JP2024005458A - Composition for skin formulation, and skin formulation - Google Patents

Abstract

To provide: a composition for a skin formulation capable of forming a skin formulation with an excellent histamine release inhibitory effect; and a skin formulation.SOLUTION: The invention provides a composition for a skin formulation, and a skin formulation containing the composition. The composition contains an amphoteric surfactant (A) represented by the general formula (1) in the figure, and a phosphoric acid polycondensate and/or its salt. [In the formula, R1 represents an alkyl or alkenyl group having 6 to 25 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, M1 represents a hydrogen atom, a sodium atom, a potassium atom, or triethanolammonium, and n is an integer equal to 1 or 2.]SELECTED DRAWING: None

Description

The present invention relates to compositions for dermatological preparations and dermatological preparations.

Itchy skin is one of the sensations that frequently occur in daily life. It is known that the scratching behavior caused by itch not only intensifies the itch but also worsens symptoms such as dermatitis, leading to a decline in QOL if itch cannot be suppressed.
Adrenal corticosteroids (steroids) and the like are known as skin preparations that suppress itching.

However, adrenocortical hormones are highly irritating to the skin and cannot be used in cosmetics and quasi-drugs as stipulated by the ``Act on Assuring the Quality, Efficacy, and Safety of Pharmaceuticals, Medical Devices, etc.''. (Non-patent document 1)

Hiroshi Shimizu, “New Dermatology 2nd Edition”, Nakayama Shoten 2011, p. 86

An object of the present invention is to provide a composition and a skin preparation that have an excellent effect of suppressing histamine release and can be incorporated into cosmetics, quasi-drugs, and pharmaceuticals.

The present inventors have made extensive studies to achieve the above object, and as a result, have arrived at the present invention. That is, the present invention comprises an amphoteric surfactant (A) represented by the following general formula (1),
A skin preparation composition and a skin preparation containing a polycondensate of phosphoric acid and/or a salt thereof.
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 25 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ₁ represents a hydrogen atom, a sodium atom, a potassium atom, or a tricarbon atom. represents ethanol ammonium, n represents an integer of 1 or 2]

The composition for skin preparations and skin preparations of the present invention have an excellent effect of suppressing histamine release, and therefore have a high effect of suppressing itch.

The present invention will be explained in detail below.
Skin preparations in this application include cosmetics, quasi-drugs, and pharmaceuticals stipulated in the "Act on Assuring the Quality, Efficacy, and Safety of Pharmaceuticals, Medical Devices, etc.," such as those applied or sprayed on human skin. Includes things that do.
Among these, cosmetics include scalp cosmetics, skin cosmetics other than scalp cosmetics, bath cosmetics, lip care cosmetics, body powder, and the like. Pharmaceutical products include ointments and liquid skin preparations.

<Ampholytic surfactant (A)>
The composition for skin preparation, which is the first invention of the present application, contains an amphoteric surfactant (A) represented by the general formula (1).

[In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 25 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ₁ represents a hydrogen atom, a sodium atom, a potassium atom, or a tricarbon atom. represents ethanol ammonium, n represents an integer of 1 or 2]

In general formula (1), R ¹ represents an alkyl group or alkenyl group having 6 to 25 carbon atoms.
Examples of the alkyl group having 6 to 25 carbon atoms include n-hexyl group, n-heptyl group, n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, Undecyl group, n-dodecyl group, isododecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, isotetradecyl group, n-hexadecyl group, isohexadecyl group, n-stearyl group, isostearyl group, n- Examples include nonadecyl group, n-icosyl group and n-tetracosyl group.
Examples of alkenyl groups having 6 to 25 carbon atoms include n-hexenyl group, n-heptenyl group, n-octenyl group, n-decenyl group, isodecenyl group, n-undecenyl group, n-dodecenyl group, n-tetradecenyl group, iso Examples include hexadecenyl group, n-octadecenyl group, and n-octadecadienyl group.
Of R ¹ , from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations, preferably an alkyl group having 6 to 20 carbon atoms or an alkenyl group having 6 to 20 carbon atoms, more preferably a carbon It is an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms.

In the general formula (1), X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
Examples of the alkyl group having 1 to 3 carbon atoms include methyl group, ethyl group, and propyl group.
Among X, from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In general formula (1), M ₁ is a hydrogen atom, a sodium atom, a potassium atom, or triethanolammonium.
Among _M1 , from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations, sodium atoms or triethanolammonium are preferable, and sodium atoms are more preferable.

In general formula (1), n represents an integer of 1 or 2.
n is preferably 2 from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations.

Specific examples of the amphoteric surfactant (A) represented by general formula (1) include sodium β-hexylaminopropionate, sodium β-heptylaminopropionate, sodium β-octylaminopropionate, β-isooctyl Sodium aminopropionate, sodium β-2-ethylhexylaminopropionate, sodium β-nonylaminopropionate, sodium β-isononylaminopropionate, sodium β-decylaminopropionate, sodium β-isodecylaminopropionate, β - Sodium undecylaminopropionate, sodium β-dodecylaminopropionate, potassium β-dodecylaminopropionate, triethanolammonium β-dodecylaminopropionate, sodium β-coconut oil fatty acid aminopropionate (coconut oil fatty acid is Refers to fatty acids obtained from coconut oil, and is a mixed fatty acid mainly composed of fatty acids with a distribution of carbon numbers of 8 to 18), β-coconut oil fatty acid aminocominopropionate triethanolammonium, β-isododecylamino Sodium propionate, Sodium β-tridecylaminopropionate, Sodium β-tetradecylaminopropionate, Sodium β-pentadecylaminopropionate, Sodium β-isopentadecylaminopropionate, Sodium β-isotetradecylaminopropionate , β-sodium hexadecylaminopropionate, sodium β-isohexadecylaminopropionate, sodium β-stearylaminopropionate, sodium β-isostearylaminopropionate, sodium β-nonadecylaminopropionate, β-icosyl Sodium aminopropionate, sodium β-tetracosylaminopropionate, sodium β-hexenylaminopropionate, sodium β-heptenylaminopropionate, sodium β-octenylaminopropionate, sodium β-decenylaminopropionate , β-isodecenylaminopropionate sodium, β-undecenylaminopropionate sodium, β-dodecenylaminopropionate sodium, β-tetradodecenylaminopropionate sodium, β-isohexade Sodium senylaminopropionate, sodium β-octadecenylaminopropionate and sodium β-octadecadienylaminopropionate are mentioned.
One of these may be used alone or two or more may be used in combination.

The amphoteric surfactant (A) represented by the general formula (1) is preferably sodium β-dodecylaminopropionate, β-dodecyl These are potassium aminopropionate and triethanolammonium β-dodecylaminopropionate, and more preferably sodium β-dodecylaminopropionate.
In addition, since the constituent components are sodium β-dodecylaminopropionate, potassium β-dodecylaminopropionate, and triethanolammonium β-dodecylaminopropionate, sodium β-coconut oil fatty acid aminopropionate, β-coconut oil fatty acid Potassium aminopropionate and triethanolammonium β-coco fatty acid aminopropionate are also preferred, and sodium β-coco fatty acid aminopropionate is even more preferred.

The amphoteric surfactant (A) represented by the general formula (1) can be obtained by a known method described in JP-A-2008-162914, etc. It can be obtained by subjecting 1 mole of methyl acrylate to Michael addition to obtain a Michael adduct, and then hydrolyzing the Michael adduct with an alkaline compound such as sodium hydroxide.
For example, the reaction is carried out by dropping 1.17 mol of methyl acrylate to 1 mol of a primary amine having 6 to 25 carbon atoms at preferably 50 to 150°C, more preferably 70 to 100°C, followed by hydration with an alkali. By decomposition, an amphoteric surfactant aqueous solution containing the amphoteric surfactant (A) is obtained.

The content of the amphoteric surfactant (A) contained in the amphoteric surfactant aqueous solution obtained by the above method can be determined by measuring the amphoteric surfactant aqueous solution with N,N-dimethylformamide dimethyl acetal by the method described below. After converting into ester by methyl esterification, the ester contained in the solution after methyl esterification was analyzed using gas chromatography [hereinafter sometimes abbreviated as GC]. Quantitative analysis method using GC>

<Quantitative analysis method by GC of amphoteric surfactant aqueous solution>
Add hydrochloric acid (35% by weight aqueous solution, Fuji Film Wako Pure Chemical Industries, Ltd.) to an amphoteric surfactant aqueous solution (80 g) to adjust the pH to 2, and then add 20 g of petroleum ether (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and mix. Then, the amphoteric surfactant (A) contained in the amphoteric surfactant aqueous solution is extracted into petroleum ether.
Next, the mixture is separated into an aqueous layer and an oil layer using a 200 mL separatory funnel, and the oil layer is taken out. Using a rotary evaporator (rotation speed 50 rpm/min), the oil layer is depressurized at a pressure of 0.09 MPa for 3 hours in a 60° C. hot bath to distill off petroleum ether contained in the oil layer. After recording the weight of the residue after distilling off the petroleum ether, N,N-dimethylformamide dimethyl acetal (1 g) was added to a sample (0.03 g) sampled from the residue and heated at 60°C for 15 minutes. Then, the amphoteric surfactant (A) contained in the residue is subjected to a methyl esterification reaction.
The obtained reaction mixture was analyzed by GC under the following measurement conditions, and the content of ester contained in the reaction mixture obtained by the methyl esterification treatment was measured. Calculate the number of moles of ester contained. The number of moles of the amphoteric surfactant (A) contained in 80 g of an amphoteric surfactant aqueous solution is converted to the weight of the amphoteric surfactant (A) based on the molecular weight of the amphoteric surfactant (A), and 80 g of methyl ester is calculated. The content of the amphoteric surfactant (A) contained in the amphoteric surfactant aqueous solution before chemical treatment.

[GC measurement conditions]
Equipment: GC-9A (manufactured by Shimadzu Corporation)
Detector: FID
GC packed column: SE-30 (dimethylpolysiloxane content 5% by weight, inner diameter 3.2 mm, length 2.1 m, manufactured by GL Science Co., Ltd.)
Column temperature: Raise the temperature from 80°C to 280°C (heating rate: 10°C/min)
Sample injection volume: 5μL

<Polycondensate of phosphoric acid and its salt>
The composition for skin preparation, which is the first invention of the present application, contains a polycondensate of phosphoric acid and/or a salt thereof.

A polycondensate of phosphoric acid is a polymer containing phosphoric acid as a constituent monomer, and is sometimes called polyphosphoric acid.
The structure of the polycondensate of phosphoric acid may be linear, branched, cyclic, or network-like.
Among these, linear or cyclic ones are preferably used from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations.
The degree of polymerization of phosphoric acid in the polycondensate of phosphoric acid is preferably from 2 to 2000, from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations. Those with a polymerization degree of 2 to 1,000 are more preferably used, and those with a polymerization degree of 3 are particularly preferably used.
Examples of the cyclic polyphosphoric acid include trimetaphosphoric acid, tetrametaphosphoric acid, pentametaphosphoric acid, hexametaphosphoric acid, and cyclic long-chain polyphosphoric acid (degree of polymerization 30 to 1000).
Examples of linear polyphosphoric acids include pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, pentapolyphosphoric acid, hexapolyphosphoric acid, and long-chain polyphosphoric acid (degree of polymerization 30 to 1000).
As the polycondensate of phosphoric acid, linear polyphosphoric acid is preferred, and tripolyphosphoric acid is most preferred.

Examples of salts of polycondensates of phosphoric acid include alkali metal salts (lithium, potassium, sodium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), ammonium salts, amine salts, and the like. Among these, alkali metal salts are preferably used, and sodium salts are particularly preferably used, from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations.

A polycondensate of phosphoric acid can be obtained by dehydrating and condensing phosphoric acid. A salt of a polycondensate of phosphoric acid can be obtained by dehydrating and condensing phosphoric acid and then neutralizing it with an alkali compound such as sodium hydroxide, or it can also be obtained by dehydrating and condensing a phosphate.
As a specific manufacturing method, it can be manufactured by a known method such as that described in "Manufacture of condensed phosphates" (written by Shiro Ueda, Electrochemistry and Industrial Physical Chemistry, 11, 30, 1962).

As the phosphoric acid polycondensate and its salt, commercially available products may be used.
Commercially available polycondensates of phosphoric acid and their salts include sodium tripolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd. or Mitejima Kagaku Co., Ltd.], sodium tetrapolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.], Sodium hexametaphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd. or Organo Food Tech Co., Ltd.], sodium pentapolyphosphate [manufactured by Taihei Kagaku Sangyo Co., Ltd.], sodium polyphosphate with a degree of polymerization of 30 to 1000 [product name: long chain Sodium polyphosphate {manufactured by Rin Kagaku Kogyo Co., Ltd.}], trisodium trimetaphosphate [manufactured by Yoneyama Chemical Co., Ltd.], tetrasodium pyrophosphate [manufactured by Organo Food Tech Co., Ltd.], and potassium tripolyphosphate [manufactured by Organo Food Tech Co., Ltd.] Co., Ltd.], etc.

Among these polycondensates of phosphoric acid and their salts, from the viewpoint of suppressing histamine release in compositions for skin preparations and skin preparations, alkali metal salts of linear or cyclic polycondensates of phosphoric acid are preferred. Specific examples include sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, sodium pentapolyphosphate, sodium polyphosphate with a degree of polymerization of 30 to 1000, trisodium trimetaphosphate, tetrasodium pyrophosphate, and potassium tripolyphosphate. Alkali metal salts of linear or cyclic polycondensates of phosphoric acid with a degree of polymerization of 3 to 6 are more preferably used, and specific examples thereof include sodium tripolyphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, Sodium pentapolyphosphate and potassium tripolyphosphate are mentioned, and alkali metal salts of tripolyphosphate are particularly preferably used, and a specific example thereof is sodium tripolyphosphate.

<Composition for skin preparation>
The composition for skin preparation, which is the first invention of the present application, does not contain any other components as long as it contains the amphoteric surfactant (A) and the polycondensate of phosphoric acid and/or its salt. Among them, it is preferable to include water.
The composition for skin preparations, which is the first invention of the present application, can be used as a raw material for skin preparations or as a skin preparation.

The weight proportion of the amphoteric surfactant (A) based on the total weight of the composition for skin preparations is preferably 0.003 to 10% by weight, more preferably 0.003% by weight from the viewpoint of suppressing histamine release. ~9% by weight.

The total weight proportion of the polycondensate of phosphoric acid and its salt based on the total weight of the composition for skin preparations is preferably 0.003 to 10% by weight, more preferably It is 0.003 to 9% by weight.

The total weight ratio of the phosphoric acid polycondensate and its salt to the weight of the amphoteric surfactant (A) contained in the composition for skin preparations is 0.1 to 1000 from the viewpoint of the histamine release inhibiting effect. It is preferably % by weight, more preferably 100 to 500% by weight.

When the composition for skin preparations contains water, the content of water is 10 to 95% by weight based on the total weight of the composition for skin preparations, from the viewpoint of solubility of polycondensates of phosphoric acid and its salts. It is preferably 30 to 90% by weight, and more preferably 30 to 90% by weight.

The water contained in the composition for skin preparations may directly contain the water used as a reaction solvent when synthesizing the amphoteric surfactant (A), or may contain ordinary water at a predetermined weight ratio. In addition to purified water, hard water, soft water, natural water, deep ocean water, hot spring water, electrolyzed alkaline ionized water, electrolyzed acidic ionized water, ion-exchanged water, cluster water, etc., combined with amphoteric surfactant (A) and phosphoric acid The condensate and its salt may be mixed.

Any other components contained in the composition for skin preparations include amphoteric surfactants other than the amphoteric surfactant (A), anionic surfactants, and cationic surfactants contained in the skin preparations described below. agent, nonionic surfactant solvent, oily component, water, solvent, humectant, chelating agent, conditioning agent, thickener, whitening agent, pH adjuster, cooling agent, coloring agent, ultraviolet scattering agent, ultraviolet absorber, Known cosmetic ingredients such as preservatives and antioxidants may be mentioned.
In addition, the composition for skin preparations may contain unreacted substances and residues of the reaction catalyst during the synthesis of the amphoteric surfactant (A) and the polycondensate of phosphoric acid and/or its salt. good.

The composition for skin preparations is prepared by mixing an amphoteric surfactant (A), a polycondensate of phosphoric acid and/or its salt, and water used as necessary in a predetermined ratio using a known mixing method using a stirring device. It can be obtained by mixing in a device or the like. Examples of the stirring device include a Henschel mixer, a ball mill, a jet mill, a kneader, a planetary mixer, a sand mill, an attritor, a ribbon blender, a disper mixer, a homo mixer, and the like, with a disper mixer being preferably used.

<Skin preparations>
The second invention of the present application is a skin preparation containing a polycondensate of the amphoteric surfactant (A) and phosphoric acid and/or a salt thereof.
Dermatological preparations include cosmetics and pharmaceuticals.
Examples of cosmetics include scalp cosmetics, non-scalp cosmetics, bath cosmetics, lip care cosmetics, and body powders, and also includes cosmetics marketed as quasi-drugs.

Scalp cosmetics include hair styling products (hair oil, styling products, setting products, hair sticks, pomades, hair creams, hair milk, hair wax, hair spray, hair mist, hair foam, etc.), hair nourishing products (tonics, hair lotions, hair essences, etc.) , hair treatments, hair conditioners, hair packs, etc.), scalp products (scalp treatments, etc.), hair washing products (shampoos, hair washing powders, etc.), and hair rinses.

Cosmetics for skin other than the scalp include lotions (skin lotions, lotions, softening lotions, astringent lotions, astringents, etc.), lotions (moisturizing lotions, serums, essences, etc.), and creams (oil-based creams, medium-oil-based creams, etc.). and mild oil-based creams, etc.), emulsions (milk lotions, skin milk, milk, etc.), sunscreen cosmetics (UV care creams, UV care gels, suntan and sunscreen agents, etc.), cleaning products (facial washes, cleansing, powder washes, cleansers, (makeup remover, makeup remover, face wash, facial soap, scrub body shampoo, body soap, body wash, hand soap, etc.), shaving cosmetics (pre-shave, aftershave, etc.), packs, body rinse, massage fees, etc.) can be mentioned.

Cosmetics for makeup include foundations (face color and concealer, etc.), makeup bases (makeup base, makeup primer, pre-makeup, etc.), powders (face powder, lucent powder, finishing powder, highlights, shading, etc.) ), lipstick (lipstick, lip rouge, lip color, lip pencil, lipstick, lip gloss, lip liner, etc.), eye makeup (eyeshadow, eye color, eyeliner, eyebrow ink, eyebrow, eyebrow pencil, eyebrow blush mascara, etc.) ) etc.

Examples of bath cosmetics include bath salts, bath oils, bath essences, bubble baths, foam baths, and the like.

Lip care cosmetics include lip treatments, lip balms, lip balms, lip oils, and the like.

Examples of body powder include talcum powder, bath powder, perfume powder, baby powder, and turmeric powder.

Dosage forms of dermatological preparations include sprays (pump sprays or aerosols), foams, gels, gel sprays, lotions, creams, mousses, packs, sheets, ointments, patches, suspensions, or powders. .

The weight proportion of the amphoteric surfactant (A) based on the total weight of the skin preparation is preferably 0.001 to 10% by weight, more preferably 0.05 to 10% by weight from the viewpoint of histamine release inhibiting effect. Weight%.

The total weight proportion of the polycondensate of phosphoric acid and its salt based on the total weight of the skin preparation is preferably 0.001 to 10% by weight, more preferably 0.05% by weight from the viewpoint of suppressing histamine release. ~10% by weight.

The total weight ratio of the phosphoric acid polycondensate and its salt to the weight of the amphoteric surfactant (A) contained in the skin preparation should be 0.1 to 5000% by weight from the viewpoint of the histamine release inhibiting effect. is preferable, and more preferably 1 to 3000% by weight.

The skin preparation of the present invention may contain any other component in addition to the polycondensate of the amphoteric surfactant (A) and phosphoric acid and its salt.
Optional other components include amphoteric surfactants other than the amphoteric surfactant (A), anionic surfactants, cationic surfactants, nonionic surfactant solvents, oily components, water, solvents, and humectants. , chelating agents, conditioning agents, thickeners, whitening agents, pH adjusters, refreshing agents, coloring agents, ultraviolet scattering agents, ultraviolet absorbers, preservatives, antioxidants, and other known cosmetic ingredients.
Further, the skin preparation may contain unreacted substances and residues of the reaction catalyst during the synthesis of the amphoteric surfactant (A).

Examples of amphoteric surfactants other than the amphoteric surfactant (A) include alkyldimethylacetate betaines, fatty acid amidopropyl betaines, alkylimidazolinium betaines, sulfobetaine type amphoteric surfactants, and amino acid type surfactants.

Examples of the alkyldimethylaminoacetic acid betaine include lauryldimethylaminoacetic acid betaine [alias: laurylbetaine], myristyldimethylaminoacetic acid betaine [alias: myristylbetaine], and stearyldimethylaminoacetic acid betaine [alias: stearylbetaine].

Examples of fatty acid amidopropyl betaine include amidopropyl betaine laurate [also known as lauramidopropyl betaine], amidopropyl betaine myristate [also known as myristamidopropyl betaine], amidopropyl betaine isostearate, and amidopropyl betaine coconut oil fatty acid [also known as: cocamidopropyl betaine] and the like.

Alkylimidazolinium betaines include N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium [also known as sodium lauroamphoacetate] and N-coco fatty acid acyl-N'-carboxymethyl-N'-hydroxyethyl Examples include sodium ethylenediamine [also known as sodium cocoamphoacetate].

Examples of the sulfobetaine type amphoteric surfactants include lauramidopropylhydroxysultaine and cocamidopropylhydroxysultaine.

Examples of amino acid surfactants include sodium lauryl aspartate, sodium myristyl aspartate, sodium lauryl-β-aminopropionate, sodium lauroylmethyl-β-alanine [also known as: Na lauroylmethylalanine], and the like.

Examples of the anionic surfactant include ether carboxylic acids or salts thereof, sulfate ester salts, sulfonates, phosphate ester salts, fatty acid salts, and acylated amino acid salts.

Ether carboxylic acid salts or salts thereof include polyoxyethylene (average degree of polymerization 4) sodium lauryl ether carboxylate [also known as Na laureth-4 carboxylate], polyoxyethylene (average degree of polymerization 6) sodium lauryl ether carboxylate [ Other names: Sodium laureth-6 carboxylate], polyoxyethylene (average degree of polymerization 4) sodium tridecyl ether carboxylate [other name: Na trideceth-4 carboxylate] and polyoxyethylene (average degree of polymerization 7) tridecyl ether carboxylic acid Examples include sodium [also known as: Na trideceth-7 carboxylate].

Sulfate ester salts include sodium lauryl sulfate [alias: Na lauryl sulfate], polyoxyethylene (average degree of polymerization 3) sodium lauryl ether sulfate [alias: Na laureth-3 sulfate], polyoxyethylene (average degree of polymerization 3) lauryl Ether sulfate triethanolamine [also known as laureth-3 sulfate TEA], polyoxyethylene (average degree of polymerization 3) coconut oil fatty acid monoethanolamide sodium sulfate [also known as PEG-3 coconut fatty acid amide MEA sulfate Na] and polyoxyethylene ( Average degree of polymerization 3) Alkyl (carbon number 12-13) ether sodium sulfate [also known as (C12, C13) Pareth-3 Na sulfate] and the like.

Sulfonic acid salts include sodium dodecylbenzenesulfonate [also known as Na dodecylbenzenesulfonate], polyoxyethylene (average degree of polymerization 2) lauryl disodium sulfosuccinate [also known as 2Na laureth sulfosuccinate], and disodium lauryl sulfosuccinate [also known as 2Na laureth sulfosuccinate]. Other name: 2Na lauryl sulfosuccinate] and polyoxyethylene (average degree of polymerization 5) lauroylethanolamide disodium sulfosuccinate.

Examples of phosphate ester salts include sodium lauryl phosphate [also known as Na lauryl phosphate] and sodium polyoxyethylene lauryl ether phosphate [also known as trilaureth-4 phosphate].

Fatty acid salts include sodium myristate [also known as: Na myristate], potassium myristate [also known as K myristate], triethanolamine myristate [also known as TEA myristate], and sodium laurate [also known as Na laurate]. , potassium laurate [also known as K laurate], triethanolamine laurate [also known as TEA laurate], sodium stearate [also known as Na stearate], triethanolamine stearate [also known as TEA stearate], palmitin Examples include sodium acid [also known as: Na palmitate] and triethanolamine palmitate [also known as: TEA palmitate].

Acylated amino acid salts include N-coconut oil fatty acid methyltaurate sodium [also known as cocoyl methyltaurine Na], N-coconut oil fatty acid sarcosine sodium [also known as cocoyl sarcosine Na], N-lauroyl sarcosine sodium [also known as lauroyl sarcosine Na] ], N-coconut oil fatty acid sarcosine triethanolamine [also known as acylglutamic acid TEA], N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine [other name: cocoyl glutamic acid TEA], N-coconut oil fatty acid acyl-L-glutamic acid Examples include sodium [also known as: Na cocoyl glutamate] and lauroyl-L-glutamate triethanolamine [also known as: lauroyl glutamate TEA].

Cationic surfactants include quaternary ammonium salts and amine salts.

Quaternary ammonium salts include stearyltrimethylammonium chloride [alias: steartrimonium chloride], behenyltrimethylammonium chloride [alias: behentrimonium chloride], distearyldimethylammonium chloride [alias: distearyldimonium chloride], and ethyl Examples include lanolin sulfate fatty acid aminopropylethyldimethylammonium [also known as quaternium-33].

Examples of the amine salt include stearic acid diethylaminoethylamide [also known as stearamide ethyl diethylamine] and behenic acid dimethylaminoethylamide [also known as behenamide propyl dimethylamine].

Examples of nonionic surfactants include alkylene oxide (carbon numbers 2 to 8) adducts of alcohols having carbon numbers of 4 to 24, and esters of polymers of alkylene oxide (carbon numbers 2 to 8) and fatty acids having 8 to 24 carbon atoms. , alkylene oxide adducts of higher fatty acid esters of polyvalent (divalent to decavalent) alcohols, glycerin fatty acid esters, polyglycerin fatty acid esters, and fatty acid alkanolamides.

Examples of alkylene oxide (carbon number 2 to 8) adducts of alcohols having 4 to 24 carbon atoms include polyoxyethylene (average degree of polymerization 10) polyoxypropylene (average degree of polymerization 7) butyl ether [other name: PPG-7 buteth-10 ], polyoxyethylene (average degree of polymerization 20) lauryl ether [also known as Laureth-20], polyoxyethylene (average degree of polymerization 20) oleyl ether [other name: Oles-20], polyoxyethylene (average degree of polymerization 12) poly Examples include oxypropylene (average degree of polymerization 2) cetyl ether [also known as: PPG-2 Ceteth-12] and a mixture of polyoxyethylene cetearyl ether and polyoxyethylene oleyl ether [also known as Ceretos-5].

Examples of esters of fatty acids having 8 to 24 carbon atoms and polymers of alcohols or alkylene oxides (having 2 to 8 carbon atoms) include glyceryl monostearate [also known as glyceryl stearate], glyceryl monocaprylate [also known as glyceryl caprylate] , glyceryl monomyristate [also known as glyceryl myristate], glyceryl monooleate [also known as glyceryl oleate], ethylene glycol monostearate [also known as glycol stearate], sorbitan monolaurate [also known as sorbitan laurate], mono Sorbitan palmitate [also known as sorbitan palmitate], sorbitan monostearate [also known as sorbitan stearate], sorbitan monooleate [also known as sorbitan oleate], coconut oil fatty acid sorbitan, polyoxyethylene monooleate (average degree of polymerization) 6) Sorbitan [other name: PEG-6 sorbitan oleate], polyoxyethylene (average degree of polymerization 20) stearyl ether [other name: Steareth-20], polyoxyethylene glycol monostearate (average degree of polymerization 23) [other name: stearin acid PEG-23], polyoxyethylene glycol distearate (average degree of polymerization 3) [also known as PEG-3 distearate], polyoxyethylene glycol distearate (average degree of polymerization 150) [also known as PEG-150 distearate], Examples include polyoxyethylene glycol distearate (average degree of polymerization 190) [also known as PEG-190 distearate] and polyoxyethylene (average degree of polymerization 60) hydrogenated castor oil [also known as PEG-60 hydrogenated castor oil].

Alkylene oxide adducts of higher fatty acid esters of polyhydric (divalent to decavalent) alcohols include addition polymerization of polyethylene oxide (average degree of polymerization 6) to glycerin esters of caprylic acid and capric acid [also known as (caprylic acid) / capric acid) PEG-6 glycerides], polyoxyethylene monolaurate (average degree of polymerization 10) sorbitan [also known as PEG-10 sorbitan laurate], polyoxyethylene monolaurate (average degree of polymerization 80) sorbitan [also known as lauric acid PEG-80 sorbitan], polyoxyethylene monooleate (average degree of polymerization 6) sorbitan [also known as PEG-6 sorbitan oleate], polyoxyethylene monooleate (average degree of polymerization 3) sorbitan [also known as PEG- oleate] 3 sorbitan], polyoxyethylene monooleate (average degree of polymerization 40) sorbitan [also known as PEG-40 sorbitan oleate], polyoxyethylene monostearate (average degree of polymerization 6) sorbitan [also known as PEG-6 sorbitan stearate] ], polyoxyethylene monostearate (average degree of polymerization 40) sorbitan [also known as PEG-40 sorbitan stearate], polyoxyethylene triisostearate (average degree of polymerization 160) sorbitan [also known as PEG-160 sorbitan triisostearate] and polyoxyethylene (degree of polymerization 120) methyl dioleate glucoside [also known as PEG-120 methyl glucose dioleate].

Examples of polyglycerin fatty acid esters include decaglyceryl monooleate [also known as polyglyceryl oleate-10], decaglyceryl monolaurate [also known as polyglyceryl laurate], decaglyceryl isostearate [also known as polyglyceryl isostearate-10], Polyglyceryl distearate [also known as polyglyceryl distearate-10], polyglyceryl stearate [also known as polyglyceryl stearate-10], hexaglyceryl polyricinoleate [also known as polyglyceryl-6 polyricinoleate], and diglyceryl monoisostearate [also known as: Polyglyceryl-2 isostearate] and the like.

Examples of the fatty acid alkanolamide include coconut oil fatty acid monoethanolamide [also known as: cocamide MEA], coconut oil fatty acid N-methylethanolamide [also known as: cocamide methyl MEA], and coconut oil fatty acid diethanolamide [also known as: cocamide DEA].

Examples of water include ordinary water, purified water, hard water, soft water, natural water, deep ocean water, hot spring water, electrolyzed alkaline ionized water, electrolyzed acidic ionized water, ion exchange water, cluster water, and the like.

Examples of oily components include liquid oils, solid oils, hydrocarbon oils, synthetic ester oils, silicone oils, and essential oils.

Liquid oils include avocado oil, camellia oil, turtle oil, macadamia seed oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, Safflower oil, cottonseed seed oil, soybean oil, peanut oil, tea seed oil, rice bran oil, jojoba oil, rice germ oil, glyceryl tri-2-ethylhexanoate [also known as triethylhexanoin], and triisopalmitic acid Examples include glyceryl [also known as triisopalmitine].

Solid fats and oils include cacao butter, coconut oil, candelilla wax, beeswax, shea butter, horse oil, hydrogenated coconut oil, palm oil, beef tallow, lanolin, hydrogenated beef tallow, palm kernel oil, hydrogenated palm oil, pork fat. , Japanese owl oil, hydrogenated castor oil, and the like.

Hydrocarbon oils include 2,2,4,6,6-pentamethylheptane [also known as isododecane], 2,2,4,4,6,8,8-heptamethylnonane [also known as isohexadecane], and hexadecane. Methyltetracosane [also known as squalane], 2,6,10,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaene [also known as squalene], petrolatum, paraffin, water Examples include added polyisobutene, ozokerite, 2,6,10,14-tetramethylpentadecane, ceresin, and microcrystalline wax.

Synthetic ester oils include isopropyl myristate, cetyl ethylhexanoate, octyldodecyl myristate, cetyl palmitate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl ethylhexanoate, Cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl hydroxystearate, glycol diethylhexanoate, neopentyl glycol dicaprate, triester of caprylic acid, capric acid, and glycerin [also known as tri(capryl)] Glyceryl acid/capric acid], hydroxystearic acid, hydroxystearic acid, hexaester of stearic acid and rosin acid with dipentaerythritol [also known as: hexa(hydroxystearic acid/stearic acid/rosin acid) dipentaerythritol], dipentaerythrityl malate Isostearyl, glyceryl diisostearate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triethylhexanoate, pentaerythrityl tetraethylhexanoate, trimethylolpropane triisostearate, ethylhexyl palmitate, glyceryl trimyristate [other names: trimyristin], methyl ricinoleate, oleyl oleate, diisobutyl adipate, ester of lauroylglutamic acid, phytosterol, and octyldodecanol [also known as: di(phytosteryl/octyldodecyl) lauroylglutamate], diheptylundecyl adipate, lauric acid Ethyl, diethylhexyl sebacate, isocetyl myristate, hexyldecyl palmitate, dihexyldecyl adipate, diisopropyl sebacate, diethylhexyl succinate, triethyl citrate, polyoxyethylene triisostearate (average degree of polymerization 3), trimethylolpropane [ Other names include PEG-3 trimethylolpropane triisostearate], diglyceryl triisostearate [also known as polyglyceryl-2 triisostearate], and sucrose tetraisostearate.

Examples of the silicone oil include chain polysiloxanes, cyclic polysiloxanes, modified polysiloxanes (amino-modified polysiloxanes, polyether-modified siloxanes, alkyl-modified polysiloxanes, fluorine-modified polysiloxanes, etc.).

Examples of chain siloxanes include methylphenylpolysiloxane [also known as diphenyl dimethicone], caprylylmethicone, dimethicone, dimethylpolysiloxane cross-linked with divinyldimethylpolysiloxane [also known as (dimethicone/vinyl dimethicone) crosspolymer], and phenylvinyl dimethyl polysiloxane. Dimethylpolysiloxane copolymer crosslinked with siloxane [also known as (dimethicone/phenylvinyl dimethicone) crosspolymer], etc.

Examples of the cyclic siloxane include decamethylcyclopentasiloxane [also known as cyclopentasiloxane] and dodecamethylcyclohexasiloxane [also known as cyclohexasiloxane].

Modified polysiloxanes include aminopropyl dimethicone, alkyl (C26-28) dimethicone, alkyl (C30-45) dimethicone, polyoxyethylene (average degree of polymerization 10)/methylpolysiloxane copolymer [also known as PEG-10 dimethicone], Polyoxyethylene (average degree of polymerization 12)/methylpolysiloxane copolymer [also known as PEG-12 dimethicone] and polyoxyethylene (average degree of polymerization 9) dimethylsiloxyethyl dimethicone [also known as PEG-9 polydimethylsiloxyethyl dimethicone] etc.

Solvents include ethanol, isoprene diol [also known as isopentyldiol], denatured alcohol, dipropylene glycol [also known as DPG], 1,2-hexanediol [also known as 1,2-hexanediol], isododecane, isopropanol, acetic acid. Examples include butyl, diethylene glycol monoethyl ether [also known as ethoxydiglycol], and propylene glycol [also known as PG].

Moisturizers include glycerin, 1,3-butylene glycol [also known as BG], hydrogenated rapeseed oil alcohol [also known as hydrogenated rapeseed oil alcohol], sorbitol, sodium acetate [also known as sodium lactate], sodium pyrrolidone carboxylate [also known as :PCN-Na], sodium hyaluronate [also known as hyaluronate Na], and sodium chondroitin sulfate [also known as chondroitin sulfate Na].

Examples of the chelating agent include ethylenediaminetetraacetic acid [also known as EDTA], disodium salt of ethylenediaminetetraacetic acid [also known as EDTA-2Na], gluconic acid, sodium gluconate [also known as Na gluconate], and ascorbic acid.

Conditioning agents include polymers of quaternary ammonium salts obtained by adding glycidyltrimethylammonium chloride to hydroxyethylcellulose [also known as polyquaternium-10], polymers of quaternary ammonium salts obtained from acrylic acid amide and dimethyldiallylammonium chloride, and Copolymer [also known as: polyquaternium-7], copolymer of dimethyldiallylammonium chloride and acrylic acid [also known as polyquaternium-22], copolymer of vinyl acetate and vinylpyrrolidone [also known as (VP/VA) copolymer], guar gum Quaternary ammonium salt added with glycidyltrimethylammonium chloride [also known as guar hydroxypropyltrimonium chloride], polyethylene glycol 20000 [also known as PEG-400], sodium polyacrylate [also known as Na polyacrylate], and hydroxyethyl cellulose and Examples include D-pantothenyl alcohol [also known as panthenol].

Thickeners include guar gum, xanthan gum, starch, behenyl alcohol, stearyl alcohol, cetearyl alcohol, cetanol, myristyl alcohol, carboxyvinyl polymer [also known as carbomer], hydroxypropyl methylcellulose, polyvinyl alcohol, sodium polyacrylate [also known as poly Sodium acrylate], sodium salt of starch grafted with acrylic acid [also known as Na acrylate grafted starch], dimethyl distearylammonium hectorite [also known as disteardimonium hectorite], talc, coconut oil fatty acid N- Methylethanolamide [also known as cocamide methyl MEA], glycol distearate and acrylic acid/alkyl methacrylate (C10-30) copolymer [also known as (acrylates/alkyl acrylate (C10-30)) crosspolymer], etc. Can be mentioned.

Examples of whitening agents include tranexamic acid, arbutin, and hydroquinone.

Examples of the pH adjuster include lactic acid, citric acid, phosphoric acid, malic acid, tartaric acid, hydrochloric acid, acetic acid, sodium hydroxide, potassium hydroxide, and triethanolamine.

Examples of the coloring agent include Blue No. 1, Blue No. 2, Green No. 3, and Red No. 1.

Cooling agents include menthol, peppermint oil, thymol, methyl salicylate, camphor, and the like.

Examples of the ultraviolet scattering agent include titanium oxide and zinc oxide.

Examples of the ultraviolet absorber include ethylhexyl methoxycinnamate, ester of dimethyl para-aminobenzoic acid and 2-ethylhexyl alcohol [also known as dimethyl PABA ethylhexyl], and t-butylmethoxydibenzoylmethane.

Examples of preservatives include phenoxyethanol, o-cymen-5-ol, methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, and isobutylparaben.

Antioxidants include vitamin E [also known as tocopherol], dibutylated hydroxytoluene [also known as BHT], butylated hydroxyanisole [also known as BHA], dipotassium glycyrrhizinate [also known as glycyrrhizic acid 2K], ascorbyl palmitate, and rosemary leaf. Examples include extracts.

The types and contents of known cosmetic ingredients that can be used as needed in the skin preparation of the present invention are as follows.
Amphoteric surfactants other than amphoteric surfactant (A), anionic surfactants, cationic surfactants, nonionic surfactants, water, oily components, solvents, and humectants are included in the total weight of the skin preparation. Based on the above, it is preferably 50% by weight or less, and more preferably 10% by weight or less.
The amount of the chelating agent, conditioning agent, thickener, and whitening agent is preferably 30% by weight or less, and more preferably 10% by weight or less, based on the total weight of the skin preparation.
The pH adjuster, cooling agent, coloring agent, ultraviolet scattering agent, ultraviolet absorber, preservative, and antioxidant are each preferably 10% by weight or less, more preferably 5% by weight, based on the total weight of the skin preparation. % or less.

The dermatological preparation can be produced by mixing the amphoteric surfactant (A), the polycondensate of phosphoric acid and its salt, and any other ingredients with a stirrer. Examples of the stirrer include a Henschel mixer, a ball mill, a jet mill, a kneader, a planetary mixer, a sand mill, an attriter, a ribbon blender, a disper mixer, a homomixer, and the like, and a disper mixer is preferably used.

The skin preparation of the present invention is preferably solid, liquid or pasty at 25°C, and liquid is more preferred from the viewpoint of ease of handling.

The skin preparations of the present invention are preferably used as hair washes, scalp preparations, lotions, sunscreen cosmetics, packs, and pharmaceuticals, including shampoos, face washes, lotions, creams, hand creams, cleansing oils, conditioners, and packs. It is more preferable to use the composition as a make-up remover sheet, a sweat-wiping sheet, a hair-wiping sheet, an ointment, or a liquid medicine.

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Manufacture example 1>
Laurylamine [Nissanamine BB (manufactured by NOF Corporation, NissanAmine is a registered trademark of NOF Corporation) was placed in a 2 L four-necked flask equipped with a stirrer, reflux condenser, dropping funnel, and thermometer. }] After purging with nitrogen, the temperature was raised to 70° C., and 101 g of methyl acrylate [manufactured by Toagosei Co., Ltd.] was added dropwise from the dropping funnel over 3 hours, and the reaction was carried out at the same temperature. Thereafter, the temperature was raised to 100° C. and reaction was carried out for 7 hours, and the pressure was reduced at the same temperature until the gauge pressure reached 2.7 kPa to remove the remaining methyl acrylate.
The obtained reaction solution was charged with 32 g of a 49% by weight aqueous sodium hydroxide solution and 964 g of water, and a hydrolysis reaction was carried out at 150° C. for 6 hours.
Lactic acid was added while measuring the pH so that the resulting solution after hydrolysis had a pH of 6.0. The total weight of lactic acid added was 62.5 g.
By heating the solution after adding lactic acid at 90° C., methanol in the solution was distilled off, and an amphoteric surfactant aqueous solution 1 was obtained.
1 g of amphoteric surfactant aqueous solution 1 was sampled, the amphoteric surfactant contained in the sampled solution was identified, and its content was measured in the same manner as in Example 1.
Amphoteric surfactant aqueous solution 1 contained 29.00% by weight of sodium β-dodecylaminopropionate as an amphoteric surfactant.

<Quantitative analysis method by GC of amphoteric surfactant aqueous solution 1>
20 g of petroleum ether [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] was added to a sample made by adding hydrochloric acid [35% by weight aqueous solution, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] to pH 2 to amphoteric surfactant aqueous solution 1 (80 g). The mixture was added and mixed, and sodium β-dodecylaminopropionate contained in the amphoteric surfactant aqueous solution 1 was extracted into petroleum ether.
Next, the mixture was separated into an aqueous layer and an oil layer using a 200 mL separatory funnel, and the oil layer was taken out. Using a rotary evaporator (rotation speed: 50 rpm/min), the oil layer was depressurized at a pressure of 0.09 MPa for 3 hours in a 60° C. hot bath, and petroleum ether was distilled off. After recording the weight of the residue after distilling off the petroleum ether, 1 g of N,N-dimethylformamide dimethyl acetal (Tokyo Kasei Kogyo Co., Ltd.) was added to a sample (0.03 g) from the residue, and 60 The mixture was heated at ℃ for 15 minutes to carry out a methyl esterification reaction of sodium β-dodecylaminopropionate contained in the residue. The obtained reaction mixture was used as a measurement sample for GC analysis.
After adding 2 g of a 1% by weight ethanol solution of n-decane to a sample weighed and sampled from the obtained reaction mixture for GC measurement, 50 mL of ethanol was further added to prepare a sample solution, which was analyzed by GC. From the peak area ratio of methyl β-dodecylaminopropionate and n-decane in the GC spectrum obtained, calculate the content of methyl β-dodecylaminopropionate contained in the sample sampled for GC measurement from the residue. did.
By converting the content of methyl β-dodecylaminopropionate into the weight of sodium β-dodecylaminopropionate based on the molecular weight of sodium β-dodecylaminopropionate, the amount of β-dodecyl contained in the amphoteric surfactant aqueous solution 1 The content of sodium aminopropionate was determined.

[GC measurement conditions]
Equipment: GC-9A (manufactured by Shimadzu Corporation)
Detector: FID
GC packed column: SE-30 (dimethylpolysiloxane content 5% by weight, inner diameter 3.2 mm, length 2.1 m, manufactured by GL Science Co., Ltd.)
Column temperature: Raise the temperature from 80°C to 280°C (heating rate: 10°C/min)
Sample injection volume: 5μL

<Examples 1 to 7 and Comparative Examples 1 to 3>
The amphoteric surfactant aqueous solution 1 obtained in Production Example 1, the polycondensate of phosphoric acid and its salt, adrenal cortical hormone, and water were mixed in the proportions shown in Table 1, and the preparations of the present invention according to Examples 1 to 7 were prepared. Compositions for skin preparations and comparative compositions for skin preparations according to Comparative Examples 1 to 3 were obtained.
Note that the numbers in parentheses in Table 1 are values converted to the proportion of the components (sometimes referred to as active ingredients) remaining after water is removed from each raw material.
Furthermore, for each of the compositions for skin preparations of Examples 1 to 7 and Comparative Examples 1 to 3, the histamine release inhibition rate was calculated and the skin irritation was measured by the method described below, and the results are listed in Table 1.

(Calculation method of histamine release inhibition rate)
Rat mast cells [RBL-2H3 cells (JCRB cell bank, National Institute of Biomedical Innovation, Health and Nutrition)] were incubated in Eagle's minimal essential medium containing 10% fetal bovine serum (FBS, manufactured by Sigma-Aldrich). DMEM (manufactured by Nacalai Tesque) medium was seeded with 100 μL into each well of a 96-well plate (manufactured by Corning) at a density of 100,000 cells/mL, using a CO2 incubator [product name: MCO-18AIC (manufactured by SANYO)]. After culturing for 24 hours at 37°C and 5% CO2, the supernatant in each well was removed.
Furthermore, 100 μL of Eagle's minimal essential medium (DMEM, manufactured by Nacalai Tesque) containing 450 ng/mL DNP-IgE (manufactured by Sigma-Aldrich) was added to the solution remaining in each well, and the mixture was incubated at 37°C and 5% CO2. The cells were cultured for 24 hours under water, and the supernatant in each well was removed.
Add 100 μL of each of the compositions for skin preparations according to Examples 1 to 7 and Comparative Examples 1 to 3 diluted 60 times with purified water, and purified water for comparison to the solution remaining in each well. The reaction was then carried out at 37°C for 10 minutes. Furthermore, DNP-BSA was added so that the concentration of DNP-BSA (manufactured by Sigma-Aldrich) in each well was 10 μg/mL, and the reaction was further performed at 37°C for 30 minutes, and the supernatant after the reaction was collected. This was used as a sample for measuring the amount of histamine released.
The amount of histamine released was determined by treating the sample for measuring the amount of histamine released using the method described in the Histamine ELISA Kit (manufactured by Oxford Biomedical Research) and measuring the absorbance (620 nm) of the solution using a plate reader [product name: infinite 200Pro (manufactured by TECAN)]. was calculated using the obtained absorbance and a calibration curve.
The histamine release inhibition rate (%) was calculated by dividing the histamine release amount of each sample by the histamine release amount of the sample to which purified water was added and multiplying the value by 100.

(Skin irritation test)
The compositions for skin preparations according to Examples 1 to 7 and Comparative Examples 1 to 3 and purified water for comparison were added to 500 μL human three-dimensional cultured epidermis model [manufactured by J-TEC], and placed in a CO2 incubator [product name :MCO-18AIC (manufactured by SANYO Corporation)] and allowed to stand for 24 hours at 37°C and a CO2 concentration of 5 to 10%.
After standing still, the composition for skin preparations was removed from the human three-dimensional cultured epidermis model, and the human three-dimensional cultured epidermis model was washed three times with 500 μL of a pH 7 phosphate buffer [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]. After washing, 500 μL of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] solution (also known as MTT solution) was washed on the human three-dimensional cultured epidermis. Added model. After leaving the human three-dimensional cultured epidermis model to which MTT solution was added for 3 hours at 25°C and 5-10% CO2 concentration using a CO2 incubator [product name: MCO-18AIC (manufactured by SANYO)], human 3 A dimensional cultured epidermal model was taken out.
The removed human three-dimensional cultured epidermis model was immersed in 300 μL of isopropyl alcohol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.] for 2 hours, and the absorbance of the isopropyl alcohol solution after immersion was measured using a microplate reader [trade name: infinite 200Pro (manufactured by TECAN)]. ] was used to measure the absorbance at 570 nm.
The cell survival rate of the human 3D cultured epidermis model in the composition for each skin preparation is calculated from the relative value of the absorbance when the above treatment is performed with purified water, assuming that the cell survival rate of the human 3D cultured epidermis model is 100%. was calculated.
When the cell survival rate was greater than 60%, it was evaluated that there was no irritation, and when the cell survival rate was less than 60%, it was evaluated that there was irritation.

In addition, as the components listed in Table 1, the following were used.
・Sodium tripolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Sodium tetrapolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Sodium hexametaphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Long-chain sodium polyphosphate (degree of polymerization 30-1000) [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Trisodium trimetaphosphate [manufactured by Yoneyama Chemical Industry Co., Ltd.]
・Dexamethasone [manufactured by Sigma-Aldrich]

<Skin preparations: Examples 8 to 30 and Comparative Examples 4 to 14>
The amphoteric surfactant aqueous solution 1 of the present invention obtained in Production Example 1, the polycondensate of phosphoric acid and its salt, and any other components described below were mixed in the proportions shown in Tables 2 to 10, and Example 8 -13 and Comparative Examples 4-5, the skin preparation shampoo according to Example 14, the skin preparation pump former facial cleanser according to Examples 15-16, the cream facial cleanser according to Example 17. Lotion, cream according to Example 18, hand cream according to Example 19 and Comparative Example 6, cleansing oil according to Example 20 and Comparative Example 7, conditioner according to Example 21 and Comparative Example 8, Example 22 and Comparative Example Non-cationic conditioner according to Example 9, UV care cream according to Example 23 and Comparative Example 10, UV care gel according to Example 24 and Comparative Example 11, pack according to Example 25 and Comparative Example 12, Example 26 and Comparative Example 13 A makeup removing sheet according to Example 27, a sweat wiping sheet according to Example 27, a hair wiping sheet according to Example 28, and an ointment according to Examples 29 to 30 and Comparative Example 14 were prepared. Furthermore, the itch suppression effect of these skin preparations was evaluated using the method described below, and the results are listed in Tables 2 to 10.

<Itching suppressing effect of shampoo>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly experience itching on their scalps thoroughly wet their hair with 40°C hot water and then applied 1 g of the shampoos of Examples 8 to 13 and Comparative Examples 4 to 5. After washing the scalp with water, rinsing thoroughly with hot water at 40°C, and drying the hair with a hair dryer for 5 minutes, this process was repeated once a day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itching suppression effect of pump former facial cleanser and cream facial cleanser>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly feel itchy skin thoroughly wet their faces with 40°C hot water, and then applied the pump former facial cleansers and creams of Examples 14 to 16. After washing the face with 1 g of face wash, thoroughly rinsing with hot water at 40°C, and towel drying for 5 minutes, this process was repeated once a day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itch suppression effect of lotions, creams, hand creams, and cleansing oils>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly experience itching on their skin applied the lotions, creams, hand dreams, and cleansing oils of Examples 17-20 and Comparative Examples 6-7 to their skin. Repeated once a day, every day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itch suppression effect of conditioner and non-cationic conditioner>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly experience itching on their scalps thoroughly wet their hair with 40°C hot water and then applied polyoxyethylene (polymerization degree 2) diluted to 10% by weight. It was washed with 1 g of sodium lauryl ether sulfate aqueous solution [Emar 20C, manufactured by Kao Corporation (Emar is a registered trademark of Kao Corporation)], and thoroughly rinsed with 40° C. hot water. Next, apply 1 g of the conditioners of Examples 21 to 22 and Comparative Examples 8 to 9 evenly to the hair, let it blend throughout the hair, rinse thoroughly with warm water at 40°C, and then dry the hair with a hair dryer for 5 minutes. Dry. The procedure of washing the hair, applying conditioner, rinsing and drying the hair as described above was repeated once a day every day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itching suppression effect of UV care cream and UV care gel>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly feel itchy skin applied the UV care creams and UV care gels of Examples 23-24 and Comparative Examples 10-11 to their faces for a day. Repeated once every day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itching suppression effect of the pack>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly feel itchy skin applied the packs of Example 25 and Comparative Example 12 for 10 minutes once a day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itching suppression effect of makeup remover sheet, sweat wipe sheet, and hair wipe sheet>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly feel itchy skin tried wiping it off with the make-up removal sheets, sweat wiping sheets, and hair wiping sheets of Examples 26 to 28 and Comparative Example 13. Repeated once a day, every day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

<Itching suppressing effect of ointment>
A total of 10 Japanese men and women between the ages of 20 and 60 who regularly feel itchy skin repeatedly applied the ointments of Examples 29 to 30 and Comparative Example 14 to their skin once a day.
On the 7th day after the start of use, evaluation was performed according to the following criteria.
・5 to 10 people felt that the itch had lessened: ○ ・1 to 4 people felt that the itch had lessened: △
・0 people felt that the itching had lessened: ×

The following components were used as listed in Tables 2 to 10.
・Sodium tripolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Sodium tetrapolyphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Sodium hexametaphosphate [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Long-chain sodium polyphosphate (degree of polymerization 30-1000) [manufactured by Rin Kagaku Kogyo Co., Ltd.]
・Trisodium trimetaphosphate [manufactured by Yoneyama Chemical Industry Co., Ltd.]
・26% by weight aqueous solution of polyoxyethylene (degree of polymerization 2) sodium lauryl ether sulfate [Product name: Viewlite NA-25S {manufactured by Sanyo Chemical Industries, Ltd. (Viewlite is a registered trademark of Sanyo Chemical Industries, Ltd.) )}]
・28% by weight aqueous solution of polyoxyethylene (degree of polymerization 2) sodium lauryl ether acetate [Product name: Viewlite LCA-25N {manufactured by Sanyo Chemical Industries, Ltd.}]
・29% by weight aqueous solution of sodium lauryl glycol carboxylate [Product name: Viewlite SHAA {manufactured by Sanyo Chemical Industries, Ltd.}]
・29% by weight aqueous solution of sodium N-coconut oil fatty acid acyl-L-glutamate [Product name: Plantapon Amino SCG-L {manufactured by BASF (Plantapon is a registered trademark of Cognis IP Management Gesellschaft mit Beschrenchtel Haftsung) be)}]
・30% by weight aqueous solution of triethanolamine lauroyl-L-glutamic acid [Product name: Amisoft LT-12 {manufactured by Ajinomoto Healthy Supply Co., Inc. (Amisoft is a registered trademark of Ajinomoto Co., Inc.)}]
・30% by weight aqueous solution of sodium N-lauroyl sarcosine [Product name: Soipon SLE {manufactured by Kawaken Fine Chemical Co., Ltd. (Soipon is a registered trademark of Kawaken Fine Chemical Co., Ltd.)}]
・N-coconut oil fatty acid acylglycine potassium [Product name: Amilite GCK-11 {manufactured by Ajinomoto Healthy Supply Co., Inc. (Amilite is a registered trademark of Ajinomoto Co., Inc.)}]
・37% aqueous solution of sodium olefin (carbon number 14-16) sulfonate [Product name: Liporan LJ-441 {manufactured by Lion Co., Ltd. (Liporan is a registered trademark of Lion Specialty Chemicals Co., Ltd.)}]
・30% by weight aqueous solution of cocamidopropyl betaine [Product name: Levon HC-30W {manufactured by Sanyo Chemical Industries, Ltd.}]
・43% by weight aqueous solution of 2-coconut oil fatty acid-N-hydroxyethyl-N-hydroxyethylimidazolinium betaine [Product name: Levon CIB {manufactured by Sanyo Chemical Industries, Ltd.}]
・Lauric acid [Product name: NAA-122 {manufactured by NOF Corporation (NAA is a registered trademark of NOF Corporation)}]
・Stearic acid [Product name: NAA-172 {manufactured by NOF Corporation}]
・Palmitic acid [Product name: NAA-160 {manufactured by NOF Corporation}]
・1,3-Butylene glycol [manufactured by Nacalai Tesque Co., Ltd.]
・Glycerin [Product name: Concentrated glycerin for cosmetics {manufactured by Kao Corporation}]
・Polyquaternium-22 (40% by weight aqueous solution) [Product name: MERQUAT280 {manufactured by Lubrizol (MERQUAT is a registered trademark of Lubrizol Advanced Materials, Inc.)}]
・Polyquaternium-7 (9% by weight aqueous solution) [Product name: MERQUAT550 (manufactured by Lubrizol)]
・Polyquaternium-10 [Product name: Sensor 10M Polymer (manufactured by Lubrizol)]
・Dimethicone [Product name: KF-96A-2CS {manufactured by Shin-Etsu Chemical Co., Ltd.}]
・Vitamin E [Product name: D-α-tocopherol {manufactured by Tokyo Chemical Industry Co., Ltd.}]
・Coconut oil fatty acid N-methylethanolamide [Product name: Aminone C-11S {manufactured by Kao Corporation (Aminone is a registered trademark of Kao Corporation)}]
・PEG-160 sorbitan triisostearate [Product name: Rheodor TW-IS399C {manufactured by Kao Corporation (Rheodor is a registered trademark of Kao Corporation)}]
・PEG-190 distearate [Product name: Emulmin 862 {manufactured by Sanyo Chemical Industries, Ltd. (Emulin is a registered trademark of Sanyo Chemical Industries, Ltd.)}]
・Glycol distearate [Product name: EMALEX EG-di-S {manufactured by Nippon Emulsion Co., Ltd. (EMALEX is a registered trademark of Nippon Emulsion Co., Ltd.)}]
・Menthol [Product name: l-menthol {manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.}]
・Citric acid [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
・Potassium hydroxide [manufactured by Nacalai Tesque Co., Ltd.]
・Isoprene diol [manufactured by Kuraray Co., Ltd.]
・Ethanol [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
・Xanthan gum [manufactured by Jungbunzlauer International AG]
・Hyaluronic acid Na [Product name: Hyaluronic acid FCH-120 {manufactured by Kikkoman Biochemifa Co., Ltd.}]
・Sodium acrylate grafted starch [Product name: Salandur ST-100MC {manufactured by Sanyo Chemical Industries, Ltd. (Sarandur is a registered trademark of Sanyo Chemical Industries, Ltd.)}]
・Behenyl alcohol [manufactured by Kyukyu Alcohol Kogyo Co., Ltd.]
・Stearyl alcohol [Product name: Hynol 18SS {manufactured by Kyukyu Alcohol Industries Co., Ltd. (Hinol is a registered trademark of Kyukyu Alcohol Industries Co., Ltd.})
・Isostearic acid [Product name: Isostearic acid EX {manufactured by Kyukyu Alcohol Kogyo Co., Ltd.}]
・Tri(caprylic acid/capric acid) glyceryl [Product name: TCG-M {manufactured by Kyukyu Alcohol Kogyo Co., Ltd.}]
・Hexa(hydroxystearic acid/stearic acid/rosin acid) dipentaerythrityl [Product name: Cosmol 168ARV {manufactured by Nisshin Oilio Group Co., Ltd. (Cosmol is a registered trademark of Nisshin Oilio Group Co., Ltd.)}]
・Jojoba oil [Product name: Deodorized jojoba oil M {manufactured by Watahan Trading Co., Ltd.}]
・Ethylhexyl palmitate [Product name: Koyo POC {manufactured by Koyo Fine Chemical Co., Ltd.}]
・Shea butter [Product name: Refined shea butter {manufactured by Life Tree Co., Ltd.}]
・Triethylhexanoin [Product name: T.I.O {manufactured by Nisshin Oilio Co., Ltd.}]
・Hydrogenated rapeseed oil alcohol [Product name: Alcohol NO. 20-B {Kyoku Alcohol Industry Co., Ltd.}]
・Cyclopentasiloxane [Product name: KF-995 {manufactured by Shin-Etsu Chemical Co., Ltd.}]
・Mineral oil [Product name: Carnation {manufactured by Sonneborn LLC (Carnation is a registered trademark of Sonneborn LLC)}]
・PEG-60 hydrogenated castor oil [Product name: HCO-60 {manufactured by Nikko Chemicals Co., Ltd.}]
・PPG-2 Seteth-12 [Product name: Alphapur HSG {manufactured by Sanyo Chemical Industries, Ltd. (Alphapur is a registered trademark of Sanyo Chemical Industries, Ltd.)}]
・Sorbitan oleate [Product name: Ionet S-80 {manufactured by Sanyo Chemical Industries, Ltd. (Ionet is a registered trademark of Sanyo Chemical Industries, Ltd.)}]
・PEG-9 oleic acid [Product name: Ionet MO-400 {manufactured by Sanyo Chemical Industries, Ltd.}]
・Setress-5 [Product name: Emulmin 50 {manufactured by Sanyo Chemical Industries, Ltd.}]
・Phenoxyethanol [Product name: Newport EFP {manufactured by Sanyo Chemical Industries, Ltd. (Newport is a registered trademark of Sanyo Chemical Industries, Ltd.)}]
・Methylparaben [Product name: Microcare MHB {manufactured by So Japan Co., Ltd. (Microcare is a registered trademark of So Specialties (UK) Limited)}]
・Behentrimonium chloride [Product name: VARISOFT BT 85 Pellets {manufactured by Evonik Operations GmbH (VARISOFT is a registered trademark of Evonik Goldschmidt Corporation)}]
・Cetearyl alcohol [Product name: Conol 1668 {manufactured by Shin Nippon Rika Co., Ltd. (Conol is a registered trademark of Shin Nippon Rika Co., Ltd.)}]
・Cetyl alcohol [Product name: Cetanol {manufactured by Kyukyu Alcohol Industries Co., Ltd.}]
・Glyceryl stearate [Product name: TG-C {manufactured by Sanyo Chemical Industries, Ltd.}]
・Hydroxypropyl methylcellulose [Product name: Metrose for food additives {manufactured by Shin-Etsu Chemical Co., Ltd.}]
・Titanium oxide [Product name: MICRO TITANIUM DIOXIDE MT-100TV {manufactured by Teika Co., Ltd.}]
・Zinc oxide [Product name: MICRO ZINC OXIDE MZ-300 {manufactured by Teika Co., Ltd.}]
・Diisostearyl malate [Product name: Cosmol 222 {manufactured by Nisshin Oilio Co., Ltd.}]
・Ethylhexyl methoxycinnamate [Product name: Uvinul MC80 {manufactured by BASF Corporation (Uvinul is a registered trademark of BASF Societas Europe)}]
・t-Butylmethoxydibenzoylmethane [Product name: Escalol 517 {manufactured by Asuland (Escalol is a registered trademark of ISP Investments, Inc.)}]
・Carbomer [Product name: NTC-CARBOMER 380 {manufactured by Nikko Chemicals Co., Ltd.}]
・Tranexamic acid [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
・Isopropyl methylphenol [Product name: Biosol {manufactured by Osaka Kasei Co., Ltd. (Biosol is a registered trademark of Osaka Kasei Co., Ltd.)}]
・Vaseline [Product name: Nomcoat W {manufactured by Nisshin Oilli Group Co., Ltd.}]

As described in Table 1, a composition for skin preparation containing an amphoteric surfactant (A) and a polycondensate of phosphoric acid and/or a salt thereof has an excellent effect of suppressing histamine release and has little skin irritation.
Furthermore, as shown in Tables 2 to 10, skin preparations containing the amphoteric surfactant (A) and the polycondensate of phosphoric acid and/or its salt have excellent itch-suppressing effects.

The composition for skin preparations of the present invention is excellent in suppressing the release of histamine and has low skin irritation, so it is suitable as a raw material for cosmetics and external skin preparations. Furthermore, the skin preparation of the present invention has an excellent anti-itch effect and is therefore suitable for cosmetics and external skin preparations.

Claims (4)

An amphoteric surfactant (A) represented by the following general formula (1),
A composition for skin preparation containing a polycondensate of phosphoric acid and/or a salt thereof.
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 25 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ₁ represents a hydrogen atom, a sodium atom, a potassium atom, or a tricarbon atom. represents ethanol ammonium, n represents an integer of 1 or 2] The composition for skin preparations according to claim 1, wherein the total weight proportion of the polycondensate of phosphoric acid and its salts in the composition for skin preparations is 0.0005 to 10% by weight. A skin preparation containing an amphoteric surfactant (A) represented by the following general formula (1) and a polycondensate of phosphoric acid and/or a salt thereof.
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 6 to 25 carbon atoms, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and M ₁ represents a hydrogen atom, a sodium atom, a potassium atom, or a tricarbon atom. represents ethanol ammonium, n represents an integer of 1 or 2] The skin preparation according to claim 3, wherein the total weight proportion of the polycondensate of phosphoric acid and its salt in the skin preparation is 0.01 to 10% by weight.