JP2007169175A - Biphenyl ether derivative or its salt, and external preparation composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a component which improves the feel of dermis or hair and has high capability for adsorbing protein, especially keratin protein which is the main constituent protein of dermis or hair; an external preparation composition containing the above component and improving the feel of an objective; and an external preparation composition maintaining the effects of a useful component used at the same time. <P>SOLUTION: The external preparation composition contains a biphenyl ether derivative represented by general formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>are each independently a 1-3C alkylene or 2-3C alkenylene group; and X<SP>1</SP>and X<SP>2</SP>are each independently an anionic group) or its salt. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a biphenyl ether derivative or a salt thereof having high adsorptivity to proteins, particularly keratin proteins, and an external preparation composition containing the same.

  Until now, various devices have been made to maximize the effect of the active ingredient in the external preparation composition. In the skin, attempts have been made to improve the effectiveness of drugs by continuously administering the drugs with a drug delivery system. Specifically, a method of applying or applying a patch, plaster, cream preparation or gel preparation containing a drug to the skin is used. However, patches and plasters have a problem that they are easily peeled off due to insufficient expansion and contraction with respect to the movement of the skin surface. On the other hand, if the adhesiveness is increased, there is a risk of causing skin irritation, and cream preparations and gel preparations are easily washed away with water or soap, so that the drug can be administered continuously. There wasn't.

  On the other hand, for hair, it is common to change the color and shape according to each person's preference, and damage due to chemical treatment such as permanent treatment and hair dyeing treatment, and damage due to sunlight etc. are known . Despite this, such treatment continues and hair damage is increased compared to before. However, since hair does not have self-healing power unlike skin, various hair care agents have been used to improve the feel and appearance of damaged sites. However, although a conventional hair care agent can provide a good feel and appearance when applied, it is easily removed by washing with a shampoo or the like and cannot be said to have sufficient application durability.

  Furthermore, in an external detergent composition such as a shampoo or body soap, a polymer compound having a film-forming property on the hair or skin after rinsing in order to increase the retention of the active ingredient in the hair or skin when washed away A technique for blending these into a composition has been proposed. Moreover, in the face cleansing agent containing an acne prevention component, in order to improve the persistence to the skin of an acne prevention component, it was necessary to suppress the compounding quantity of the cleaning base which reduces a persistence to the minimum required amount. However, even with such a measure, satisfactory application sustainability cannot be obtained, and a technique with excellent application sustainability has been desired.

  Therefore, as a method for maintaining the effect even after washing, it has a high adsorptivity with proteins, particularly keratin proteins, and is not easily removed even by washing, and its own effect lasts for a long time or is useful. There has been a demand for a compound capable of maintaining the effect of a useful substance for a long time by interacting with the substance.

  As a method for binding to such a keratin protein and maintaining the effect, hair cosmetics containing antibodies (see Patent Document 1: JP-A-5-163123, Patent Document 2: JP-A-5-155740, Patent Document 3: JP-A-5-155541, Patent Document 4: JP-A-5-279231, a method using a photoactivatable diazirine compound (Patent Document 5: JP-A-2003-335638), Cosmetic composition containing a complexing agent (Patent Document 6: see JP 2004-115518 A), a cosmetic composition containing a biotin compound and a complexing agent having a specific dissociation constant (Patent Document 7: JP 2004/2004) No. 2398, Patent Document 8: Japanese Patent Laid-Open No. 2005-23016) and the like have been proposed. However, in the method using an antibody, it is difficult to produce the antibody and practical application is difficult. In addition, since the method using a photoactivatable diazirine compound or a complexing agent forms a covalent bond with keratin, there is a problem that the covalent bond causes an irreversible change such as damage to the keratin protein itself.

JP-A-5-163123 JP-A-5-155740 Japanese Patent Application Laid-Open No. 5-155541 JP-A-5-279231 JP 2003-335638 A JP 2004-115518 A Japanese Patent Laid-Open No. 2004-2398 Japanese Patent Laid-Open No. 2005-23016

  The present invention has been made in view of the above circumstances, and it is an object to provide a component that improves the feel of skin and hair and has a high adsorptivity to keratin protein, which is a main constituent protein of skin and hair. And Moreover, it aims at providing the external preparation composition which contains this component and improves the touch of a target object, and the external preparation composition with which the effect of the active ingredient used together is maintained. The present invention solves at least one of the above problems.

  As a result of intensive studies to achieve the above object, the present inventor has found that a biphenyl ether derivative having a specific structure has a high adsorptivity with a protein, particularly keratin protein, and improves the feel of skin and hair. Furthermore, the external preparation composition containing this biphenyl ether derivative or a salt thereof has been found to be capable of maintaining the effects of active ingredients such as the biphenyl ether derivative or a salt itself, a drug used in combination or a conditioning agent for a long period of time due to the above-described action. The present invention has been made.

  Therefore, this invention provides the biphenyl ether derivative or its salt represented by following General formula (1), and the external preparation composition containing this.

（式中、Ｒ¹，Ｒ²はそれぞれ独立に、炭素数１〜３のアルキレン基又は炭素数２〜３のアルケニレン基を示し、Ｘ¹，Ｘ²はそれぞれ独立にアニオン性基を示す。）

(In the formula, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms or an alkenylene group having 2 to 3 carbon atoms, and X ¹ and X ² each independently represent an anionic group.)

  According to the present invention, it is possible to provide a biphenyl ether derivative or a salt thereof having improved skin and hair feel and having high adsorptivity to proteins, particularly keratin proteins, and an external preparation composition containing the same. .

（式中、Ｒ¹，Ｒ²はそれぞれ独立に、炭素数１〜３のアルキレン基又は炭素数２〜３のアルケニレン基を示し、Ｘ¹，Ｘ²はそれぞれ独立にアニオン性基を示す。） The biphenyl ether derivative of the present invention is represented by the following general formula (1), and can be used singly or in appropriate combination of two or more.

(In the formula, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms or an alkenylene group having 2 to 3 carbon atoms, and X ¹ and X ² each independently represent an anionic group.)

In the general formula ^{(1), R 1, R} 2 each independently represent an alkylene group or alkenylene group having 1 to 3 carbon atoms having 1 to 3 carbon atoms. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group having 1 carbon atom, an ethylene group having 2 carbon atoms, and a propylene group having 3 carbon atoms. X ¹ and X ² are each independently an anionic group. An anionic group is a group that can exhibit anionicity, and examples thereof include a hydroxy group, a sulfonic acid group, a carboxyl group, a phosphonic acid group, and a phosphoric acid group, and a hydroxy group, a sulfonic acid group, and a carboxyl group are preferable. Examples of the salt of the biphenyl ether derivative of the present invention include sodium salt, potassium salt, triethanolamine salt and the like.

As the biphenyl ether derivative of the present invention,
1) R ¹ is a methylene group, R ² is an ethylene group, X ¹ is a carboxyl group, and X ² is a hydroxyl group (2-carboxymethyl, 2′-hydroxyethyl) biphenyl ether 2) R ¹ is a methylene group, R ² is an ethylene group, X ¹ and X ² are sulfonic acid groups (2-sulfomethyl, 2′-sulfoethyl) biphenyl ether 3) R ¹ and R ² are methylene groups, and X ¹ and X ² are carboxyl groups ( 2,2′-dicarboxymethylbiphenyl ether [= (2,2′-biphenylenedioxy) diacetic acid])
4) R ¹ and R ² are ethylene groups, X ¹ is a sulfonic acid group, X ² is a carboxyl group (2-sulfoethyl, 2-carboxyethyl) biphenyl ether 5) R ¹ and R ² are ethylene groups, X ¹ , X ² is a carboxyl group, 2,2′-dicarboxyethylbiphenyl ether [= (2,2′-biphenylenedioxy) dipropionic acid]
6) 2,2′-dicarboxypropylbiphenyl ether [= (2,2′-biphenylenedioxy) dibutyric acid] wherein R ¹ and R ² are propylene groups and X ¹ and X ² are carboxyl groups
7) 2,2′-disulfomethylbiphenyl ether [= (2,2′-biphenylenedioxy) dimethylsulfonic acid] in which R ¹ and R ² are methylene groups and X ¹ and X ² are sulfonic acid groups
8) 2,2′-disulfoethylbiphenyl ether [= (2,2′-biphenylenedioxy) diethylsulfonic acid] in which R ¹ and R ² are ethylene groups and X ¹ and X ² are sulfonic acid groups
9) 2,2′-disulfopropylbiphenyl ether [= (2,2′-biphenylenedioxy) dipropylsulfonic acid] in which R ¹ and R ² are propylene groups and X ¹ and X ² are sulfonic acid groups
10) 2,2′-dihydroxymethylbiphenyl ether in which R ¹ and R ² are methylene groups and X ¹ and X ² are hydroxyl groups 11) R ¹ and R ² are ethylene groups and X ¹ and X ² are hydroxyl groups 2,2'-dihydroxyethylbiphenyl ether 12) 2,2'-dihydroxypropylbiphenyl ether in which R ¹ and R ² are propylene groups and X ¹ and X ² are hydroxyl groups 13) R ¹ is a methylene group, R ² Is an ethylene group, X ¹ and X ² are hydroxyl groups (2-hydroxymethyl, 2′-hydroxyethyl) biphenyl ether 14) R ¹ is a methylene group, R ² is an ethylene group, and X ¹ and X ² are carboxyl groups (2-carboxymethyl, 2′-carboxyethyl) biphenyl ether, which is In addition, examples of the salt of the biphenyl ether derivative include each of these sodium salts, potassium salts, triethanolamine salts, and the like.

Among them, (2,2′-biphenylenedioxy) dipropionic acid and (2,2′-biphenylenedioxy) diacetic acid in which R ¹ = R ² and X ¹ = X ² are obtained from the viewpoint of ease of production and stability. , Sodium (2,2′-biphenylenedioxy) dipropionate, sodium (2,2′-biphenylenedioxy) diacetate, potassium (2,2′-biphenylenedioxy) diacetate, (2,2′- Biphenylenedioxy) diacetate triethanolamine, (2,2′-biphenylenedioxy) dimethylsulfonic acid, (2,2′-biphenylenedioxy) diethylsulfonic acid, (2,2′-biphenylenedioxy) dimethylsulfone Acid sodium, sodium (2,2′-biphenylenedioxy) diethylsulfonate, 2,2′-dihydroxymethylbiphenyl ether, 2,2′-dihydroxy Cyethyl biphenyl ether, 2,2′-dihydroxypropyl biphenyl ether, (2-carboxymethyl, 2′-hydroxyethyl) biphenyl ether are preferable, and (2, 2'-biphenylenedioxy) diacetic acid, (2,2'-biphenylenedioxy) dipropionic acid, (2,2'-biphenylenedioxy) dimethylsulfonic acid, (2,2'-biphenylenedioxy) diethylsulfone More preferred are acid, sodium (2,2′-biphenylenedioxy) dimethylsulfonate, and sodium (2,2′-biphenylenedioxy) diacetate.

  The biphenyl ether derivative of the present invention (having a hydrophilic group at the terminal) or a salt thereof can be produced, for example, by a method in which biphenol is reacted with monochlorocarboxylic acid ester or the like, followed by hydrolysis and reduction reaction. . Details will be described in a production example described later.

  The external preparation composition of this invention contains the 1 type (s) or 2 or more types chosen from the biphenyl ether derivative represented by General formula (1), and its salt. This biphenyl ether derivative or a salt thereof improves the feel of skin and hair and has high adsorptivity to keratin protein, which is a main constituent protein of skin and hair. The external preparation composition containing the salt maintains the effect of the biphenyl ether derivative or the salt itself, or the active ingredient used in combination. This effect is particularly noticeable for damaged hair.

  Although the compounding quantity of a biphenyl ether derivative or its salt is not specifically limited, It is 0.0001 mass% or more normally with respect to the external preparation composition whole quantity, Preferably it is 0.001-20 mass%, More preferably, it is 0.00. 01 to 5% by mass. In view of the above effects, the blending amount is preferably 0.0001% by mass or more, and preferably 20% by mass or less from the economical point of view.

  The external preparation composition of the present invention can be widely used in many product forms such as liquid, cream, foam, spray, gel, powder, solid, etc., and cosmetics such as hair cosmetics, skin It can be suitably used for external preparations and the like.

  When used as a hair cosmetic, by using a biphenyl ether derivative represented by the general formula (1) or a salt thereof in combination with one or more selected from a quaternary ammonium salt, an amidoamine and a salt thereof, It is possible to obtain a hair cosmetic that is excellent in sustaining conditioning effects on hair, particularly damaged hair. The quaternary ammonium salt includes alkyl quaternary ammonium salts represented by the following general formula (2), and 1 to 3 ester groups in the molecules represented by the following general formulas (3) to (8). A quaternary ammonium salt is mentioned, As an amidoamine or its salt, the amidoamine represented by following General formula (9) or its salt is mentioned.

（式中、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶のうち１〜２個は、炭素数８〜２４のアルキル基、アルケニル基又はヒドロキシアルキル基を示し、残りは炭素数３以下のアルキル基を示し、Ｚはハロゲン原子を示す。）

(Wherein 1 to 2 of R ³ , R ⁴ , R ⁵ and R ⁶ represent an alkyl group, alkenyl group or hydroxyalkyl group having 8 to 24 carbon atoms, and the rest are alkyl groups having 3 or less carbon atoms. Z represents a halogen atom.)

  Specific examples of the quaternary ammonium salt represented by the general formula (2) include lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, benzalkonium chloride, and stearyldimethylbenzyl chloride. Examples include ammonium, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide, and the like.

  Examples of the quaternary ammonium salt containing one ester group in the molecule include compounds represented by the general formula (3).

In General Formula (3), R ⁷ is a linear or branched alkyl group or alkenyl group having 12 to 26 carbon atoms and containing one ester group, and R ⁸ is a methyl group, an ethyl group, or a C 1 to C 1 group. 4 represents a hydroxyalkyl group. X ⁻ represents an anion, and examples thereof include CH ₃ SO ₄ —, C ₂ H ₅ SO ₄ ⁻ , Cl ⁻ , Br ^{− and the} like. R ⁸ may be the same as or different from each other. As the quaternary ammonium salt containing one ester group in the molecule, a compound represented by the following general formula (4) is preferable.

In general formula (4), R ⁹ represents a linear or branched alkyl group or alkenyl group having 9 to 23 carbon atoms. R ⁹ is preferably a linear alkyl group having 13 to 21 carbon atoms or alkenyl group. Specifically, it is preferably a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid.

  Examples of the quaternary ammonium salt containing two ester groups in the molecule include compounds represented by the following general formula (5).

In the general formula (5), R ⁷ , R ⁸ and X ⁻ have the same meaning as in the general formula (3). R ⁷ and R ⁸ may be the same or different from each other. As the quaternary ammonium salt containing two ester groups in the molecule, a compound represented by the following general formula (6) is preferable.

In general formula (6), R ⁹ has the same meaning as in general formula (4). R ⁹ may be the same as or different from each other. In general formula (6), R ⁹ is preferably a linear alkyl group having 13 to 21 carbon atoms or an alkenyl group. Specifically, it is preferably a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid.

  Examples of the quaternary ammonium salt containing three ester groups in the molecule include compounds represented by the following general formula (7).

In the general formula (7), R ⁷ , R ⁸ and X ⁻ have the same meaning as in the general formula (3). R ⁷ may be the same as or different from each other. As the quaternary ammonium salt containing three ester groups in the molecule, a compound represented by the following general formula (8) is preferable.

In general formula (8), R ⁹ has the same meaning as in general formula (4). R ⁹ may be the same as or different from each other. In general formula (8), R ⁹ is preferably a linear alkyl group or alkenyl group having 13 to 21 carbon atoms. Specifically, it is preferably a residue obtained by removing a carboxyl group from a fatty acid such as stearic acid, palmitic acid, myristic acid, oleic acid, and elaidic acid. Incidentally, R ^7, R ^8, R ⁹ and X in each formula ^- is, R ⁷ in the other formula, R ^8, R ⁹ and X ^- and are each independently.

R ⁹ is a residue obtained by removing a carboxyl group from a fatty acid having 10 to 24 carbon atoms, and is a group derived from any of a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, and a branched fatty acid. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the mass ratio is preferably cis / trans = 25/75 to 80/20, more preferably 40/60 to 80/20. The following fatty acids can be exemplified as the base of R ⁹ . Stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodinated 10-60), partially hydrogenated beef tallow fatty acid (iodinated 10-60) and the like It is done. Among these, oleic acid, elaidic acid, linoleic acid, and stearic acid are preferable. Particularly preferred is a combination of a predetermined amount of plant-derived stearic acid, palmitic acid, myristic acid, oleic acid and elaidic acid, with a saturation / unsaturation ratio of 95/5 to 50/50 (mass / mass), cis / trans isomer. The mass ratio was 40/60 to 80/20, the ratio of carbon number 18 was 60% by mass or more, the carbon number 20 fatty acid was adjusted to 2% by mass or less, and the carbon number 22 fatty acid was adjusted to 1% by mass or less. It is preferred to use a fatty acid composition.
A quaternary ammonium salt containing 1 to 3 ester groups in the molecule is a condensation reaction between the fatty acid composition or the fatty acid methyl ester composition and triethanolamine, followed by 4 by a quaternizing reagent such as dimethyl sulfate. It can be synthesized by a grading reaction.

（式中、Ｒ¹⁰は炭素数８〜２４のアルキル基、アルケニル基又はヒドロキシアルキル基を示し、Ｒ¹¹は炭素数１〜３のアルキレン基、Ｒ¹²，Ｒ¹³はそれぞれ独立に炭素数１〜３のアルキル基を示す。）

(In the formula, R ¹⁰ represents an alkyl group, alkenyl group or hydroxyalkyl group having 8 to 24 carbon atoms, R ¹¹ represents an alkylene group having 1 to 3 carbon atoms, and R ¹² and R ¹³ each independently represents 1 to 1 carbon atoms. 3 represents an alkyl group.)

  Specific examples of the amidoamine represented by the general formula (9) or a salt thereof include lauric acid dimethylaminopropylamide, palmitic acid dimethylaminopropylamide, stearic acid dimethylaminopropylamide, stearic acid diethylaminopropylamide, and stearic acid. Examples thereof include dihydroxyethylaminopropylamide, stearic acid diethylaminoethylamide, behenic acid amidopropyldimethylamide, stearic acid dimethylaminopropylamine, and sodium and triethanolamine salts thereof.

  Although the compounding quantity of the 1 type, or 2 or more types of compound chosen from a quaternary ammonium salt, an amidoamine, and its salt is not specifically limited, 0.0001-10 mass% is preferable with respect to external preparation composition whole quantity, More preferably Is 0.1 to 5% by mass, more preferably 0.3 to 2% by mass.

  In the external preparation composition of the present invention, a cationic polymer compound, an anionic polymer compound, an amphoteric polymer compound and Polymer compounds such as nonionic polymer compounds can be used in combination.

  In the external preparation composition of the present invention, in addition to the essential biphenyl ether derivative or a salt thereof and the above optional components, an appropriate amount of components usually used in the external preparation composition is blended within a range not impairing the effects of the present invention. be able to. The components usually used in the external preparation composition include anionic surfactants, amphoteric surfactants, semipolar surfactants, and cations other than the cationic surfactants represented by the general formulas (2) to (8). Surfactants, nonionic surfactants other than the compound represented by formula (9), solid or liquid oil, silicones, higher alcohols, ester oils, polyhydric alcohols, preservatives, hydrotropes, inorganic salts , Thickeners, fragrances, animal and plant extracts, medicinal ingredients and anti-dandruff agents, emulsions, pearling agents, UV absorbers, UV scattering agents, tonic agents, pH adjusters, pigments, antioxidants, lower alcohols Vitamins, volatile oils, hydrophobic solvents, diluting solvents, and the like. About these additional components, it can mix | blend according to the objective and can be used individually by 1 type or in combination of 2 or more types.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. Unless otherwise specified,% of the composition is% by mass.

[Production Example 1: (2,2′-biphenylenedioxy) diacetic acid]
A mixture of 17.4 g of 2,2′-biphenol, 22.4 g of methyl monochloroacetate, 38.7 g of potassium carbonate, 0.1 g of tetrabutylammonium bromide and 200 mL of acetone was reacted at 60 ° C. for 6 hours, and then methyl monochloroacetate. 17.4 g and potassium carbonate 22.0 g were added, and the mixture was further reacted for 6 hours. The insoluble material was filtered off and concentrated, and the resulting residue was crystallized from ethyl acetate and hexane to obtain 24.3 g of methyl (2,2′-biphenylenedioxy) diacetate (yield 77%). ). To this ester intermediate, 243 mL of a 1 mol / L aqueous sodium hydroxide solution was added and reacted at room temperature for 1 day. The reaction solution was ice-cooled, 22 mL of concentrated hydrochloric acid was added, and the precipitated crystals were collected by filtration and dried to obtain 20.6 g of (2,2′-biphenylenedioxy) diacetic acid (yield 92%). ¹ H-NMR (δ, DMSO-d ⁶ ): 4.61 (s, 4H), 6.93 (d, 2H), 7.00 (m, 2H), 7.26 (m, 2H), 7 .28 (m, 2H).

[Production Example 2: (2,2′-biphenylenedioxy) dipropionic acid]
Under the same conditions as in Production Example 1, methyl monochloropropionate was used in place of methyl monochloroacetate to obtain (2,2′-biphenylenedioxy) dipropionic acid (yield 75%). ¹ H-NMR (δ, DMSO-d ⁶ ): 2.78 (m, 4H), 4.18 (m, 4H), 6.92 (d, 2H), 6.99 (m, 2H), 7 .26 (m, 2H), 7.28 (m, 2H).

[Production Example 3: (2,2′-biphenylenedioxy) diacetate sodium]
After dissolving 1.02 g of (2,2′-biphenylenedioxy) diacetic acid obtained in Production Example 1 in 100 mL of ion-exchanged water, adding 30 mL of a 0.1 mol / L aqueous sodium hydroxide solution, and thoroughly stirring and mixing Then, water was removed by lyophilization to obtain 1.09 g of a powder of sodium (2,2′-biphenylenedioxy) diacetate (yield 100%).

[Production Example 4: 2,2′-dihydroxyethylbiphenyl ether]
4.0 g of (2,2′-biphenylenedioxy) diacetic acid obtained in Production Example 1 was reduced with 0.50 g of lithium aluminum hydride in anhydrous diethyl ether to obtain 3.3 g of 2,2′-dihydroxyethylbiphenyl ether. Got. Yield 90%, ¹ H-NMR (δ, DMSO-d ⁶ ): 3.9 to 4.0 (br.m, 8H), 6.91 (d, 2H), 6.99 (m, 2H) 7.26 (m, 2H), 7.28 (m, 2H).

[Production Example 5: (2-Carboxymethyl, 2′-hydroxyethyl) biphenyl ether]
4.1 g of (2,2′-biphenylenedioxy) diacetic acid obtained in Production Example 1 was reacted with 0.41 g of lithium aluminum hydride in anhydrous diethyl ether while confirming the reaction by TLC. A mixture of '-biphenylenedioxy) diacetic acid, (2-carboxymethyl, 2'-hydroxyethyl) biphenyl ether and 2,2'-dihydroxyethylbiphenyl ether was obtained. A sodium hydroxide aqueous solution was added thereto, and the organic layer was separated and washed with diethyl ether. After concentrated sulfuric acid treatment, column purification was performed to obtain 3.3 g of (2-carboxymethyl, 2′-hydroxyethyl) biphenyl ether. Yield 90%, ¹ H-NMR (δ, DMSO-d ⁶ ): 3.9 to 4.0 (br.m, 4H), 4.62 (s, 2H), 6.91 (d, 1H) 6.93 (d, 1H), 6.99 to 7.01 (m, 2H), 7.26 to 7.28 (m, 4H).

[Production Example 6: (2,2′-biphenylenedioxy) diethylsulfonic acid]
1.4 g of thionyl chloride was reacted with 3.3 g of 2,2′-dihydroxyethyl biphenyl ether synthesized in the same manner as in Production Example 5 to obtain di (2-chloroethyl) biphenyl ether. This was added to 4.6 g of an aqueous sodium sulfite solution, stirred vigorously and then refluxed for 21 hours. This was cooled at room temperature, and the resulting precipitate was washed with diethyl ether to obtain sodium (2,2′-biphenylenedioxy) diethylsulfonate. This was applied to a cation exchange column to obtain 1.1 g of (2,2′-biphenylenedioxy) diethylsulfonic acid. Yield 40%, ¹ H-NMR (δ, D ₂ O): 3.31 (m, 4H), 4.30 (m, 4H), 6.93 (d, 2H), 7.00 (d, 2H), 7.26 (d, 2H), 7.28 (d, 2H).

[Production Example 7: (2,2′-biphenylenedioxy) sodium diethylsulfonate]
0.68 g of (2,2′-biphenylenedioxy) diethylsulfonic acid powder obtained by the method of Production Example 6 was dissolved in 50 mL of ion-exchanged water, and 20 mL of 0.1 mol / L sodium hydroxide aqueous solution was added. After stirring and mixing, water was removed by freeze-drying to obtain 0.75 g of sodium (2,2′-biphenylenedioxy) diethylsulfonate.

[Examples 1-7, Comparative Examples 1-2]
Sample solutions shown in Table 1 (solutions having the same molarity of the biphenyl ether derivative) were prepared, and the adsorptivity to proteins was evaluated by the following method.

[Evaluation method of protein adsorptivity, feel and contact angle]
The method for evaluating the adsorptivity to protein is as follows.
Since 80% or more of hair is composed of a protein generically called keratin, the adsorptivity to the protein was evaluated using a hair sample prepared as follows.
(1) Preparation of hair sample for adsorption test An Asian hair bundle (undamaged hair) having a length of 30 cm and a mass of 10 g is placed in a model bleach solution having the following composition 1 of 10 times (100 mL) at room temperature for 30 minutes. Soaked. Thereafter, the human hair bundle was thoroughly washed with tap water and dried. This human hair bundle was chopped to a length of about 1 mm to obtain a hair sample for an adsorption test.
(Composition 1) Model bleach solution Hydrogen peroxide 6
Ammonia 3
Sodium chloride 5
Sodium hydroxide appropriate amount (adjusted to pH 10.8)
Purified water balance
Total 100%

(2) Adsorption test In 20 mL of a sample solution at 25 ° C, 2.0 g of a hair sample for adsorption test was added and dispersed, and the mixture was sufficiently stirred for 5 minutes while maintaining the temperature at 25 ° C. This was filtered to obtain a filtrate. The sample solution before adding the hair sample and the filtrate were each appropriately diluted to the same dilution ratio with water, and then the absorbance at 260 nm was measured with a spectrophotometer (V-560 manufactured by JASCO Corporation). The adsorption rate was determined.
Adsorption rate (%) = (A ⁰ −A ¹ ) × 100 / A ⁰
A ⁰ : Absorbance at 260 nm of the sample solution before adding the hair sample for adsorption test A ¹ : Absorbance at 260 nm of the filtrate

[Examples 8 to 24, Comparative Examples 3 to 5]
The external preparation composition for hair of the composition shown to Tables 2-4 was prepared, the touch improvement effect and the sustainability of the touch improvement effect were evaluated by the following method, and the contact angle was measured. The results are also shown in the table. Examples 8 and 15 were prepared as shampoo compositions, and the others were prepared as hair out bath compositions.

[Evaluation of feel improvement effect]
An Asian hair bundle (undamaged hair) having a length of 30 cm and a mass of 10 g was immersed in 10 times (100 mL) of the model bleach solution having the above composition 1 at room temperature for 30 minutes. Thereafter, it was thoroughly washed with tap water and dried to obtain damaged hair bundles. 1.5 g of the external preparation composition for hair was applied to the damaged hair bundle, blended into the whole hair bundle using a comb, and naturally dried to obtain a treated hair bundle.
Ten evaluators touched the treated hair bundle and the untreated hair bundle (damaged hair bundle), and compared and evaluated “no creaking”. The table shows four levels according to the following criteria.
In addition, evaluation of the shampoo compositions of Examples 8 and 15 was carried out by applying 1.5 g of the sample for 1 minute, not naturally drying, then rinsing with warm water of 40 ° C. for 30 seconds and naturally drying the hair. A bundle was used.
◎: When the number of evaluators who prefers the treated hair bundle is 9 or more ○: When the number of evaluators who prefer the treated hair bundle is 6-8 △: The direction of the treated hair bundle When the number of evaluators deemed good is 3 to 5 ×: When the number of evaluators deemed better treated hair bundles is 2 or less

[Sustainability evaluation of feel improvement effect]
Apply 1g of a model shampoo solution of composition 2 below to the treated hair bundle used to evaluate the touch improvement effect, immediately rinse with a finger and lather, then rinse with tap water for 1 minute and then naturally. Dried. Using this hair bundle after repeating this operation five times, the feeling improvement effect was determined again based on the same criteria as described above. As a comparative control, an untreated hair bundle (damaged hair bundle) obtained by repeating the same operation as described above was used.
(Composition 2) Model shampoo solution Polyoxyethylene (3) Sodium lauryl ether sulfate 6
Sodium tetradecenesulfonate 3
Lauric acid amidopropyl betaine 3
Polyoxyethylene (20) hydrogenated castor oil 2
Sodium benzoate 0.4
Citric acid 0.5
Purified water balance
Total 100%

Moreover, the contact angle of water with respect to the hair was measured using the following method as an evaluation index of the effect of the sample.
[Measurement of contact angle]
One hair is taken out from the hair bundle (hair) used for the evaluation of the sustainability of the feeling improvement effect, 1 μL of distilled water is dropped on this, and an automatic contact angle meter CA-Z (manufactured by Kyowa Interface Science Co., Ltd.) It measured using. When measured by this method, the contact angle of undamaged hair was 108 °, while that of damaged hair was 54 °.

The following sample solution (skin external preparation composition) was prepared, and the feeling improvement effect and its durability were evaluated.

[Example 25]
The following body soap had creamy foam and the skin after use was smooth.
Composition%
Potassium laurate 8
Potassium myristate 7
N-lauroyl-N-methyl-β-alanine potassium 2
N-lauroyl-sodium glutamate 2
(2,2′-Biphenylenedioxy) diacetic acid 5
Palm oil fatty acid monoethanolamide 3
Lauryldimethylamine oxide 1
Propylene glycol 6
Hydroxypropyl methylcellulose 0.5
Ethylene glycol distearate 1
Dimethyldiallylammonium chloride / acrylamide copolymer 0.3
Polystyrene polymer (n = 300) 0.1
Edetate tetrasodium tetrahydrate 0.2
Plant-based squalane 1
Dimethylpolysiloxane (100 cs) 0.5
Potassium chloride 0.1
Piroctone Olamine 0.2
Potassium hydroxide 5
Fragrance A 0.7
Purified water balance
Total 100.0

[Example 26]
The following hand soap composition has good foaming properties and foam quality, good hand feel after use, and its effect was sustained.
Composition%
Potassium laurate 5
Potassium myristate 5
N-lauroyl-N-methyl-β-alanine potassium 2
N-lauroyl-monopotassium glutamate 2
(2,2'-Biphenylenedioxy) dibutyric acid 3
Lauric acid polyoxyethylene monoethanolamide 4
Lauryldimethylamine oxide 2
Glycerin 5
Propylene glycol 6
Hydroxypropyl cellulose 0.5
Ethylene glycol distearate 1
Methacrylic acid / butyl acrylate / methyl methacrylate copolymer 1.5
Hydroxyethane diphosphonic acid 0.1
Edetate tetrasodium tetrahydrate 0.2
Plant-based squalane 0.5
Potassium chloride 0.1
Isopropylmethylphenol 0.2
Triclosan 0.2
Potassium hydroxide 5
Fragrance B 0.2
Purified water balance
Total 100.0

[Example 27]
The following hand soap composition had good foaming properties and foam quality, and had a good bacteriostatic effect in the hand after use.
Composition%
Potassium laurate 8
Potassium myristate 6
(2,2′-Biphenylenedioxy) diacetate Na 3
Lauric acid monoethanolamide 4
Lauryldimethylamine oxide 2
Glycerin 5
Propylene glycol 6
Hydroxypropyl cellulose 0.5
Ethylene glycol distearate 1
Hydroxyethane diphosphonic acid 0.1
Edetate tetrasodium tetrahydrate 0.2
Plant-based squalane 0.5
Potassium chloride 0.1
Isopropylmethylphenol 0.2
Triclosan 0.2
Potassium hydroxide 4
Fragrance C 0.3
Purified water balance
Total 100.0

[Example 28]
After preparing the oil phase part of A and the water phase part of B, respectively, the oil phase part and the water phase part were blended to prepare a cosmetic cream. This cream composition had a good feeling of use and a good skin feel after use.
Composition%
A: Oil phase liquid paraffin 5
Squalane 15
Cetostearyl alcohol 5
Beeswax 2
Glycerol monostearate 2
POE (20) sorbitan monolaurate 2
Propylparaben 0.1
Lauric acid polyoxyethylene monoethanolamide 4
Dibutylhydroxytoluene 0.1
2-ethylhexyl methoxycinnamate 0.5
B: Water phase part (2,2′-biphenylenedioxy) diacetic acid 2
Glycerin 2
Carboxyvinyl polymer 0.5
Isopropanolamide 0.1
Edetate tetrasodium tetrahydrate 0.2
Methylparaben 0.2
Fragrance D 0.05
Purified water balance
Total 100.0

[Example 29]
The emulsion composition shown below had good usability and smooth skin feel after use.
Composition%
(2,2′-Biphenylenedioxy) diacetic acid 4
Stearic acid 1
Cetanol 2
Vaseline 2.5
Squalane 4
Dimethylpolysiloxane (30 cst) 1
Ellagic acid 0.6
L-Arginine 1
Lipophilic glyceryl monostearate 1
Glycerin 2
Xanthan gum 0.3
Fragrance E 0.1
Methylparaben 0.1
Butylparaben 0.05
Purified water balance
Total 100.0

[Example 30]
The lotion composition shown below has a good feeling when used, and the skin feel after use was also smooth and moist.
Composition%
(2,2′-Biphenylenedioxy) dipropionic acid 4
Glycerin 7
Dipropylene glycol 5
Polyoxyethylene hydrogenated castor oil (20 EO) 0.5
Rose water 0.1
1,3-butylene glycol 1
Creatinine 0.3
Davilia 0.5
Sodium pyrrolidonecarboxylate 1
Carrageenan 0.2
Acrylic acid / methacrylic acid / alkyl copolymer 0.05
Isopropanolamide 0.1
Piroctone olamine 0.01
Methylparaben 0.1
Ethanol 5
Purified water balance
Total 100.0

[Example 31]
The antiperspirant composition shown below has a good feeling of use and a good persistence of the smooth feeling on the skin after use.

Composition%
(2,2′-Biphenylenedioxy) diacetic acid 2
Chlorhydroxyaluminum 4
Magnesia silica 3
Silicic anhydride 4
Isopropyl myristate 3
Methylcyclopolysiloxane 1.5
Decamethylpolysiloxane 3
Sorbitan oleate 0.5
Stearyl glycyrrhetinate 0.02
Vegetable squalane 0.1
Mulberry extract 0.3
Fragrance B 0.2
Ethanol 2
Liquefied petroleum gas balance
Total 100.0

  The fragrance compositions A, B, C, D, and E used in the above examples are based on the fragrance compositions A to E described in Tables 5 to 19 of JP-A-2003-95895. The raw materials used in the above examples are shown below.

Claims (2)

A biphenyl ether derivative represented by the following general formula (1) or a salt thereof.

(In the formula, R ¹ and R ² each independently represent an alkylene group having 1 to 3 carbon atoms or an alkenylene group having 2 to 3 carbon atoms, and X ¹ and X ² each independently represent an anionic group.) An external preparation composition comprising the biphenyl ether derivative or a salt thereof according to claim 1.