be incorporated into topical preparation compositions and used as cosmetic raw materials. Such topical preparation compositions may contain the carboxylic acid-co-modified organopolysiloxane (component (A)) described above, or may contain a carboxylic acid-co-modified organopolysiloxane composition containing the components (A), (B), and (C) described above and having a structure in which the carboxylic acid-modifying groups are partially neutralized in a hydrophilic medium, or may contain a carboxylic acid-co-modified organopolysiloxane composition containing the components (A), (B), (C), and (D) described above and having a structure in which component (D), which is a powder or colorant, is dispersed in a hydrophilic medium.

[0073] Particularly preferably, the topical preparation composition of the present invention contains the above-mentioned components (A), (B), (C), and (D), and preferably has a structure in which component (D), which is a powder or colorant, is dispersed in an aqueous phase. As described above, the use of the carboxylic acid-co-modified organopolysiloxane of the present invention allows for stable dispersion of (D1) a hydrophobic powder or colorant in an aqueous phase, and particularly allows for stable and uniform dispersion of (D1-1) hydrophobic titanium oxide or hydrophobic zinc oxide particulates having an average particle size in the range of 1 to 200 nm, which are useful as inorganic UV protection agents, in a large amount in an aqueous phase. This makes it possible to provide a topical preparation composition that has high storage stability and UV protection performance, minimizes deterioration in texture and feel when used, and provides a coating (cosmetic film) with excellent water resistance, etc. In particular, the use of the carboxylic acid-co-modified organopolysiloxane of the present invention is expected to further increase the flexibility in formulation, making it possible to provide sunscreen cosmetics and the like that combine performance such as water resistance, feel when used, and UV protection, as represented by SPF value.

[0074] The topical composition of the present invention is not particularly limited as long as it is a composition that can be applied to the human body as a cosmetic or pharmaceutical. Specific examples of the cosmetic of the present invention include skin cosmetics such as skin cleanser products, skin care products, makeup products, antiperspirant products, and UV protection products; hair cosmetics such as hair cleanser products, hair styling products, hair coloring products, hair care products, hair rinse products, hair conditioner products, and hair treatment products; and bath cosmetics. Examples of the pharmaceutical of the present invention include, but are not limited to, hair growth agents, hair restorers, analgesics, disinfectants, anti-inflammatory agents, cooling agents, and skin anti-aging agents.

[0075] The topical composition of the present invention may, and preferably, further comprise one or more selected from the group consisting of an oil, a carboxylic acid-modified silicone other than component (A), a salt of a higher fatty acid, various surfactants (which may be one or more selected from anionic, cationic, nonionic, and amphoteric surfactants, and may also be cleanser components), a water-soluble thickener, an oil-soluble film-forming agent, a water-soluble UV absorber, and a vinyl polymer emulsion. Specific examples of these components may include those disclosed in Patent Document 1 (WO 2015 / 159773) and those proposed by the applicant in an international patent application (PCT / JP19 / 029957). The combined use of these components (e.g., a vinyl polymer emulsion) may further improve the dispersibility of powders and the like in the aqueous phase, thereby improving the SPF value of the entire cosmetic composition.

[0076] The topical preparation composition of the present invention may contain other ingredients used in ordinary cosmetics, such as hydrophilic powders, moisturizers other than component (C), gelling agents, preservatives, antibacterial agents, fragrances, salts, antioxidants, pH adjusters other than component (B), chelating agents, cooling agents, anti-inflammatory agents, physiologically active ingredients (whitening agents, cell activators, skin roughness improving agents, blood circulation promoters, skin astringents, antiseborrheic agents, etc.), vitamins, amino acids, nucleic acids, hormones, inclusion compounds, etc., to the extent that the effects of the present invention are not impaired. The other ingredients are not particularly limited.

[0077] [Uses and replacements common to conventional carboxylic acid-modified silicones, especially commercially available products] The carboxylic acid co-modified organopolysiloxane according to the present invention can be used for the same purposes as carboxylic acid-modified silicones in the cosmetics and the like proposed by the present applicant in the above-mentioned Patent Document 1 (International Patent Publication No. WO2015 / 159773) and Patent Document 2 (International Patent Publication No. WO2020 / 036065), and can be used as a partial or complete replacement thereof. Similarly, the carboxylic acid co-modified organopolysiloxane according to the present invention can be used for the same purposes as the carboxylic acid-modified silicones in the formulations of the cosmetics proposed by the applicant in international patent applications (PCT / JP19 / 029957, PCT / JP19 / 029927), WO / 2020 / 036064, WO / 2020 / 036061, WO / 2020 / 036062, and WO / 2020 / 036063, and can be used to replace part or all of the carboxylic acid-modified silicones. In some cases, this can further improve the uniform dispersibility and storage stability of hydrophobic powders or colorants in the formulations without impairing the advantageous technical effects, usability, and feel of the cosmetics containing these carboxylic acid-modified silicones.

[0078] Furthermore, the carboxylic acid co-modified organopolysiloxane according to the present invention can be used for applications common to carboxylic acid-modified silicone products marketed by the applicant under the product name ES-5800 Formulation Aid (manufactured by Dow Toray Industries, Inc.) and the like. The applicant hereby explicitly teaches the use of the carboxylic acid-modified silicone product as a partial or total replacement for the carboxylic acid-modified silicone product in the methods of use and formulations of cosmetics and the like that are disclosed for the carboxylic acid-modified silicone product. [Example]

[0079] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. The amount of each component is expressed in "mass %" ("wt %) unless otherwise specified. In the structural formula, Me is a methyl group, and Bu is a butyl group.

[0080] [Examples 1 to 4] The carboxylic acid-co-modified organopolysiloxanes (compounds 1 to 4) according to the present invention were synthesized by the following method.

[0081] [Example 1] A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 126.90 g of trimethylsilyl undecylenate, 78.90 g of tristrimethylsiloxyvinylsilane, and 0.025 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and 94.20 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 3 hours, and then completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 45 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to perform deprotection. Low boiling point components were then removed again under reduced pressure to obtain Compound 1. Analysis confirmed that the resulting mixture was Compound 1, which has the following chemical structure: [ka]

[0082] [Example 2] 44.54 g of trimethylsilyl undecylenate, 52.29 g of a macromonomer raw material represented by Bu-(OSiMe2)6-CH=CH2, and 0.018 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed in a flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 33.18 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 3 hours, and then the completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 20 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to carry out deprotection. Low boiling point components were then removed again under reduced pressure to obtain Compound 2. Analysis confirmed that the resulting mixture was Compound 2, which has the following chemical structure: [ka]

[0083] [Example 3] A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 235.52 g of trimethylsilyl undecylenate, 45.92 g of tristrimethylsiloxyvinylsilane, and 0.078 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and 68.57 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 3 hours, and then completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 90 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to perform deprotection. Low boiling point components were then removed again under reduced pressure to obtain Compound 3. Analysis confirmed that the compound was Compound 3, which has the following chemical structure: [ka]

[0084] [Example 4] A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 120.58 g of trimethylsilyl undecylenate, 44.24 g of a macromonomer raw material represented by Bu-(OSiMe2)6-CH=CH2, and 0.044 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and 35.18 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. After the dropwise addition, the mixture was aged at 110°C for 3 hours, and then the completion of the reaction was confirmed by hydrogen generation. Low-boiling components were distilled off under reduced pressure. 50 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to perform deprotection. The low-boiling components were then removed again under reduced pressure to obtain compound 4. Analysis confirmed that the compound was compound 4, which has the following chemical structure: [ka]

[0085] The carboxylic acid-modified silicones used in the comparative experiments (comparative compounds 1 to 3) were synthesized by the following method. [Comparative Synthesis Example 1] 230.67 g of trimethylsilyl undecylenate and 0.042 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed in a flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 129.33 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 2 hours, and then the completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 90 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to carry out deprotection. Low boiling point components were then removed again under reduced pressure to obtain comparative compound 1. Analysis confirmed that the resulting mixture was comparative compound 1, which has the following chemical structure. [ka]

[0086] [Comparative Synthesis Example 2] A flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer was charged with 100 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane and 0.02 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, and 105 g of trimethylsilyl undecylenate was added dropwise to maintain the temperature between 70 and 100°C. After the addition was complete, the mixture was aged at 110°C for 2 hours, after which completion of the reaction was confirmed using a hydrogen generation method. Low-boiling components were distilled off under reduced pressure. Water was then added, and the mixture was aged under reflux for 4 hours, followed by deprotection. The low-boiling components were then removed again under reduced pressure to obtain comparative compound 2. Analysis confirmed that the chemical structure of comparative compound 2 was represented by the following chemical formula: [ka]

[0087] [Comparative Synthesis Example 3] 581.78 g of trimethylsilyl undecylenate and 0.087 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed in a flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 168.23 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 3 hours, and then the completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 190 g of ion-exchanged water was then added, and the mixture was aged under reflux for 4 hours to carry out deprotection. Low boiling point components were then removed again under reduced pressure to obtain comparative compound 3. Analysis confirmed that the resulting mixture was comparative compound 3, which has the following chemical structure. [ka]

[0088] [Comparative Synthesis Example 4] 304.20 g of trimethylsilyl undecylenate and 0.092 g of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex were placed in a flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer, and 304.20 g of methylhydrogenpolysiloxane represented by the following general formula was added dropwise so as to maintain the temperature within the range of 70-80°C. [ka] After the dropwise addition was completed, the mixture was aged at 110°C for 3 hours, and then the completion of the reaction was confirmed by hydrogen generation. Low boiling point components were distilled off under reduced pressure. 171.6 g of methanol was then added, and the mixture was aged under reflux for 4 hours to carry out deprotection. The low boiling point components were then removed again under reduced pressure to obtain comparative compound 4. Analysis confirmed that the resulting mixture was comparative compound 4, which has the following chemical structure: [ka]

[0089] [Preparation of Aqueous Dispersions: Examples 5 to 8, Comparative Examples 1 to 12] The ingredients shown in Tables 1 and 2 below were placed in a mayonnaise jar, and 160 g of zirconia beads (YTZ balls, φ0.8 mm) were then added. The mixture was dispersed using a paint shaker, and the beads were separated to obtain aqueous dispersions of Examples 5 and 6 and Comparative Examples 1 to 5. Each aqueous dispersion was evaluated using the following method, and the results are shown in Table 1. The viscosity of each aqueous dispersion was measured using an EMD-type viscometer (manufactured by Tokyo Keiki) immediately after preparation (initial), after leaving it to stand at room temperature for 4 days, and after leaving it to stand at room temperature for 4 months, and was evaluated on a 5-point scale according to the following criteria at each time point. If the dispersion was not stable and phase separation occurred, it was evaluated as "separated."

[0090] [Appearance evaluation of aqueous dispersion] The appearance of the aqueous dispersion was observed immediately after preparation. ○: The dispersion state was good and a low viscosity dispersion was obtained ×: Poorly dispersed and creamy [Evaluation of aqueous dispersion after standing for 4 months] 1: Extremely unsuitable as a cosmetic ingredient 2: Unsuitable as a cosmetic ingredient 3: Can be used as a cosmetic ingredient 4: Useful as a cosmetic ingredient 5:Very useful as a cosmetic ingredient

[0091] [Table 1] (Note 1) Product name: Isostearic Acid EX (Kyukyu Alcohol Kogyo Co., Ltd.) (Note 2) Product name: STR-100A-LP (manufactured by Sakai Chemical Industry Co., Ltd.) *High viscosity makes it impossible to measure

[0092] [Table 2] (Note 1) Product name: Isostearic Acid EX (Kyukyu Alcohol Kogyo Co., Ltd.) (Note 3) Product name: FINEX 30S-LPT (manufactured by Sakai Chemical Industry Co., Ltd.) *High viscosity makes it impossible to measure

[0093] As shown in Tables 1 and 2, by using the carboxylic acid co-modified organopolysiloxanes according to the examples, it was possible to obtain powder compositions that were low-viscosity aqueous slurries (aqueous dispersions) in which not only hydrophobic titanium oxide but also hydrophobic zinc oxide fine particles were stably dispersed in the aqueous phase. These aqueous slurries are useful as cosmetic ingredients, etc., and it is expected that the use of the carboxylic acid co-modified organopolysiloxanes according to the examples will make it easy to design topical compositions such as sunscreen cosmetics in which these powders are stably dispersed in the aqueous phase.

[0094] On the other hand, the carboxylic acid-modified silicones and higher fatty acids according to the comparative examples were able to obtain powder compositions that were relatively stable, low-viscosity aqueous slurries (aqueous dispersions) for hydrophobic titanium oxide, but it was confirmed that the aqueous slurries (aqueous dispersions) for hydrophobic zinc oxide microparticles rapidly thickened or phase separation occurred immediately to within four days of preparation. For this reason, the known carboxylic acid-modified silicones and higher fatty acids according to the comparative examples were unable to achieve sufficient dispersibility for some hydrophobic microparticles, making it impossible to achieve stable aqueous slurries or topical preparation compositions such as sunscreen cosmetics, and there were concerns that the degree of freedom in formulation design was insufficient, and that the stability of the obtained cosmetic raw materials and the performance of the topical preparation compositions such as cosmetics would be insufficient.

[0095] [Prescription design and prescription examples] The carboxylic acid co-modified organopolysiloxane according to the present invention can be used in place of part or all of the carboxylic acid-modified silicone in formulation examples of topical agent compositions that involve known carboxylic acid-modified silicones. Specifically, the carboxylic acid-modified silicones according to the examples or formulation examples disclosed in Patent Document 1 (International Patent Publication No. WO2015 / 159773), Patent Document 2 (International Patent Publication No. WO2020 / 036065), International Patent Applications (PCT / JP19 / 029957, PCT / JP19 / 029927), International Patent Publications WO / 2020 / 036064, WO / 2020 / 036061, WO / 2020 / 036062, and WO / 2020 / 036063 are replaced with the carboxylic acid-co-modified organopolysiloxanes (compounds 1-4) according to Examples 1 to 4 above, and are included within the scope of the present invention as formulation examples of the cosmetic composition according to the present invention, and the present applicant expressly teaches such uses and formulation designs.

Claims

1. (A) A carboxylic acid-co-modified organopolysiloxane represented by the following structural formula (1) which is liquid at 50°C. Structural formula (1): 【Chemistry 1】 {During the ceremony, R １ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, R ２ represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, L １ is the following general formula (2) when i = 1: 【Chemistry 2】 （２） (In the formula, R １ is the same group as above, and R Ｃ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is an alkylene group having 2 to 10 carbon atoms. ｉ where c is the number of generations, which is the number of repetitions of the silylalkyl group, and is an integer of 1 to c, and the number of generations c is an integer of 1 to 10; L ｉ＋１ is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. ｉ a silylalkyl group having a siloxane dendron structure represented by the formula: The following general formula (2'): 【Transformation 3】 （２´） (In the formula, R １１ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and R １１ wherein at least one of the above is the monovalent hydrocarbon group; t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500; and The following general formula (2'): 【Chemistry 4】 （２´´） (In the formula, R １１ and r is as defined above), Rc is a group represented by the general formula: -Rc 1 -(OR 2 )p-(O)w-Rc 3 -COOH(Rc 1 represents a linear or branched alkylene group having 2 to 22 carbon atoms; 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms; Rc 3 represents a bond (-) or a linear or branched alkylene group having 1 to 22 carbon atoms, p represents a number from 0 to 200, and w represents a number of 0 or 1), R' is independently the R １ , R ２ , L １ and Rc, (n1+n2+n3+n4) is a number in the range of 1 to 1000, n1 is a number in the range of 0 to 999, n2 is a number in the range of 0 to 100, n3 is a number in the range of 1 to 100, and n4 is a number in the range of 0 to 100, and when n4=0, at least one of R' is Rc.} (B) a basic compound, (C) one or more hydrophilic media selected from water, polyhydric alcohols, and lower alcohols; and (D) Hydrophobized zinc oxide fine particles having an average particle size in the range of 1 to 200 nm and having a structure in which component (D) is dispersed in an aqueous phase.

2. In formula (1), L １ is a functional group represented by the following general formula (2-1), general formula (2-2), or general formula (2'): General formula (2-1): 【Transformation 5】 （２－１） General formula (2-2): 【Transformation 6】 （２－２） (In the formula, R １ , R Ｃ and Z are the same groups as defined above, １ and a ２ are each independently a number ranging from 0 to 3. General formula (2'): 【Transformation 7】 （２´） (In the formula, R １１ are each independently the same group as defined above, t is a number ranging from 2 to 10, and r is a number ranging from 1 to 500.

3. 3. The powder composition according to claim 1, wherein, in the structural formula (1), (n1+n2+n3+n4) is a number in the range of 2 to 50, n1 is a number in the range of 0 to 49, n2 is a number in the range of 0 to 10, n3 is a number in the range of 1 to 10, and n4 is a number in the range of 0 to 10, and when n4 = 0, at least one of R' is Rc.

4. 4. The powder composition according to claim 1, which is liquid at room temperature (25°C), wherein in the structural formula (1), (n1+n2+n3+n4) is a number in the range of 2 to 20, n3 is a number in the range of 1 to 10, n4 is a number in the range of 1 to 10, and (n1+n2+n3) / n4 is in the range of 0.1 to 5.

0.

5. (A) A carboxylic acid-co-modified organopolysiloxane represented by the following structural formula (1) that is liquid at 50°C: Structural formula (1): 【Transformation 8】 {During the ceremony, R １ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, R ２ represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, L １ is the following general formula (2) when i = 1: 【Chemistry 9】 （２） (In the formula, R １ is the same group as above, and R Ｃ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is an alkylene group having 2 to 10 carbon atoms. ｉ where c is the number of generations, which is the number of repetitions of the silylalkyl group, and is an integer of 1 to c, and the number of generations c is an integer of 1 to 10; L ｉ＋１ is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. ｉ a silylalkyl group having a siloxane dendron structure represented by the formula: The following general formula (2'): 【Chemistry 10】 （２´） (In the formula, R １１ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and R １１ wherein at least one of the above is the monovalent hydrocarbon group; t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500; and The following general formula (2'): 【Chemistry 11】 （２´´） (In the formula, R １１ and r is as defined above), Rc is a group represented by the general formula: -Rc 1 -(OR 2 )p-(O)w-Rc 3 -COOH(Rc 1 represents a linear or branched alkylene group having 2 to 22 carbon atoms; 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms; Rc 3 represents a bond (-) or a linear or branched alkylene group having 1 to 22 carbon atoms, p represents a number from 0 to 200, and w represents a number of 0 or 1), R' is independently the R １ , R ２ , L １ and Rc, (n1+n2+n3+n4) is a number in the range of 1 to 1000, n1 is a number in the range of 0 to 999, n2 is a number in the range of 0 to 100, n3 is a number in the range of 1 to 100, and n4 is a number in the range of 0 to 100, and when n4=0, at least one of R' is Rc. (B) a basic compound, (C) one or more hydrophilic media selected from water, polyhydric alcohols, and lower alcohols; and (D) Hydrophobized zinc oxide fine particles having an average particle size in the range of 1 to 200 nm and having a structure in which component (D) is dispersed in an aqueous phase.

6. An external preparation composition containing the powder composition described in any one of claims 1 to 4.

7. The external preparation composition according to any one of claims 5 to 6, which is a cosmetic or pharmaceutical.

8. (A) A carboxylic acid-co-modified organopolysiloxane represented by the following structural formula (1) that is liquid at 50°C: Structural formula (1): 【Chemistry 12】 {During the ceremony, R １ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom, R ２ represents a substituted or unsubstituted, linear or branched monovalent hydrocarbon group having 6 to 30 carbon atoms, L １ is the following general formula (2) when i = 1: 【Chemistry 13】 （２） (In the formula, R １ is the same group as above, and R Ｃ is an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Z is an alkylene group having 2 to 10 carbon atoms. ｉ where c is the number of generations, which is the number of repetitions of the silylalkyl group, and is an integer of 1 to c, and the number of generations c is an integer of 1 to 10; L ｉ＋１ is the silylalkyl group when i is less than c, and is a methyl group or a phenyl group when i=c. ｉ a silylalkyl group having a siloxane dendron structure represented by the formula: The following general formula (2'): 【Chemistry 14】 （２´） (In the formula, R １１ are each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, a hydroxyl group, or a hydrogen atom, and R １１ wherein at least one of the above is the monovalent hydrocarbon group; t is a number in the range of 2 to 10, and r is a number in the range of 1 to 500; and The following general formula (2'): 【Chemistry 15】 （２´´） (In the formula, R １１ and r is as defined above), Rc is a group represented by the general formula: -Rc 1 -(OR 2 )p-(O)w-Rc 3 -COOH(Rc 1 represents a linear or branched alkylene group having 2 to 22 carbon atoms; 2 represents a linear or branched alkylene group having 2 to 4 carbon atoms; Rc 3 represents a bond (-) or a linear or branched alkylene group having 1 to 22 carbon atoms, p represents a number from 0 to 200, and w represents a number of 0 or 1), R' is independently the R １ , R ２ , L １ and Rc, The method for producing an external preparation composition according to any one of claims 5 to 7, comprising a step of previously mixing (n1+n2+n3+n4) a number in the range of 1 to 1000, n1 a number in the range of 0 to 999, n2 a number in the range of 0 to 100, n3 a number in the range of 1 to 100, and n4 a number in the range of 0 to 100, and when n4 = 0, at least one of R' is Rc.}, (B) a basic compound, (C) one or more hydrophilic media selected from water, polyhydric alcohols, and lower alcohols, and (D) hydrophobized zinc oxide fine particles having an average particle size in the range of 1 to 200 nm, and blending the mixture in the form of an aqueous dispersion of component (D).

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