Pyrithione polyvalent metal salt-containing composition

Abstract

A composition including a pyrithione polyvalent metal salt, a surfactant, and water, wherein the surfactant in the pyrithione polyvalent metal salt-containing composition is a compound represented by general formula (1). (In general formula (1), R1 represents an optionally substituted C7-21 alkyl group or a coconut oil fatty acid residue. R2 represents a C1-3 alkylene group. X1 represents a monovalent cation. Z represents a hydrogen atom or -R3COOX2. R3 represents a C1-3 alkylene group. X2 represents a monovalent cation.

Description

[Technical Field]

[0001] The present invention relates to a composition containing a pyrithione polyvalent metal salt, specifically to an aqueous composition containing a pyrithione polyvalent metal salt, a surfactant, and water. [Background technology]

[0002] Pyrithione polyvalent metal salts have antibacterial and antiseptic effects and are used as antibacterial agents, antidandruff agents, antifouling agents, bactericides, fungicides, etc. in applications such as cosmetics, shampoos, soaps, and other personal care products, medical products, plastic products, textile products, and paints. Examples of commonly and widely used pyrithione polyvalent metal salts include zinc pyrithione and copper pyrithione. For example, zinc pyrithione is effective against dandruff and seborrheic dermatitis and is therefore used in cosmetics, shampoos, soaps, and other personal care products, while copper pyrithione is used in antifouling paints for ship bottoms and other applications as an agent to prevent adhesion of aquatic organisms.

[0003] Generally, pyrithione polyvalent metal salt has extremely low solubility in water, high specific gravity, and its particles are prone to aggregation.Therefore, the particles of pyrithione polyvalent metal salt are prone to aggregation and sedimentation in aqueous liquid, and it is difficult to stably disperse them.In addition, when the particles of pyrithione polyvalent metal salt are dispersed in aqueous liquid, the effect is limited to the periphery of the particles in the aqueous liquid, so in order to fully exhibit the effects of anti-dandruff effect, antibacterial effect, etc., it is necessary to increase the amount of compounding. However, from the viewpoint of environmental load, etc., there is a demand for a method that can exert the effects of pyrithione polyvalent metal salts at lower concentrations. Furthermore, particularly in the field of personal care products, there has been a demand in recent years for transparent products such as transparent shampoos and transparent soaps.

[0004] In response to this, methods have been proposed in which the pyrithione polyvalent metal salt is solubilized or used at a lower concentration.

[0005] For example, Patent Document 1 describes a method for dissolving zinc pyrithione in water using a hydrotrope such as sodium cumene sulfonate, sodium xylene sulfonate, or sodium toluene sulfonate. However, because zinc pyrithione is often used in detergents such as shampoos due to its properties, incorporating ingredients other than surfactants, such as hydrotropes, is undesirable as it reduces detergency and increases costs unnecessarily. Patent Document 1 also describes a transparent personal care formulation containing zinc pyrithione, a hydrotrope, a surfactant, and water, but it is difficult to dissolve zinc pyrithione in water using only the surfactant described in Patent Document 1. For this reason, Patent Document 1 uses a combination of a surfactant and a hydrotrope to dissolve zinc pyrithione in water.

[0006] Patent Document 2 describes a transparent disinfectant composition that uses zinc pyrithione alone or in combination with a quaternary ammonium salt and contains an organic amine and / or alkanolamine, a water-miscible solvent such as a water-soluble glycol, polyol, glycol ether, or lactam. Patent Document 2 uses the quaternary ammonium salt to reduce the amount of zinc pyrithione used. Furthermore, to obtain a transparent composition, an organic amine and / or alkanolamine and a water-miscible solvent are required.

[0007] Patent Document 3 describes a hair cosmetic composition containing a zinc pyrithione solution obtained using iodopropynyl butylcarbamate and / or N-acylethylenediamine triacetate as a solvent. In Patent Document 3, the amount of zinc pyrithione used is reduced by using iodopropynyl butylcarbamate, which exhibits antibacterial properties. Furthermore, zinc pyrithione is dissolved by using N-acylethylenediamine triacetate, which is also a chelating surfactant.

[0008] Blending many components as in Patent Documents 2 and 3 is undesirable because it leads to a decrease in cleaning power and unnecessary increase in costs. Furthermore, the use of organic solvents is not very preferable from the viewpoint of environmental load and industrial production.

[0009] Patent Document 4 describes a method for producing a suspension, emulsion, or dispersion of pyrithione salt particles in the low submicron range (less than about 0.2 μm) by contacting agglomerated pyrithione salt particles with a deflocculating agent using sonic energy or heat. Patent Document 4 uses submicron-sized particles of pyrithione salt to produce a translucent to transparent suspension, but the pyrithione salt is not dissolved. Furthermore, producing submicron-sized particles can lead to increased costs.

[0010] [Patent Document 1] IN317938B [Patent Document 2] Special Publication No. 2016-534130 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-154936 [Patent Document 4] Special Publication No. 2003-526616 Summary of the Invention

[0011] The present invention aims to provide a composition containing a pyrithione polyvalent metal salt, in which the pyrithione polyvalent metal salt is stably dissolved in water without flocculation or precipitation. This composition can exhibit a high antibacterial effect even when the pyrithione polyvalent metal salt is incorporated in a low amount. It also makes it possible to realize a transparent personal care product.

[0012] The present inventors have found that the above problems can be solved by using a specific surfactant. The present invention provides the following.

[0013] [1] A composition containing a pyrithione polyvalent metal salt, a surfactant, and water, wherein the surfactant is a compound represented by the following general formula (1):

[0014] [ka]

[0015] (In general formula (1), R 1 represents an alkyl group having 7 to 21 carbon atoms which may have a substituent, or a coconut oil fatty acid residue. 2 represents an alkylene group having 1 to 3 carbon atoms. 1 represents a monovalent cation. Z represents a hydrogen atom or -R 3 COOX 2 Represents R 3 represents an alkylene group having 1 to 3 carbon atoms. 2 represents a monovalent cation.)

[0016] [2] The pyrithione polyvalent metal salt-containing composition according to [1], wherein the compound represented by general formula (1) satisfies the following requirement I: Requirement I: The liquid obtained by mixing the pyrithione polyvalent metal salt, water, and the compound represented by general formula (1) in a weight ratio of 0.2:89.8:10 has a transmittance of 95% or more at 25°C (optical path length 1 cm) at 655 nm.

[0017] [3] The surfactant is R 2 The pyrithione polyvalent metal salt-containing composition according to [1] or [2], wherein R is a compound in which R is a methylene group.

[0018] [4] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [3], wherein the surfactant is sodium lauroamphoacetate, sodium cocoamphoacetate, or disodium cocoamphodiacetate.

[0019] [5] The composition containing a pyrithione polyvalent metal salt according to any one of [1] to [4], wherein the pyrithione polyvalent metal salt is a compound represented by the following general formula (2):

[0020] [ka]

[0021] (In general formula (2), M n+ represents a polyvalent metal ion, and n is a number indicating the valence of the polyvalent metal ion.

[0022] [6] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [5], wherein the content of the pyrithione polyvalent metal salt is 0.01% by weight to 1% by weight, and the content of the surfactant is 0.1% by weight to 30% by weight.

[0023] [7] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [6], wherein the amount of the surfactant is 10 to 100 times by weight relative to the amount of the pyrithione polyvalent metal salt.

[0024] [8] The volume average particle diameter (D 50 The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [7], wherein the particle size is 0.1 μm to 5 μm.

[0025] [9] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [8], which is a composition that is substantially free of a hydrotropic agent.

[0026]

[10] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to [9], which is a composition that is substantially free of organic solvents.

[0027]

[11] The pyrithione polyvalent metal salt-containing composition according to any one of [1] to

[10] , further comprising a surfactant, a water-soluble polymer, and an oily component as cleansing components. [Effects of the Invention]

[0028] According to the present invention, it is possible to provide a highly transparent composition containing a pyrithione polyvalent metal salt, in which the pyrithione polyvalent metal salt is stably dissolved in water without flocculation or precipitation due to the action of a specific surfactant, and it is also possible to provide a composition containing a pyrithione polyvalent metal salt that exhibits a high antibacterial effect even when the pyrithione polyvalent metal salt is incorporated in a low amount. Furthermore, a highly transparent pyrithione polyvalent metal salt-containing composition can be provided without using components that are not directly related to the cleaning function, such as hydrotropes; other antibacterial components, such as quaternary ammonium salts and iodopropynyl butylcarbamate; water-miscible solvents, such as water-soluble glycols, polyols, glycol ethers, and lactams; organic solvents, such as iodopropynyl butylcarbamate and N-acylethylenediamine triacetate; or low submicron particle diameter particles of pyrithione polyvalent metal salts.

[0029] According to the present invention, particularly in personal care product applications such as shampoo, even when a pyrithione polyvalent metal salt is blended in a low amount, it is possible to provide a transparent personal care product while effectively exhibiting the inherent anti-dandruff and antibacterial effects of the pyrithione polyvalent metal salt. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be described in detail below with reference to embodiments.

[0031] [Composition containing pyrithione polyvalent metal salt] The pyrithione polyvalent metal salt-containing composition of the present invention is a composition containing a pyrithione polyvalent metal salt, a surfactant, and water, characterized in that the surfactant is a compound represented by the following general formula (1):

[0032] [ka]

[0033] (In general formula (1), R 1 represents an alkyl group having 7 to 21 carbon atoms which may have a substituent, or a coconut oil fatty acid residue.2 represents an alkylene group having 1 to 3 carbon atoms. 1 represents a monovalent cation. Z represents a hydrogen atom or -R 3 COOX 2 Represents R 3 represents an alkylene group having 1 to 3 carbon atoms. 2 represents a monovalent cation.)

[0034] The compound represented by the above general formula (1) preferably satisfies the following requirement I. Requirement I: The liquid obtained by mixing the pyrithione polyvalent metal salt, water, and the compound represented by general formula (1) in a weight ratio of 0.2:89.8:10 has a transmittance of 95% or more at 25°C (optical path length 1 cm) at 655 nm. The light transmittance in the present invention is specifically measured by the method described in the Examples section below.

[0035] The pyrithione polyvalent metal salt-containing composition of the present invention is usually an aqueous composition containing 50% by weight or more of water.

[0036] <Pyrithione polyvalent metal salts> Examples of pyrithione polyvalent metal salts include compounds represented by the following general formula (2).

[0037] [ka]

[0038] (In general formula (2), M n+ represents a polyvalent metal ion, and n is a number indicating the valence of the polyvalent metal ion.

[0039] M in the above general formula (2) n+ Examples of M include polyvalent metal ions selected from magnesium, aluminum, iron, copper, zinc, strontium, zirconium, cadmium, barium, and bismuth. M is preferably magnesium, copper, zinc, strontium, zirconium, cadmium, barium, or bismuth, more preferably copper or zinc, and particularly preferably zinc.

[0040] In the above general formula (2), n is usually an integer of 2 to 5, preferably 2 or 3, and particularly preferably 2.

[0041] As the pyrithione polyvalent metal salt, copper pyrithione and zinc pyrithione are preferably used because of their excellent antibacterial, antifouling, and antidandruff effects. In particular, zinc pyrithione (zinc salt of 1-hydroxy-2-pyridinethione, i.e., zinc complex of 2-pyridinethiol-1-oxide) represented by the following formula (2A) is preferably used for personal care products because it is effective against dandruff and seborrheic dermatitis.

[0042] [ka]

[0043] The pyrithione polyvalent metal salt-containing composition of the present invention may use only one of these pyrithione polyvalent metal salts, or may use a mixture of two or more of them.

[0044] The pyrithione polyvalent metal salt used in the present invention is preferably in the form of particles, and its average particle diameter (D 50 ) is not particularly limited, and is usually 0.1 μm to 5 μm. From the viewpoint of solubility in water and dispersion stability when producing a pyrithione polyvalent metal salt-containing composition, the average particle diameter (D 50 ) is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, and is preferably 1 μm or less, more preferably 0.6 μm or less, particularly preferably 0.5 μm or less. Here, the average particle diameter (D 50 ) is a volume average particle size determined by a laser diffraction / scattering method, and can be measured, for example, by a Microtrac MT3000II manufactured by Nikkiso Co., Ltd.

[0045] The pyrithione polyvalent metal salt used in the present invention can be a commercially available product. For example, synpyrithione can be Tomicide (registered trademark) ZPT-50 or Tomicide (registered trademark) ZPT-100 manufactured by Mitsubishi Chemical Corporation or API Corporation.

[0046] According to the present invention, the average particle diameter (D 50 A transparent composition containing a pyrithione polyvalent metal salt can be obtained even without using particles of a pyrithione polyvalent metal salt having a particle size of less than 0.1 μm.

[0047] <Surfactant> The surfactant used in the present invention is a compound represented by the following general formula (1).

[0048] [ka]

[0049] (In general formula (1), R 1 represents an alkyl group having 7 to 21 carbon atoms which may have a substituent, or a coconut oil fatty acid residue. 2 represents an alkylene group having 1 to 3 carbon atoms. 1 represents a monovalent cation. Z represents a hydrogen atom or -R 3 COOX 2 Represents R 3 represents an alkylene group having 1 to 3 carbon atoms. 2 represents a monovalent cation.)

[0050] By using the compound represented by the above general formula (1) as a surfactant, the pyrithione polyvalent metal salt can be stably dissolved in water, and a transparent pyrithione polyvalent metal salt-containing composition can be obtained.

[0051] R 1 is an alkyl group having 7 to 21 carbon atoms which may have a substituent, or a coconut oil fatty acid residue. The number of carbon atoms in the alkyl group is preferably 9 to 17, and from the viewpoint of the solubility of the pyrithione polyvalent metal salt, more preferably 11 to 15. The number of carbon atoms is determined by the formula (R 1 When R is an alkyl group having a substituent, the number of carbon atoms includes the number of carbon atoms of the substituent. Examples of the substituent include a phenyl group, a naphthyl group, and an alkenyl group which may have a branch. For use in personal care products such as cosmetics, shampoos, and soaps, R 1 is preferably an alkyl group having no substituent. R 1 The coconut oil fatty acid residue is the alkyl group portion of coconut oil fatty acid, and is usually a mixture of saturated or unsaturated alkyl groups having 6 to 18 carbon atoms, preferably 11 to 15 carbon atoms from the viewpoint of the solubility of the pyrithione polyvalent metal salt.

[0052] R 2 is an alkylene group having 1 to 3 carbon atoms, and the number of carbon atoms is preferably 1 or 2. In particular, from the viewpoint of the solubility of the pyrithione polyvalent metal salt, R 2 is preferably a methylene group having one carbon atom.

[0053] X 1 is a monovalent cation, preferably an ammonium ion, a sodium ion, or a potassium ion, and more preferably a sodium ion from the viewpoint of cost and the like.

[0054] Z is a hydrogen atom or -R 3 COOX 2 Represents. R 3 is an alkylene group having 1 to 3 carbon atoms, and the number of carbon atoms is preferably 1 or 2, and from the viewpoint of the solubility of the pyrithione polyvalent metal salt, more preferably 1. X 2 is a monovalent cation, preferably an ammonium ion, a sodium ion, or a potassium ion, more preferably a sodium ion. X 2 is X 1 may be the same as or different from X 1is preferably the same as From the viewpoint of the solubility of the pyrithione polyvalent metal salt, Z is a hydrogen atom or -CH2COOX 2 is preferred.

[0055] As the surfactant represented by general formula (1), ammonium salts, sodium salts and potassium salts are preferred, and from the viewpoint of cost etc., sodium salts are more preferred.

[0056] As the surfactant represented by general formula (1), a compound represented by the following general formula (1A) is preferred from the viewpoint of the solubility of the pyrithione polyvalent metal salt.

[0057] [ka]

[0058] (In general formula (1A), R 1 , X 1 and Z have the same meanings as defined above.

[0059] The surfactant represented by the general formula (1) can be a commercially available product, but can also be produced by a conventional method. For example, a higher fatty acid having 8 to 22 carbon atoms (R 1 C(O) moiety) is reacted with N-(2-aminoethyl)ethanolamine (to form an acid amide bond), and then a carboxylic acid having 4 or less carbon atoms and a halogen substituent at the α- or β-position (R 2 The halogen substitution position of the halogenated carboxylic acid is preferably the α-position, and the number of carbon atoms in the carboxylic acid is preferably 2 or 3, and more preferably 2.

[0060] As the surfactant represented by general formula (1), N-fatty acid acylaminoethyl-N-2-hydroxyethylglycinate is preferred from the viewpoint of the solubility of the pyrithione polyvalent metal salt. Specifically, sodium N-coconut oil fatty acid acylaminoethyl-N-2-hydroxyethylglycinate and sodium N-laurate acylaminoethyl-N-2-hydroxyethylglycinate are preferred. In particular, sodium lauroamphoacetate (R 1 is an alkyl group having 11 carbon atoms, R 2 is a methylene group, X 1 is a sodium ion, Z is a hydrogen atom), sodium cocoamphoacetate (in general formula (1), R 1 is an alkyl group having 11 to 15 carbon atoms, R 2 is a methylene group, X 1 where R is a sodium ion and Z is a hydrogen atom), disodium cocoamphodiacetate (in general formula (1), R 1 is an alkyl group having 11 to 15 carbon atoms, R 2 is a methylene group, X 1 A mixture in which Z is a sodium ion and Z is -CH2COONa is more preferred. Sodium lauroamphoacetate is particularly preferred because it provides high solubility of pyrithione polyvalent metal salts even in the acidic pH range of 6 to 5.

[0061] The surfactant represented by general formula (1) used in the present invention is preferably one that, when a pyrithione polyvalent metal salt, water, and the surfactant are mixed in a weight ratio of 0.2:89.8:10, can form a transparent aqueous solution in which the solubility of the pyrithione polyvalent metal salt in water is high and the transmittance of the resulting solution at a wavelength of 655 nm is 95% or more. The light transmittance is preferably 97% or more, and more preferably 98% to 100%.

[0062] In particular, the surfactant represented by general formula (1) used in the present invention is preferably one that maintains high solubility of the pyrithione polyvalent metal salt in water even when the pyrithione polyvalent metal salt is mixed with water and the surfactant in a weight ratio of 0.5:89.5:10, and can form a transparent aqueous solution having a light transmittance of 95% or more at a wavelength of 655 nm. The light transmittance is preferably 97% or more, and more preferably 98% to 100%.

[0063] In the present invention, the surfactant represented by general formula (1) may be used alone or in combination of two or more. Furthermore, surfactants other than those represented by general formula (1) may be used in combination as long as they do not affect the effects of the present invention.

[0064] <Water> The type of water is not particularly limited as long as it does not affect the effects of the present invention, and any of distilled water, pure water, ultrapure water, tap water, etc. can be used.

[0065] <ph> The pH of the pyrithione polyvalent metal salt-containing composition of the present invention is not particularly limited. Typically, a composition obtained by mixing a pyrithione polyvalent metal salt, a surfactant, and water has a pH of about 5.0 to 9.0, and the higher the pH, the more easily the pyrithione polyvalent metal salt tends to dissolve. The pyrithione polyvalent metal salt-containing composition of the present invention may also have a pH of about 5.0 to 9.0.

[0066] For use in personal care products such as shampoos, the pH is preferably about 5 to 6. The pyrithione polyvalent metal salt-containing composition of the present invention may also be adjusted to about pH 5 to 6 by adding a pH adjuster such as citric acid as appropriate.

[0067] According to the present invention, by using a surfactant represented by general formula (1), a pyrithione polyvalent metal salt can be stably dissolved in water even in the acidic range of about pH 5 to 6, which is preferable for use in shampoos and the like, and a transparent pyrithione polyvalent metal salt-containing composition can be provided.

[0068] <Composition> The composition of the pyrithione polyvalent metal salt and the surfactant represented by general formula (1) in the pyrithione polyvalent metal salt-containing composition of the present invention is not particularly limited as long as it does not affect the effects of the present invention, and can be determined appropriately depending on the application.

[0069] The content (concentration) of the pyrithione polyvalent metal salt is not particularly limited as long as it is a concentration at which its effect is exhibited, but a relatively low concentration is preferable from the viewpoint of environmental load, etc. The content (concentration) of the pyrithione polyvalent metal salt is usually 0.01% by weight to 1% by weight, preferably 0.05% by weight to 0.8% by weight, more preferably 0.1% by weight to 0.6% by weight, and particularly preferably 0.15% by weight to 0.5% by weight.

[0070] The content (concentration) of the surfactant represented by general formula (1) may be a concentration that can dissolve the pyrithione polyvalent metal salt, but it is not necessary to use an excessive amount from the viewpoint of cost, etc. The content (concentration) of the surfactant represented by general formula (1) is usually 0.1% by weight to 30% by weight, preferably 1% by weight to 20% by weight, more preferably 2% by weight to 15% by weight, and particularly preferably 3% by weight to 10% by weight.

[0071] The surfactant represented by general formula (1) can dissolve the pyrithione polyvalent metal salt, and may be used in an amount sufficient to obtain a transparent composition containing the pyrithione polyvalent metal salt, but it is not necessary to use an excessive amount from the viewpoint of cost, etc. The surfactant represented by general formula (1) can be used in an amount of usually 10 to 100 times by weight, more preferably 15 to 80 times by weight, and particularly preferably 20 to 50 times by weight relative to the pyrithione polyvalent metal salt.

[0072] The pyrithione polyvalent metal salt-containing composition of the present invention is usually an aqueous composition containing water in an amount of 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, and particularly preferably 80% by weight or more.

[0073] The pyrithione polyvalent metal salt-containing composition of the present invention may contain components other than the pyrithione polyvalent metal salt, the surfactant represented by general formula (1), and water, as long as the components do not affect the effects of the present invention.

[0074] <Method for preparing a composition containing a pyrithione polyvalent metal salt> There are no particular limitations on the method for preparing the pyrithione polyvalent metal salt-containing composition of the present invention, but it can be prepared, for example, by the following procedure. (1) A predetermined amount of pyrithione polyvalent metal salt is added to water and stirred at room temperature for a period of usually about 20 seconds to 5 minutes, preferably about 30 seconds to 2 minutes. (2) Then, a predetermined amount of the surfactant represented by general formula (1) is added and stirred at room temperature for a period of usually about 1 to 20 minutes, preferably about 3 to 10 minutes. (3) Thereafter, the mixture is heated to a temperature of about 25° C. to 80° C., preferably about 40° C. to 70° C., and stirred. The stirring time is usually about 1 minute to 60 minutes, preferably about 10 minutes to 40 minutes. (4) Further cool the mixture with air while stirring until it reaches room temperature.

[0075] In the above steps (1), (2) and (3), room temperature means a temperature of about 20°C to 25°C.

[0076] The pyrithione polyvalent metal salt may be used in powder form or in an aqueous suspension (pyrithione polyvalent metal salt concentration of about 10% by weight to 80% by weight). When using an aqueous suspension of a pyrithione polyvalent metal salt, the amount of the aqueous suspension used is adjusted so that the pyrithione polyvalent metal salt concentration in the pyrithione polyvalent metal salt-containing composition to be obtained becomes the desired concentration.

[0077] The surfactant represented by general formula (1) may be used at a concentration of 100%, or may be used as a solution containing the surfactant at an appropriate concentration. When using a solution containing the surfactant, the amount of the solution used is adjusted so that the concentration of the surfactant in the pyrithione polyvalent metal salt-containing composition to be obtained becomes the desired concentration.

[0078] When the pyrithione polyvalent metal salt-containing composition of the present invention contains components other than the pyrithione polyvalent metal salt and the surfactant represented by general formula (1), it is preferable to add the other components after the step (3) above, stir at a temperature similar to that of the step (3) above, and then return the mixture to room temperature. The stirring time is usually about 1 to 60 minutes, preferably about 10 to 40 minutes.

[0079] The pyrithione polyvalent metal salt-containing composition of the present invention can be preferably prepared by the following procedure. (1') A predetermined amount of pyrithione polyvalent metal salt is added to water and stirred at room temperature (about 20°C to 25°C, for example, 23°C) for about 1 minute. (2') Then, a predetermined amount of the surfactant represented by general formula (1) is added and stirred at room temperature (about 20°C to 25°C, for example, 23°C) for about 5 minutes. (3') Further, the mixture is heated to 40°C to 70°C, for example, 60°C, and stirred for about 30 minutes. If necessary, other components other than the pyrithione polyvalent metal salt and the surfactant represented by general formula (1) are added, and the mixture is stirred at 40°C to 70°C, for example, 60°C, for about 30 minutes. (4') Cool the mixture with air while stirring to room temperature (approximately 20°C to 25°C, for example, 23°C).

[0080] In order to prevent a decrease in detergency and an increase in cost, the pyrithione polyvalent metal salt-containing composition of the present invention is preferably a composition that is substantially free of hydrotropes such as sodium cumene sulfonate, sodium xylene sulfonate, sodium toluene sulfonate, etc. Furthermore, in terms of environmental impact and industrial production, the pyrithione polyvalent metal salt-containing composition of the present invention is preferably a composition that is substantially free of water-miscible solvents such as water-soluble glycols, polyols, glycol ethers, and lactams, and organic solvents such as iodopropynyl butylcarbamate and N-acylethylenediamine triacetate. Here, "substantially free" means not only that the compound is not contained at all but also that the compound is contained in an amount so small that it can be recognized as an impurity. The content of the compound in the pyrithione polyvalent metal salt-containing composition of the present invention varies depending on the embodiment, but is 0% by weight to 0.005% by weight, preferably 0% by weight to 0.0001% by weight.

[0081] [Cleaning agent] When the pyrithione polyvalent metal salt-containing composition of the present invention is used as a cleaning agent, the pyrithione polyvalent metal salt-containing composition of the present invention may contain a surfactant other than the surfactant represented by general formula (1) as a cleaning component. Examples of surfactants contained as cleansing components include anionic surfactants, amphoteric surfactants, nonionic surfactants, cationic surfactants, and semi-polar surfactants.

[0082] Examples of anionic surfactants include alkyl ether sulfates, alkyl sulfates, olefin sulfonates, alkyl sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkenyl sulfates, paraffin sulfonates, alkylamide sulfonates, alkenylamide sulfonates, alkyl sulfoacetates, alkenyl sulfoacetates, alkyl glyceryl ether sulfonates, polyoxyalkylene aliphatic amide ether sulfates, monoglyceride sulfates, alkyl glyceryl ether sulfates, N-alkylamide alkanol sulfates, acyl isethionates, acyl glutamates, acyl lactylates, acylated taurates, alkyl ether carboxylates, acylalanines, acyl sarcosines, and higher fatty acid salts. Among these, alkyl ether sulfates, alkyl ether carboxylates, and higher fatty acid salts are preferred from the viewpoint of detergency (detergency, foaming ability, and foam quality). Acylated taurate, acylalanine salt, acylsarcosine salt, and acylglutamate are preferred from the viewpoint of conditioning properties (low irritation, smooth rinsing).

[0083] When the surfactant is a salt, the counter ion that forms the salt is not particularly limited, but examples include alkali metal ions such as sodium and potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ions; and alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine.

[0084] Examples of amphoteric surfactants include amidoamino acid type surfactants, amidobetaine type amphoteric surfactants, amidosulfobetaine type amphoteric surfactants, betaine type amphoteric surfactants, sulfobetaine type amphoteric surfactants, phosphobetaine type amphoteric surfactants, carbobetaine type amphoteric surfactants, amino acid type amphoteric surfactants, phosphate ester type amphoteric surfactants, imidazolinium type amphoteric surfactants, etc. Among these, alkylamidopropyl betaines having 12 to 14 carbon atoms are preferably used in terms of foaming and cleaning properties.

[0085] Examples of nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers or polyoxyalkylene alkenyl ethers, polyoxyethylene hydrogenated castor oil, polyoxyalkylene polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, fatty acid glycerin esters, fatty acid glycol esters, alkylene glycol fatty acid esters, polyalkylene glycol fatty acid esters, polyglycerin fatty acid esters, polyoxyalkylene glycerin fatty acid esters, alkyl sucrose Examples of surfactants include chloride surfactants, fatty acid monoethanolamides or diethanolamides or ethoxylates thereof, monoglyceride ethoxylates, fatty acid sucrose esters, polyoxyalkylene lanolin or lanolin alcohol or beeswax derivatives, polyoxyethylene sterol or hydrogenated sterol, polyoxyalkylene alkyl ether phosphoric acid or phosphate salts, polyoxyalkylene alkyl allyl ethers, polyoxyalkylene glyceryl monofatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid amides, polyoxyalkylene alkylamides, and polyalkyleneimine derivatives.

[0086] Examples of cationic surfactants include alkyltrimethylammonium salts, alkoxytrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylamines or salts thereof, alkoxydimethylamines or salts thereof, and alkylamidomethylamines and salts thereof.

[0087] Examples of semi-polar surfactants include tertiary amine oxide semi-polar surfactants such as alkylamine oxides and alkylamidoamine oxides. Among these, lauryldimethylamine oxide is preferably used because of its foaming properties and its ability to act as a viscosity adjuster.

[0088] These surfactants used as cleaning components may be used alone or in combination of two or more.

[0089] When the pyrithione polyvalent metal salt-containing composition of the present invention is used as a detergent, the pyrithione polyvalent metal salt-containing composition of the present invention may further contain a water-soluble polymer. Examples of water-soluble polymers include cationic polymers, anionic polymers, nonionic polymers, and amphoteric polymers.

[0090] Cationic polymers include cationically modified cellulose ether derivatives, cationic starch, cationized guar gum derivatives, homopolymers of diallyl quaternary ammonium salts, quaternized polyvinylpyrrolidone derivatives, polyglycol polyamine condensates, vinylimidazolium trichloride / vinylpyrrolidone copolymers, hydroxyethyl cellulose / dimethyl diallyl ammonium chloride copolymers, polydimethyl diallyl ammonium halides, dimethyl diallyl ammonium hydride / acrylic acid copolymers, dimethyl diallyl ammonium hydride / acrylic acid / acrylamide copolymers, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymers, polyvinylpyrrolidone / alkylaminoacrylate copolymers, polyvinylpyrrolidone / alkylaminoacrylate / vinyl Examples of the cationic polymers include dicaprolactam copolymer, vinylpyrrolidone / methacrylamidopropyl trimethylammonium chloride copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropyl ethylenetriamine copolymer, dimethyldiallylammonium halide polymer, dimethyldiallylammonium halide / acrylamide copolymer, propyltrimonium chloride acrylamide / dimethylacrylamide copolymer, propyltrimonium chloride acrylamide / ethyltrimonium chloride methacrylate / dimethylacrylamide copolymer, and ethyltrimonium chloride methacrylate / hydroxyethylacrylamide copolymer.

[0091] Examples of the anionic polymer include acrylic acid derivatives such as polyacrylic acid and salts thereof, acrylic acid-acrylamide-ethyl acrylate copolymers and salts thereof, methacrylic acid derivatives, and crotonic acid derivatives.

[0092] Examples of nonionic polymers include acrylic acid derivatives such as hydroxyethyl acrylate-methoxyethyl acrylate copolymer and polyacrylamide, vinylpyrrolidone derivatives such as polyvinylpyrrolidone, vinylpyrrolidone, vinyl acetate copolymer, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, etc.

[0093] Examples of amphoteric polymers include dimethyldiallylammonium chloride derivatives such as acrylamide-acrylic acid-dimethyldiallylammonium chloride copolymer and acrylic acid-dimethyldiallylammonium chloride copolymer.

[0094] When the pyrithione polyvalent metal salt-containing composition of the present invention is used as a detergent, the pyrithione polyvalent metal salt-containing composition of the present invention may further contain an oily component. Examples of oily components include higher alcohols such as lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, 2-octyldodecanol, and cetostearyl alcohol; silicone oils such as dimethylpolysiloxane, amino-modified silicone, polyether-modified silicone, methylphenylpolysiloxane, fatty acid-modified silicone, alcohol-modified silicone, alkoxy-modified silicone, epoxy-modified silicone, fluorine-modified silicone, cyclic silicone, and alkyl-modified silicone; fluorine oils such as perfluoropolyether; hydrocarbons such as squalane, squalene, liquid paraffin, liquid isoparaffin, and cycloparaffin; polyhydric alcohol fatty acid esters; fatty acid esters; and fats. acid alkyl esters, polybasic acid esters, ester oils such as alkyl glyceryl ethers and their fatty acid esters, higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, isostearic acid, and isopalmitic acid, glycerides such as olive oil, waxes such as jojoba oil, beeswax, lanolin, and carnauba wax, esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate, and tridodecyl isononanoate, isostearyl glyceryl ether, and polyoxypropylene butyl ether. Of these, higher alcohols, when blended, give a cleanser composition that has an appropriate viscosity and generates fine foam. Alcohols having 12 to 18 carbon atoms are preferred, and of these, cetanol is preferred.

[0095] Furthermore, the incorporation of silicone oil improves the dry feeling after drying. If a transparent composition is desired, it is recommended to use a microemulsified silicone oil, such as an amino-modified silicone.

[0096] When the pyrithione polyvalent metal salt-containing composition of the present invention is used as a cleaning agent, the pyrithione polyvalent metal salt-containing composition of the present invention may further contain other ingredients that are commonly used in cleaning agents, such as moisturizers, preservatives, ultraviolet absorbers, dyes, and fragrances.

[0097] [Hair cleanser] The pyrithione polyvalent metal salt-containing composition of the present invention, particularly the zinc pyrithione-containing composition of the present invention, is preferably used as an antibacterial or antidandruff agent for hair cleansers such as shampoos because of the antidandruff and antibacterial effects of the pyrithione polyvalent metal salt contained therein.Furthermore, the pyrithione polyvalent metal salt-containing composition of the present invention, which contains surfactants, water-soluble polymers, oily components, etc. as cleansing ingredients, is preferably used as a hair cleanser such as shampoos because of the antidandruff and antibacterial effects of the pyrithione polyvalent metal salt contained therein. Examples of shampoos include anti-dandruff shampoos that emphasize cleansing, anti-aging shampoos that provide firmness and body, gray hair dye shampoos, color shampoos, conditioning shampoos, damage care shampoos, and mild shampoos for babies. [Example]

[0098] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0099] [Pyrithione polyvalent metal salts, surfactants] In the following Examples and Comparative Examples, the pyrithione polyvalent metal salt used was zinc pyrithione "Tomicide (registered trademark) ZPT-50" manufactured by Mitsubishi Chemical Corp. The surfactants used were those shown in Table 1 below. "Tomicide (registered trademark) ZPT-50" is an aqueous suspension containing about 50% by weight of zinc pyrithione (a zinc complex of 2-pyridinethiol-1-oxide), and the volume average particle size (D 50 ) is 0.3 μm to 0.5 μm. Each product shown in Table 1 below is a transparent liquid made of each surfactant and water.

[0100] [Table 1]

[0101] [Other ingredients] The ingredients used in addition to the pyrithione polyvalent metal salt and surfactant are as shown in Table 3. As "PQ10" (Polyquaternium-10) in Table 3, "Cationized Cellulose JR400" manufactured by Dow Chemical Company was used.

[0102] [Physical property evaluation method] The physical properties of the pyrithione polyvalent metal salt-containing compositions (hereinafter sometimes simply referred to as "compositions") obtained in the following Examples and Comparative Examples were evaluated as follows.

[0103] (1) Solubility The resulting compositions were visually observed and evaluated according to the following criteria. ○: Transparent, no solid particles observed. ×: Sedimentation or dispersion of solid particles is observed.

[0104] (2) Light transmittance The obtained composition was poured into a spectrophotometer cell, taking care not to mix in any bubbles, and the transmittance of light with a wavelength of 655 nm (%, optical path length 1 cm, 25°C) was measured using a V-530 spectrophotometer (JASCO Corporation). Prior to the measurement, distilled water was placed in the spectrophotometer cell, and the measured value was set to 100%. In addition, for those that were evaluated as "X" in the solubility evaluation above, light transmittance was not measured because pyrithione polyvalent metal salt had precipitated (indicated as "-" in Table 2), and light transmittance was measured only for those whose solubility was evaluated as "○".

[0105] (3) pH Measurements were made using a HORIBA pH meter "F-52."

[0106] [Examples 1 to 3, Comparative Examples 1 to 3] Compositions (evaluation samples) were prepared using the following preparation method so as to have the composition shown in Table 2, and the zinc pyrithione solubility of each surfactant was evaluated. The light transmittance was measured for those with a solubility of "○". The results are shown in Table 2. Preparation method: After stirring raw material A (water and zinc pyrithione) for 1 minute at room temperature (23°C), raw material B (surfactant) was added and stirred for 5 minutes at room temperature (23°C).The mixture was then heated to 60°C and stirred for 5 minutes, after which it was cooled to room temperature (23°C) to obtain an evaluation sample with the composition shown in Table 2.

[0107] [Table 2]

[0108] Table 2 shows that when sodium cocoamphoacetate and disodium cocoamphodiacetate are mixed in a weight ratio of zinc pyrithione:water:sodium cocoamphoacetate or disodium cocoamphodiacetate = 0.20:89.80:10.00, they exhibit good zinc pyrithione solubility and a light transmittance of 95% or more. When sodium lauroamphoacetate was mixed at a weight ratio of zinc pyrithione:water:sodium lauroamphoacetate=0.50:89.50:10.00, it showed good zinc pyrithione solubility and a light transmittance of 99%. From this, it is clear that even when the zinc pyrithione concentration is increased and mixed at a weight ratio of zinc pyrithione:water:sodium lauroamphoacetate=0.2:89.8:10, a light transmittance of 95% or more will naturally be shown.

[0109] In contrast, when sodium laureth sulfate, cocamidopropyl betaine, or sodium cocoamphopropionate was used, zinc pyrithione did not dissolve even at a low zinc pyrithione concentration of 0.2 wt %, and a homogeneous aqueous solution could not be prepared.

[0110] [Examples 4 to 7] Solutions (evaluation samples) were prepared by the following preparation method so as to have the compositions shown in Table 3, and the pH and water permeability of the resulting aqueous solutions were measured. The results are shown in Table 3 together with the results of Example 1. Preparation method: After stirring raw material A for 1 minute at room temperature (23°C), raw material B was added and stirred for 5 minutes at room temperature (23°C).The mixture was then heated to 60°C and stirred for 5 minutes, and then raw materials C, D, and E, which are common shampoo ingredients, were added in this order.After stirring for 5 minutes, the mixture was cooled to room temperature (23°C) to obtain an evaluation sample with the composition shown in Table 3.

[0111] [Table 3]

[0112] Table 3 shows that when sodium lauroamphoacetate is used as a surfactant, high zinc pyrithione solubility is achieved even in the acidic pH range of 6 to 5. Therefore, it is clear that even in the acidic pH range of about 5 to 6, which is preferred for shampoos, highly transparent personal care products such as shampoos can be obtained with an amount of zinc pyrithione that effectively exerts anti-dandruff and antibacterial effects.

[0113] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2020-188104, filed on November 11, 2020, the entire contents of which are incorporated by reference.< / ph>

Claims

1. A composition containing a pyrithione polyvalent metal salt, a surfactant, and water, wherein the pyrithione polyvalent metal salt has a volume average particle diameter (D 50 ) of 0.1 μm to 1 μm, the surfactant is a compound represented by the following general formula (1), the content of the pyrithione polyvalent metal salt is 0.01 wt % to 1 wt %, and the content of the surfactant is 0.1 wt % to 30 wt %: 【Chemistry 1】 (In general formula (1), R １ represents an alkyl group having 7 to 21 carbon atoms which may have a substituent, or a coconut oil fatty acid residue. ２ represents an alkylene group having 1 to 3 carbon atoms. １ represents a monovalent cation. Z represents a hydrogen atom or -R ３ COOX ２ Represents R ３ represents an alkylene group having 1 to 3 carbon atoms. ２ represents a monovalent cation.)

2. 2. The composition containing a pyrithione polyvalent metal salt according to claim 1, wherein the compound represented by general formula (1) satisfies the following requirement I: Requirement I: The liquid obtained by mixing the pyrithione polyvalent metal salt, water, and the compound represented by general formula (1) in a weight ratio of 0.2:89.8:10 has a transmittance of 95% or more at 25°C (optical path length 1 cm) at 655 nm.

3. 3. The pyrithione polyvalent metal salt-containing composition according to claim 1, wherein the surfactant is sodium lauroamphoacetate, sodium cocoamphoacetate, or disodium cocoamphodiacetate.

4. 3. The composition according to claim 1, wherein the pyrithione polyvalent metal salt is a compound represented by the following general formula (2): 【Chemistry 2】 (In general formula (2), M ｎ＋ represents a polyvalent metal ion, and n is a number indicating the valence of the polyvalent metal ion.

5. The pyrithione polyvalent metal salt-containing composition according to claim 1 or 2, further comprising one or more cleansing components selected from the group consisting of surfactants, water-soluble polymers, and oily components.

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