JP5217176B2 - External preparation composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to an external preparation composition containing a gallic acid derivative, and in particular, external use that improves the feel of fibers and hair, prevents discoloration of the composition under high temperature storage, and prevents decomposition of the gallic acid derivative. It is related with an agent composition.

  In recent years, as a method of administering a drug that has almost no pain and has an effect that lasts for a long time, a method of applying or applying a patch, a plaster, a cream preparation, a gel preparation or the like containing the drug to the skin has been used. However, patches and plasters have a problem that they are not easily expanded and contracted with respect to the movement of the skin surface and easily peel off. In addition, cream preparations and gel preparations are easily washed away with water, soap, etc., and thus cannot be said to have sufficient sustainability.

  In addition, hair is a tissue made by keratinization of cells, and it is known that it is damaged by chemical treatment such as permanent treatment and hair dyeing treatment, sunlight, etc., but it cannot repair damage by itself. Therefore, various hair care agents are used. However, while conventional hair care agents can provide a good feel when applied, they are easily removed by washing with a shampoo or the like and cannot be said to have a sufficient persistence of the repair effect.

  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 (Patent Document 1: Japanese Patent Laid-Open No. 5-163123, Patent Document 2: Japanese Patent Laid-Open No. 5-155740, Patent Document 3: Japanese Patent Laid-Open No. 5-155541, Patent Document 4: Japanese Patent Laid-Open No. 5-279231), a method using a photoactivatable diazirine compound (Patent Document 5: Japanese Patent Laid-Open No. 2003-335638), complexation Cosmetic composition containing an agent (Patent Document 6: see JP 2004-115518 A), cosmetic composition containing a biotin compound and a complexing agent having a specific dissociation constant (Patent Document 7: JP 2004-2398 A) And Japanese Patent Application Laid-Open No. 2005-23016). 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. From the above, a compound having a high adsorptivity to a protein without irreversible denaturation of the protein due to a bond different from the covalent bond has been desired. In addition, the following is mentioned as a prior art document relevant to this invention.

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 is a composition containing a gallic acid derivative, having an effect of improving the feel of an object, and further having an effect of sustaining the improvement of touch, and the discoloration of the composition at high temperature storage, And it aims at providing the external preparation composition which prevents decomposition | disassembly of a gallic acid derivative.

As a result of intensive studies to achieve the above object, the present inventor has improved the feel of fibers, hair, and the like with a specific gallic acid derivative, and is a protein, particularly keratin protein, which is the main constituent protein of skin and hair. The composition for external use having a high adsorptivity and containing a gallic acid derivative enhances the hair adsorptivity of useful components such as the gallic acid derivative itself or a drug or a conditioning agent used in combination by the action of the gallic acid derivative. It was found that these effects can be maintained for a long time.
However, the composition containing this gallic acid derivative was discolored over time, and it was found that the gallic acid derivative was easily decomposed, and this had a strong tendency to discolor and decompose particularly at high temperatures. As a result of further intensive studies, the inventor can prevent discoloration / decomposition at high temperatures by adding an inorganic acid, an amino acid, or an organic acid having 1 to 3 hydroxyl groups to a composition containing a gallic acid derivative. This has led to the present invention.

Accordingly, the following invention is provided.
[1]. (A) An external preparation composition containing 4-glyceryl gallic acid, sodium 4-glyceryl gallate, or 4- (1-hydroxyethyl) gallic acid , and (B) citric acid .
[2]. The external preparation composition according to [1], wherein the component (A) is 4-glyceryl gallic acid or sodium 4-glyceryl gallate.
[3]. The external preparation composition according to [1] or [2], wherein the amount of component (A) is 0.05 to 5% by mass and the amount of component (B) is 0.01 to 3% by mass.
[4]. Furthermore, the external preparation composition in any one of [1]-[3] containing 0.01-20 mass% of quaternary ammonium salts.
[5]. The external preparation composition according to any one of [1] to [4], which is a hair cosmetic.

  According to the present invention, an external preparation composition containing a gallic acid derivative and having an effect of improving the feel of an object, and further having an effect of sustaining the improvement of the touch, the discoloration of the composition at high temperature storage, and the gallic acid derivative It is possible to provide an external preparation composition that prevents the decomposition of the composition.

  The (A) gallic acid derivative of the present invention is represented by the following general formula (1), has a good feel to fibers, hair, etc., and has high adsorptivity with proteins, particularly keratin proteins. This effect is particularly pronounced for damaged hair.

［式中、Ｒ¹は水素原子、アルカリ金属、アルカリ土類金属、遷移金属、置換もしくは非置換のアンモニウム、又は炭素数１〜２２のアルキル基もしくはアルケニル基を示し、Ｒ²、Ｒ³及びＲ⁴はそれぞれ独立に、水素原子、又は下記構造式（２）もしくは下記構造式（３）

（式中、ｎは１〜１０の整数を示す。）

（式中、Ｒ⁵は水素原子又はメチル基を示し、ｐは１〜１００の整数を示す。）
で表される一価の基であり、Ｒ²、Ｒ³及びＲ⁴のうち、少なくとも一つが上記構造式（２）又は（３）で表される一価の基である。］

[Wherein, R ¹ represents a hydrogen atom, an alkali metal, an alkaline earth metal, a transition metal, a substituted or unsubstituted ammonium, or an alkyl or alkenyl group having 1 to 22 carbon atoms, and R ² , R ³ and R ⁴ is independently a hydrogen atom, the following structural formula (2) or the following structural formula (3)

(In the formula, n represents an integer of 1 to 10.)

(In the formula, R ⁵ represents a hydrogen atom or a methyl group, and p represents an integer of 1 to 100.)
And at least one of R ² , R ³ and R ⁴ is a monovalent group represented by the structural formula (2) or (3). ]

R ¹ is a hydrogen atom, an alkali metal, an alkaline earth metal, a transition metal, a substituted or unsubstituted ammonium, or an alkyl group or alkenyl group having 1 to 22 carbon atoms. Alkali metal or alkaline earth metal is a metal atom having a cationic property such as sodium ion, potassium ion, calcium ion, etc., and the alkyl group or alkenyl group having 1 to 22 carbon atoms may be linear, It may be branched. Examples of the substituted ammonium include alkylammonium such as primary amine, secondary amine and tertiary amine, and hydroxyalkylammonium such as monoethanolamine, diethanolamine and triethanolamine. When R ¹ is an alkali metal, alkaline earth metal, transition metal, or substituted or unsubstituted ammonium, —COOR ¹ forms a salt.

R ² , R ³ and R ⁴ are each independently a hydrogen atom or a monovalent group represented by the structural formula (2) or (3), and at least of R ² , R ³ and R ⁴ One is a monovalent group represented by the structural formula (2) or (3). Examples of the monovalent group represented by the structural formula (2) include a glyceryl group, a diglyceryl group, a triglyceryl group, and a decaglyceryl group. Examples of the monovalent group represented by the structural formula (3) include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene / polyoxypropylene group. Among these, a glyceryl gallate derivative in which at least one of R ² , R ³ and R ⁴ is a monovalent group represented by the structural formula (2) is preferable.

Examples of the gallic acid derivative represented by the general formula (1) include gallic acid derivatives shown below in the general formula (1).
1) 4-glyceryl gallic acid in which R ¹ , R ² and R ⁴ are hydrogen atoms and R ³ is a group represented by n = 1 in the above structural formula (2) 2) R ¹ , R ² and R ⁴ Is a hydrogen atom, R ³ is a group represented by n = 2 in the above structural formula (2) 4- (diglyceryl) gallic acid 3) R ¹ , R ² and R ⁴ are hydrogen atoms, R ³ is 4- (decaglyceryl) gallic acid which is a group represented by n = 10 in the structural formula (2) 4) R ¹ is a sodium atom, R ² and R ⁴ are hydrogen atoms, and R ³ is the above structure In formula (2), sodium 4-glyceryl gallate which is a group represented by n = 1 5) R ¹ is a methyl group, R ² and R ⁴ are hydrogen atoms, R ³ is the above structural formula (2) in, n = is a group 4-glyceryl gallic acid methyl ester 6 represented by 1) R ¹ and R ⁴ are hydrogen atoms, R ² and R ³ is the structural formula (2), n = 1 Is a group represented by 3,4 diglyceryl gallate 7) R ¹ and R ³ are hydrogen atoms, in R ² and R ⁴ are the structural formula (2), a group represented by n = 1 3 , 5-Diglyceryl gallic acid 8) 3,4,5-triglyceryl gallic acid 9) R in which R ¹ is a hydrogen atom, R ² , R ³ and R ⁴ are n = 1 in the above structural formula (2) ^1, R ^2, R ⁴ is a hydrogen atom, in R ³ is the structural formula (3), R ⁵ is a hydrogen atom, a group represented by p = 1 4- (1- hydroxyethyl) gallate,
10) R ¹ is sodium atom, R ² and R ⁴ are hydrogen atoms, in R ³ is the structural formula (3), R ⁵ is a hydrogen atom, a group represented by p = 1 4- (1 -Hydroxyethyl) sodium gallate,
11) 3,4-di (1-hydroxy) wherein R ¹ and R ⁴ are hydrogen atoms, R ² and R ³ are the group represented by the formula (3), R ⁵ is a hydrogen atom, and p = 1 Ethyl) gallic acid,
12) 3,5-di (1-hydroxy) wherein R ¹ and R ³ are hydrogen atoms, R ² and R ⁴ are the above-described structural formula (3), R ⁵ is a hydrogen atom and p = 1 Ethyl) gallic acid,
13) 3,4,5-tri (1), wherein R ¹ is a hydrogen atom, R ² , R ³ , R ⁴ are the group represented by the formula (3), R ⁵ is a hydrogen atom, and p = 1 -Hydroxyethyl) gallic acid,
14) 4-polyoxyethylene (20) gallic oxide in which R ¹ , R ² , and R ⁴ are hydrogen atoms, R ³ is a hydrogen atom in the structural formula (3), and R ⁵ is a group represented by p = 20 acid,
Etc.

  Among these, 4-glyceryl gallic acid, sodium 4-glyceryl gallate, 3,4-diglyceryl gallic acid, 3,5-diglyceryl gallic acid, 3,4,5- Triglyceryl gallic acid, 4- (1-hydroxyethyl) gallic acid, sodium 4- (1-hydroxyethyl) gallate, 3,4-di (1-hydroxyethyl) gallic acid, 3,5-di (1- Hydroxyethyl) gallic acid and 3,4,5-tri (1-hydroxyethyl) gallic acid are preferable, and 4-glyceryl gallic acid, 3,4 is preferable because of its ease of incorporation into an external preparation composition and the like. -Diglyceryl gallic acid and 3,4,5-triglyceryl gallic acid are more preferred.

The gallic acid derivative represented by the general formula (1) can be produced, for example, by the following synthesis method. Details will be described in a production example described later.
The gallic acid derivative represented by the general formula (1) including the monovalent group represented by the structural formula (2) can be obtained by dihydroxylation of the corresponding olefin compound. Examples of the dihydroxylation method include a method in which an olefin is directly dihydroxylated with osmium oxide, a method in which an epoxy compound is used as an intermediate using a peroxide of an organic acid, and this is ring-opened. For example, when methyl-4-O-allyl ether gallate is reacted with an organic acid such as formic acid or peracetic acid, the olefin is oxidized and then reacted with the organic acid to produce a mixture of esters and dihydroxyl compounds. . When these compounds are subjected to hydrolysis without isolation or purification, the target compound can be obtained. The olefin compound as an intermediate can be obtained by reacting a gallic acid ester with allyl bromide in the presence of a base. Moreover, as a method of hydrolyzing a gallic acid ester, there are a method of treating with basic water, a method of treating with acidic water, etc., and any of them can be applied.

  The gallic acid derivative represented by the general formula (1) including the monovalent group represented by the structural formula (3) is a corresponding EO (ethylene oxide), PO (propylene oxide), or both to gallic acid. It can be obtained in addition. For example, the method given in the following production example can be mentioned.

  The external preparation composition of the present invention contains one kind or two or more kinds of gallic acid derivatives represented by the above general formula (1). This gallic acid derivative improves the feel of fibers, hair, etc., and has high adsorptivity to keratin protein, which is the main constituent protein of skin and hair. The agent composition can maintain the effects of the gallic acid derivative itself and the active ingredient used in combination. This effect is particularly pronounced for damaged hair.

  Although the compounding quantity of the gallic acid derivative represented by General formula (1) is not specifically limited, Usually 0.001 mass% or more with respect to the external preparation composition whole quantity, Preferably it is 0.01-20 mass%, More preferably 0.05-5 mass%. If the blending amount is less than 0.001% by mass, the desired effect may not be obtained.

  The component (B) used in the present invention is an inorganic acid, an amino acid, an organic acid having 3 or less hydroxyl groups, or a salt thereof, which can be used alone or in combination of two or more. Examples of inorganic acids include hydrochloric acid, phosphoric acid and the like, and amino acids include cysteine, leucine, arginine, aspartic acid, glutamic acid, glycine, alanine, valine, isoleucine, serine, threonine, methionine, asparagine, glutamine, proline, phenylalanine, Examples include tyrosine, tryptophan, lysine, histidine and the like. Examples of the organic acid having 3 or less hydroxyl groups include hydroxycarboxylic acids such as citric acid, lactic acid, glycolic acid, malic acid, and salicylic acid, maleic acid, succinic acid, thioglycolic acid, and the like. Examples of these salts include metal salts such as sodium salts, potassium salts, calcium salts, and magnesium salts, ammonium salts, and amine salts. Of these, hydroxycarboxylic acids and salts thereof are preferably used, and citric acid, glycolic acid, and salts thereof are particularly preferably used.

  Although the compounding quantity of (B) component is not specifically limited, 0.001 mass% or more is preferable with respect to external preparation composition whole quantity, More preferably, it is 0.01-10 mass%, More preferably, it is 0. It is selected in the range of 0.01 to 3% by mass. If it is less than 0.001% by mass, it may be difficult to obtain a sufficient discoloration / decomposition preventing effect, and if it exceeds 10% by mass, the stability of the external preparation composition may be affected.

  The external preparation composition of the present invention can be widely used in many product forms such as liquid form, cream form, foam form, spray form, gel form, powder form, solid form and the like, and is an external preparation for hair such as hair cosmetics. It can be suitably used for an external preparation for skin. Examples of hair cosmetics include shampoos, rinses, conditioners, hair colors, flushing treatments, non-rinsing treatments, and hair styling agents such as foaming agents.

  In addition, when using the external preparation composition of this invention especially as hair cosmetics, by using together the gallic acid derivative represented by the said General formula (1), and a quaternary ammonium salt, with respect to damaged hair Thus, it is possible to obtain a hair cosmetic with improved feel and superior conditioning effect durability. Examples of the quaternary ammonium salt include quaternary ammonium salts represented by the following general formula (4).

（式中、Ｒ⁶、Ｒ⁷、Ｒ⁸及びＲ⁹のうち１〜２個は炭素数８〜２４のアルキル基、アルケニル基、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、Ｘはハロゲン原子を示す。）

(In the formula, 1-2 of R ⁶ , R ⁷ , R ⁸ and R ⁹ represent an alkyl group having 8 to 24 carbon atoms, an alkenyl group, or a hydroxyalkyl group, and the rest represent an alkyl group having 3 or less carbon atoms. X represents a halogen atom.)

  Specific examples of the quaternary ammonium salt represented by the general formula (4) include lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, benzalkonium chloride, stearyl chloride. Examples thereof include dimethylbenzylammonium, dicocoyldimethylammonium chloride, distearyldimethylammonium chloride, lauryltrimethylammonium bromide, stearyltrimethylammonium bromide and the like, which can be used alone or in combination of two or more.

  Although the compounding quantity of a quaternary ammonium salt is not specifically limited, 0.01-20 mass% is preferable normally with respect to the external preparation composition whole quantity, More preferably, it is 0.1-5 mass%. Within this range, particularly good feeling for damaged hair and conditioning effect can be obtained.

  In the external preparation composition of the present invention, in addition to the essential gallic acid derivative and the optional component, an appropriate amount of components usually used in the external preparation composition can be blended within a range not impairing the effects of the present invention. Examples of the components usually used in the external preparation composition include, for example, cationic surfactants other than the above, anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic polymer compounds, anionic polymers Compounds, nonionic polymer compounds, polymers such as amphoteric polymer compounds, silicones, fungicides, UV absorbers, antioxidants, higher alcohols, hydrocarbons, animal and vegetable oils, ester oils, colorants, fragrances, solvents (ethanol , Water, etc.), fatty acids and the like can be used. These additive components can be used singly or in appropriate combination of two or more.

  The manufacturing method of the external preparation composition of this invention is not specifically limited, It can prepare based on the conventional method of each dosage form. For example, it can be obtained by mixing the component (A), the component (B) and water (remainder).

  Since the external preparation composition of the present invention has a remarkable effect particularly on damaged hair, it is suitable for damaged hair damaged by hair, particularly permanent hair or hair dye.

  As for pH (25 degreeC) of the external preparation composition of this invention, 3-7 are preferable. The pH can be measured by inserting the electrode of a pH meter directly into the hair cosmetic and reading the pH value after stabilization using the method defined in the general test method for cosmetic raw material standards.

  The external preparation composition of the present invention is filled in a container and used for use. Containers include, for example, aluminum laminated tubes, EVAL tubes, aluminum tubes, glass-deposited plastic tubes, etc., dispensers and squeeze containers by mechanical or differential pressure, laminated film containers, dropper containers, stick containers, bottle containers Etc. Laminate film usually has two or more layers, and the material is polyethylene, polyethylene terephthalate, polyester, biaxially stretched polypropylene, unstretched polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, etc., paper, aluminum It consists of vapor-deposited plastic. In consideration of strength, flexibility, weather resistance and the like, generally 2 to 5 layers can be used. As the material of the bottle, for example, polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyvinyl chloride, ethylene-vinyl alcohol resin, acrylonitrile / styrene resin, ABS resin, polyamide, etc., and a single layer or a combination of two or more layers are used. be able to. Furthermore, the aerosol container can be filled.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, unless otherwise specified, “%” in the composition indicates mass%, and the amount of each component indicates a numerical value (AI) converted to a pure component.

[Production Example 1: Synthesis of 4-glyceryl gallic acid]
To a mixed solution of 36.8 g of methyl gallate, 300 mL of acetone, and 60 mL of DMF (dimethylformamide), 33.2 g of potassium carbonate was added, stirred, heated, refluxed for 20 minutes, and then 24.2 g of allyl bromide was added dropwise. Refluxed for another 5 hours. After distilling off the solvent under reduced pressure, 200 mL of ethyl acetate and 200 mL of water were added for liquid separation, and the resulting organic layer was washed with 100 mL of saturated brine and concentrated. To the obtained residue, 300 mL of hexane was added and stirred to obtain crude crystals as a precipitate. After the hexane solution was decanted, the crude crystals were crystallized using ethyl acetate and hexane, which was collected by filtration and dried to obtain 9.4 g of methyl 4-O-allyl gallate.
In a mixed solution of 6 mL of formic acid and 6 mL of 30% hydrogen peroxide solution, 2 g of methyl 4-O-allyl gallate obtained by the above method was prepared while adjusting the temperature so that the internal temperature was 30-35 ° C. The reaction was divided into several times and added over 1 hour, followed by reaction for 2 hours while adjusting the temperature so that the internal temperature was 35-40 ° C. 20 mL of water and 30 mL of toluene were added to the reaction system for liquid separation, and after removing the toluene layer, 30 mL of ethyl acetate was added to the aqueous layer for liquid separation extraction. Further, 30 mL of ethyl acetate was added to the aqueous layer to perform re-extraction, and combined with the previous ethyl acetate layer. The organic layer was washed successively with 20 mL of water, 20 mL of aqueous sodium bicarbonate, and 20 mL of aqueous sodium bisulfite solution, and then washed with aqueous sodium hydroxide solution until the aqueous layer became neutral. After confirming that no peroxide remained on potassium iodide starch paper, the mixture was concentrated and the resulting residue was purified by silica gel column chromatography (silica gel 60 g, developing solvent: hexane / ethyl acetate = 1). / 4 (volume ratio)). The obtained 4-glyceryl gallic acid methyl ester and its formate were combined to obtain 0.35 g. This was added to an aqueous solution of 1 mL of water and 0.2 g of sodium hydroxide, and reacted at room temperature for 3 hours. 14 mol / L hydrochloric acid was added to adjust the reaction solution to pH 1. The precipitated crystals were collected by filtration, then shaken with 2 mL of water and dried to obtain 0.20 g of 4-glyceryl gallic acid powder.
Results of ¹ H-NMR (DMSO-d6) of this powder; 3.46 (2H, m), 3.77 (1H, m), 3.85 (1H, m), 4.06 (1H, m) , 4.0-5.5 (2H, br), 6.93 (2H, s), 9.39 (2H, br)

[Production Example 2: Synthesis of sodium 4-glyceryl gallate]
Dissolve 0.59 g of 4-glyceryl gallic acid powder obtained by the method of Production Example 1 in 50 mL of water, add 20 mL of a 100 mmol / L aqueous sodium hydroxide solution, thoroughly stir and mix, and then remove the water by lyophilization. Then, 0.35 g of sodium 4-glyceryl gallate powder was obtained.

[Production Example 3: Synthesis of 4- (1-hydroxyethyl) gallic acid]
Add 184.0 g of methyl gallate and 4.0 g of sodium hydroxide into 1000 mL of methanol, and add 50 g of ethylene oxide under the condition that the pressure does not exceed 0.2 MPa, so that the temperature is 80-100 ° C. The reaction was carried out for 2 hours while adjusting the temperature. The reaction was carried out under pressure using an autoclave. After cooling, after distilling off the solvent under reduced pressure, 500 mL of ethyl acetate and 500 mL of water were added for liquid separation, and the resulting organic layer was washed with 200 mL of saturated brine and concentrated. 20 g of the obtained residue was purified by silica gel column chromatography (silica gel 1000 g, developing solvent: hexane / ethyl acetate = 1/4 (volume ratio)), 4- (1-hydroxyethyl) gallic acid methyl ester11. 4 g was obtained. This was added to an aqueous solution of 50 mL of water and 10.0 g of sodium hydroxide, and reacted at room temperature for 3 hours. 14 mol / L hydrochloric acid was added to adjust the reaction solution to pH 1. The precipitated crystals were collected by filtration, then washed with 50 mL of water and dried to obtain 10.5 g of 4- (1-hydroxyethyl) gallic acid powder. It was.
¹ H-NMR (DMSO-d6) result of the powder; 3.90 (2H, t), 4.18 (2H, t), 6.96 (2H, s)

[Examples 1 to 4, Reference Examples 1 to 3 , Comparative Examples 1 to 7]
Preparations of external preparations for hair (hair cosmetics) having the compositions shown in Tables 1 and 2 were prepared, and the following methods were used to improve the feeling, the durability of the feeling improvement effect, and the storage stability (discoloration and gallic composition at 40 ° C.) (Decomposition of acid derivatives) was evaluated. The results are also shown in the table.

<Evaluation of feel improvement effect>
An Asian human hair bundle (undamaged hair bundle) having a length of 30 cm and a mass of 10 g was immersed in a model bleach solution having the following composition 1 (10 times the amount of human hair bundle (100 mL)) at room temperature for 30 minutes. Thereafter, the human hair bundle was sufficiently washed with tap water and dried to obtain a damaged hair bundle. 1.5 g of the external preparation composition for hair was applied to the damaged hair bundle, and the hair was blended with the whole damaged hair bundle using a comb, and then naturally dried to obtain a treated hair bundle.
(Composition 1) Model bleach solution composition Mass (%)
Hydrogen peroxide 6
Ammonia 3
Sodium chloride 5
Sodium hydroxide appropriate amount (adjusted to pH 10.8)
Purified water balance total 100

10 evaluators touched the treated hair bundle with the hair external preparation composition and the untreated hair bundle (damaged hair bundle) that was not treated with the hair external preparation composition. Comparative evaluation was made. The table shows four levels according to the following criteria.
◎: The number of evaluators who said that the treated hair bundle was better 9 or more ○: The number of evaluators who said that the treated hair bundle was better △: The treated hair bundle was better The number of evaluators is 3 to 5 ×: The number of evaluators who thinks that the treated hair bundle is better is 2 or less

<Sustainability evaluation of feel improvement effect>
1 g of a model shampoo solution of the following composition 2 is applied to the treated hair bundle and the untreated hair bundle by the external preparation composition for hair used for evaluating the touch improvement effect, and immediately washed with a finger and foamed. After rinsing with tap water for 1 minute, it was 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.
(Composition 2) Model shampoo solution Mass (%)
Sodium polyoxyethylene lauryl ether sulfate 5
Sodium tetradecenesulfonate 9
Lauric acid amidopropyl betaine 4.5
Polyoxyethylene (20) oleyl ether 1.5
Polyoxyethylene (30) hydrogenated castor oil 4
Sodium benzoate 0.1
Citric acid 0.5
Purified water balance
Total 100.0

<Discoloration of composition>
30 mL of the external preparation composition for hair having the composition shown in Tables 1 and 2 was stored in a 50 mL vial, and the degree of discoloration after 40 ° C. and 1 month was evaluated according to the following criteria.
A: No discoloration was observed after the storage test.
○: Slightly discolored (very light yellow), but no problem in commercial value.
Δ: Yellow discoloration, there is a problem in commercial value.
X: Discolored to deep yellow.

<Disassembly>
30 mL of a composition for external use for hair having the composition shown in Tables 1 and 2 is stored in a 50 mL vial, the composition after 1 month at 40 ° C. is measured by HPLC, and the degree of change in peak area corresponding to the gallic acid derivative Was evaluated according to the following criteria.
A: 95% or more of initial value B: 85-94% of initial value
Δ: 70 to 84% of initial value
X: 69% or less of initial value HPLC conditions:
Using a Hitachi D-7000 HPLC system, the measurement was performed under the following conditions.
Column: Inertsil ODS-2 (φ4.6 × 250 mm) (manufactured by GL Sciences)
Column temperature: 40 ° C
Mobile phase: acetonitrile / 0.1% aqueous trifluoroacetic acid solution = 7/93
Flow rate; 1 mL / min detection; absorbance at 254 nm

[Example 5 ]
An aerosol foam composition for hair styling comprising the following composition was prepared.
Composition%
Cationized cellulose (A) 0.2
N-coconut oil fatty acyl-sodium L-glutamate 0.2
Cetyltrimethylammonium chloride 0.7
Dimethylpolysiloxane (100 mm ² / s) 8.0
Dimethylpolysiloxane (10 million mm ² / s) 2.0
Methyl paraoxybenzoate 0.05
4-Glyceryl gallic acid 0.3
Sodium pyrrolidonecarboxylate 0.4
Fragrance composition B 0.05
Citric acid 0.4
Sodium hydroxide appropriate amount (adjusted to pH 5.5)
Ethanol 15.0
Purified water balance
Liquefied petroleum gas (0.49 MPa) 7.0
Total 100.0
<Preparation method>
Components other than dimethylpolysiloxane and liquefied petroleum gas were mixed, and this mixed solution was filled into a pressure-resistant aluminum can, and then filled with dimethylpolysiloxane and clinched with an aerosol valve. Finally, liquefied petroleum gas was filled into a foam agent.

[ Reference Example 4 ]
An aerosol foam composition for hair styling comprising the following composition was prepared.
Composition%
Stearic acid dimethylaminopropylamide 0.6
3-Methyl-1,3-butanediol 5.0
Plant-based squalane 0.5
Polyoxyethylene (30) stearyl ether 0.2
Polyoxyethylene (20) sorbitan monopalmitate 0.4
3,4-diglyceryl gallic acid 0.5
Cationic polymer compound (A) 0.4
Dimethylpolysiloxane (1 million mm ² / s) 1.0
Dimethylpolysiloxane (30 mm ² / s) 2.0
Lactic acid 0.1
Sodium hydroxide appropriate amount (adjusted to pH 5.0)
Methyl paraoxybenzoate 0.15
Oxybenzonesulfonic acid 0.1
Ethanol 10.0
Purified water The remaining liquefied petroleum gas (0.29 MPa) 8.5
Dimethyl ether 1.5
Total 100.0
<Preparation method>
Components other than vegetable squalane, dimethylpolysiloxane, lactic acid, liquefied petroleum gas, and dimethyl ether were mixed, and then adjusted to pH 5.0 with sodium hydroxide to obtain a stock solution. After filling this undiluted solution into a transparent pressure-resistant PET container, it was filled with plant squalane and dimethylpolysiloxane in this order, and crimped with an aerosol valve. Finally, liquefied petroleum gas and dimethyl ether were charged in this order to form a foam agent.

[ Reference Example 5 ]
A non-aerosol foam preparation for hair styling having the following composition was prepared.
Composition%
Stearyltrimethylammonium chloride 1.0
Lauryldimethylamine oxide 0.5
Amphoteric polymer compound (A) 0.3
Polyoxyethylene (25) cetyl ether 0.3
Amino-modified silicone emulsion (A) 1.0
3,4,5-triglyceryl gallic acid 0.3
Gallic acid-3,5-diglucoside 0.2
Methyl paraoxybenzoate 0.1
Propyl paraoxybenzoate 0.05
Oxybenzonesulfonic acid 0.1
Lactic acid 0.08
Sodium hydroxide appropriate amount (adjusted to pH 4.5)
Fragrance composition C 0.15
Ethanol 23.0
Purified water balance
Total 100.0
<Preparation method>
The above components were mixed and dissolved, and this mixed solution was filled in a non-aerosol type pump foam container to obtain a non-aerosol foam agent.

[ Reference Example 6 ]
An aerosol spray for treatment with the following composition was prepared.
Composition%
DL-pantothenyl alcohol 0.5
Polyether-modified silicone (A) 1.0
Amidopropyltrimethylammonium chloride 0.4
4- (1-hydroxyethyl) gallic acid 0.1
Oxybenzone 0.1
Hydrolyzed silk solution 0.6
Hydroxypropyl chitosan solution 0.6
Ammonium glycolate 0.25
Ethanol 10.0
Purified water balance
Dimethyl ether 30.0
Total 100.0
<Preparation method> Components other than dimethyl ether were mixed and dissolved, and this mixed solution was filled in a pressure-resistant aluminum can and then clinched with a tilt type aerosol valve. Finally, dimethyl ether was filled in this order to obtain an aerosol spray.

[Example 6 ]
A non-washing treatment gel having the following composition was prepared.
Composition%
Hydroxyethyl cellulose 1.0
Stearyltrimethylammonium chloride 0.8
Amino-modified silicone emulsion (B) 1.5
Polyoxypropylene (14) diglyceryl ether 0.7
Propylene glycol 3.0
Sodium 4-glyceryl gallate 0.5
Rosmarinic acid crude product 0.1
Citric acid 0.1
Sodium citrate 0.1
Sodium pyrophosphate 0.05
Glycolic acid 0.05
Fragrance composition A 0.05
Dihydroxybenzophenone 0.05
Methyl paraoxybenzoate 0.1
Ethanol 25.0
Purified water balance
Total 100.0
<Preparation method>
Hydroxyethyl cellulose was dispersed in propylene glycol, and water was added to dissolve it, and then the remaining components were mixed. Stirring was continued until the liquid became more viscous. This composition was filled in a pump-type container to obtain a gel agent.

[ Reference Example 7 ]
A treatment spray having the following composition was prepared.
Composition%
Dipropylene glycol 1.5
Monoisostearic acid POE (20) hydrogenated castor oil 0.2
Polyoxyethylene (20) isostearyl ether 0.5
Stearyltrimethylammonium chloride 0.7
Lauryldimethylaminoacetic acid betaine 0.5
Polyether-modified silicone (B) 0.5
Trimethylglycine 0.3
4-glyceryl gallic acid 0.6
Birch extract 1.0 *
Eucalyptus extract 0.5 *
Black tea extract 0.5 *
Succinic acid 0.3
Methyl paraoxybenzoate 0.1
Fragrance composition E 0.3
Ethanol 15.0
Purified water balance
Total 100.0
<Preparation method>
The above components were mixed and dissolved, and this composition was filled in a pump spray container having an injection port diameter of φ0.3 mm to obtain a spray agent.

[Example 7 ]
A treatment hair cream having the following composition was prepared.
Composition%
(A)
N- [3-Alkyl (12,14) oxy-2-hydroxypropyl] -L-arginine hydrochloride solution 1.2
Amidopropyltrimethylammonium chloride behenate 0.6
Cetyl alcohol 4.0
Stearyl alcohol 2.5
Jojoba oil 1.0
Camellia oil 2.5
Vegetable squalane 1.0
Sorbitan monostearate 2.0
Lipophilic glyceryl monostearate 1.5
Pyroglutamic acid isostearate POE (25) glyceryl 1.0
Propyl paraoxybenzoate 0.1
(B)
Methyl paraoxybenzoate 0.4
Sodium 4-glyceryl gallate 0.8
Citric acid 0.15
Birch extract 2.0 *
Purified water balance (C)
Fragrance composition D 0.5
Total 100.0
<Preparation method>
While (A) was heated to 80 ° C. and stirred well, the mixed solution of (B) that was also heated to 80 ° C. was added with stirring. The mixed solution was cooled to 45 ° C. with stirring, and (C) was added to obtain a hair cream. The average particle diameter of the emulsion was 2 μm, and the viscosity at 25 ° C. was 4.3 Pa · s as a result of measurement with a BL type viscometer (No. 3 rotor, 12 rpm).

[ Reference Example 8 ]
A hair rinse agent having the following composition was prepared.
Composition%
(A)
Acryl myristate palmitate amidobutylguanidine 0.1
N- [3-alkyl (12,14) oxy-2-hydroxypropyl] -L-arginine hydrochloride solution 0.1
Polyethylene glycol 0.2
Behenyltrimethylammonium chloride 0.8
Diglycerin isopalmitic acid ester sebacic acid condensate 1.0
Phosphoric acid 0.3
Cetyl alcohol 1.5
Behenyl alcohol 0.2
Oleyl alcohol 0.3
Oleic acid 0.2
Isostearic acid 0.2
Glyceryl monostearate 0.1
Sorbitan monolaurate 0.1
Propyl paraoxybenzoate 0.3
Dimethylpolysiloxane (1 million mm ² / s) 1.0
Dimethylpolysiloxane (100,000 mm ² / s) 1.0
Dimethylpolysiloxane (50 mm ² / s) 1.0
(B)
Glycine 0.7
Trimethylglycine 0.2
Arginine 0.3
3,4-diglyceryl gallic acid 0.5
Methyl paraoxybenzoate 0.3
Purified water balance (C)
Ethanol 2.0
Fragrance composition B 0.5
Total 100.0
<Preparation method>
While (A) was heated to 80 ° C. and stirred well, the mixed solution of (B) that was also heated to 80 ° C. was added with stirring. The mixed solution was cooled to 50 ° C. with stirring, and (C) was added to obtain a hair rinse agent. This emulsion average particle diameter was 1 μm, and the viscosity at 25 ° C. was 3.8 Pa · s as a result of measurement with a BL type viscometer (No. 3 rotor, 12 rpm).

[ Reference Example 9 ]
A hair rinse agent having the following composition was prepared.
Composition%
(A)
2-Ethylhexyl paradimethylaminobenzoate 0.05
4-tert-butyl-4'-methoxy-dibenzoylmethane 0.05
Isostearyl myristate 1.0
Amphoteric polymer compound (B) 1.5
Stearyltrimethylammonium chloride 1.0
Stearyl alcohol 4.0
Polyoxyethylene (20) hydrogenated castor oil 1.0
Propylene glycol 5.0
(B)
3,4,5-triglyceryl gallic acid 0.5
Malic acid 0.2
Sodium hydroxide appropriate amount (adjusted to pH 3.7)
Purified water balance (C)
Ethanol 3.0
Fragrance composition A 0.3
Total 100.0
<Preparation method>
While (A) was heated to 70 ° C. and stirred well, the mixed solution of (B) that was also heated to 70 ° C. was added with stirring. The mixed solution was cooled to 50 ° C. with stirring, and (C) was added to obtain a hair rinse agent. The composition had an emulsified average particle size of 1 μm and a viscosity at 25 ° C. of 4 Pa · s as a result of measurement with a BL type viscometer (No. 3, rotor, 12 rpm).

[ Reference Example 10 ]
A rinse-off treatment agent having the following composition was prepared.
Composition%
(A)
4-Guanidinobutyllaurylamide 1.0
N-coconut oil fatty acid acyl-L-arginine ester 0.5
Stearic acid dimethylaminopropylamide 1.5
Diglycerin isopalmitic acid ester sebacic acid condensate 1.5
Cetyl alcohol 1.5
Behenyl alcohol 3.0
Stearyl alcohol 2.0
Isostearic acid 0.2
Glycerin 3.0
Propylene glycol 5.0
Glyceryl monostearate 0.1
Sorbitan monolaurate 0.1
Polyethylene glycol 0.4
Propyl paraoxybenzoate 0.2
(B)
4- (1-hydroxyethyl) gallic acid 0.1
Phosphoric acid 0.1
Methyl paraoxybenzoate 0.4
Purified water balance (C)
Dimethylpolysiloxane (100,000 mm ² / s) 1.0
Dimethylpolysiloxane (30 mm ² / s) 1.5
Fragrance composition 0.5
Total 100.0
<Preparation method>
While (A) was heated to 70 ° C. and stirred well, the mixed solution of (B) that was also heated to 70 ° C. was added with stirring. The mixed solution was cooled to 50 ° C. with stirring, and (C) was added to obtain a treatment agent. This composition had an emulsified average particle diameter of 3 μm and a viscosity at 25 ° C. of 130 Pa · s as measured by a BH viscometer (No. 6 rotor, 4 rpm).

[Example 8 ]
A shampoo agent having the following composition was prepared.
Composition%
(A)
Behenyltrimethylammonium chloride 2.5
Cetyl alcohol 3.0
Stearyl alcohol 3.0
Polyoxyethylene (11) stearyl ether 0.5
Polyoxyethylene (20) hydrogenated castor oil 0.1
(B)
Sodium tetradecenesulfonate 1.5
Amidopropyl betaine laurate 9.0
Synthetic bentonite 0.2
Lauryldimethylamine oxide 1.0
Cationized cellulose (B) 0.1
Hydroxypropylcellulose 0.05
Purified water 20.0
(C)
Dimethylpolysiloxane (million mm ² / s) 3.0
(D)
Propylene glycol 5.0
Sorbitol 0.3
Hydrolyzed wheat protein 0.1 *
Red No. 106 0.0001
Sodium benzoate 0.9
4-glyceryl gallic acid 1.5
Methylchloroisothiazolinone / methylisothiazoline solution 0.01
Citric acid 0.3
Fragrance composition A 0.5
Purified water balance
Total 100.0
<Preparation method>
While (B) was heated to 80 ° C. and stirred well, the mixed solution of (A) that was also heated to 80 ° C. was added with stirring. The mixed solution was cooled to 50 ° C. with stirring, (C) was added and further stirred sufficiently, and then (D) was added to obtain a shampoo agent. The pH of this composition was 5.5, the average emulsion particle size was 18 μm, and the viscosity at 25 ° C. was 2.6 Pa · s as a result of measurement with a BL type viscometer (No. 3 rotor, 12 rpm).

The sustainability of the feeling improvement effect and the feeling improvement effect of Examples 5 to 8 and Reference Examples 4 to 10 are both good, and even when stored at 40 ° C. for 1 month, discoloration of the composition and decomposition of the gallic acid derivative are observed. There wasn't.

  In addition, the fragrance | flavor composition A, B, C, D, and E used in each said example apply to the fragrance | flavor compositions A-E described in Tables 5-19 of Unexamined-Japanese-Patent No. 2003-95895.

  The raw materials used in the above examples are shown below.

＊：配合量は溶媒を含めた全量で示した。

*: The blending amount is shown as the total amount including the solvent.

Claims (5)

(A) An external preparation composition containing 4-glyceryl gallic acid, sodium 4-glyceryl gallate, or 4- (1-hydroxyethyl) gallic acid , and (B) citric acid . The external preparation composition according to claim 1, wherein the component (A) is 4-glyceryl gallic acid or sodium 4-glyceryl gallate. The external preparation composition according to claim 1 or 2, wherein the amount of the component (A) is 0.05 to 5% by mass, and the amount of the component (B) is 0.01 to 3% by mass. Furthermore, the external preparation composition of any one of Claims 1-3 which contains 0.01-20 mass% of quaternary ammonium salts. It is a hair cosmetic, The external preparation composition of any one of Claims 1-4.