JPS6160806B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hair treatment agent, and more particularly to a hair treatment agent containing a specific keratin substance decomposition derivative and a glycoside or/and a polyphenol compound and having excellent hair style formation and retention properties. Hair style is one of the most important points in beauty, and various beauty treatments are performed.
Examples of this include a so-called permanent treatment using a permanent wave method, and a temporary treatment using a setting lotion, hair spray, etc., and the hair style is maintained by these treatments. However, treatments using the permanent wave method can cause significant damage to the hair and leave it in a state where it is impossible to recover, while treatments with setting lotions, hair sprays, etc. only temporarily fix the hair and remove moisture. These methods have the disadvantage that the set is easily disrupted due to factors such as the following, and none of them are fully satisfactory. The inventors of the present invention have conducted extensive research in order to obtain a hair treatment agent that can easily form hair styles without damaging the hair and that has excellent retention properties. It was discovered that a hair treatment agent obtained by using a decomposed derivative and a glycoside or/and a polyphenol compound in combination satisfies the above requirements, and the present invention was completed. That is, the present invention provides a compound selected from the group consisting of the following two components (A) and (B): (A) an alkali salt of an oxidative decomposition product of a keratin substance and an alkali salt of a derivative in a thiol group of a reductive decomposition product of a keratin substance; (B) 0.05 to 10.0% by weight of one or a mixture of two or more keratin substance decomposition derivatives; (B) 0.001 to 5.0% by weight of one or a mixture of two or more compounds selected from the group consisting of glycosides and polyphenol compounds; The present invention provides a hair treatment agent containing the following. The keratin substance decomposition derivative, which is the component (A) of the present invention, can be obtained either by oxidatively decomposing the keratin substance and converting it into an alkali salt; It is produced by any of the methods of making an alkali salt. The raw material keratin substance (hereinafter simply referred to as "keratin") includes, for example, animal hair, hair, feathers,
Examples include nails, horns, hooves, scales, etc., among which wool, hair, and feathers are particularly preferred. These keratins can be directly subjected to oxidation or reduction reactions, but
If necessary, it may be cut or pulverized into appropriate sizes, or may be subjected to pretreatment such as washing and degreasing. Decomposition of keratin is carried out by one of the following methods. (1) Oxidative decomposition reaction Oxidation of keratin is carried out by various methods known per se [NHLeon; Textile Progress, Vol. 7, p. 1 (1975)]. As an oxidizing agent,
Organic or inorganic oxidizing agents of the type that act electrophilically on disulfide bonds (S-S bonds) in the keratin structure are preferred, such as organic peracids, inorganic peroxoacids or salts thereof, permanganic acid or salts thereof. , chromic acid or its related compounds,
Examples include halogens, peroxides, oxygen acids, or salts thereof, and organic peracids such as peracetic acid, performic acid, and perbenzoic acid are particularly preferred. In doing so, the disulfide bonds of keratin are cleaved to produce sulfonic acid (-SO ₃ H). (2) Reductive decomposition and chemical modification reactions Reducing agents used to reduce keratin are those that cleave the disulfide bonds in the structure to give thiol groups (-SH), and generally Organic or inorganic reducing agents of the nucleophilically acting type are preferred.
Specifically, organic reducing agents such as mercaptoethanol, thioglycolic acid, benzyl mercaptan, 1,4-dithiothreitol, and tributylphosphine; sulfides such as sodium bisulfite and sodium hydrosulfide; lithium aluminum hydride; Examples include inorganic reducing agents such as metal hydrides. The reductive decomposition product of keratin thus obtained is
The thiol group is chemically modified to produce a derivative thereof (hereinafter referred to as a "keratin reduced derivative"). As the derivative of the thiol group,
Examples include: −SCH ₂ COOH, −SCH ₂ CH ₂ COOH,

【formula】

【formula】

[Formula] −SO ₃ H, −SSO ₃ H, − SCH ₂ CH ₂ SO ₃ H,

【formula】

[Formula] − SCH ₂ CH ₂ SO ₂ CH ₂ COOH In this, −
SCH ₂ COOH,

[Formula] is particularly preferred. The chemical modification method of the thiol group can be carried out by means known per se, for example, NHLeon; Textile Progress;
Vol. 7, p. 1 (1975), "Organic Sulfur Compounds" by Shigeru Oki, published by Kagaku Dojin (1968) and "Course on Polymer Experiments" by Masami Oku, Vol. 12, Kyoritsu Shuppan (1957)
It is carried out based on. Examples of the alkali salts of keratin oxidative decomposition products and keratin reduced derivatives include inorganic alkali metal salts such as sodium and potassium, ammonium salts,
Or ethanolamine, diethanolamine, triethanolamine, 2-amino-2-
Examples include salts with organic bases such as methylpropanol, aminomercaptopropanediol, triisopropanolamine, glycine, histidine, and arginine. These can be prepared in a separate system and added to the hair treatment agent, but it is also possible to combine the oxidized decomposition product of keratin or the reduced derivative of keratin and an alkaline substance in the hair treatment agent and form salts in that system. can. In this case, the alkaline substances include, for example, inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and ammonia, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol. , 2-amino-2-methyl-1,3
-Propanediol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1
-butanol, triisopropanolamine,
Organic alkaline substances such as diisopropanolamine, monoisopropanolamine, lysine, arginine, histidine, and hydroxylysine are mentioned, and these are added in an amount of 0.1 to 8 equivalents to the carboxyl group or sulfonic acid group in the oxidized keratin decomposition product or keratin reduced derivative. It is preferable to mix them. The component (A) thus obtained can be used alone or in a mixture of two or more to form a hair treatment agent as described above.
It is blended in an amount of 0.05 to 10.0% by weight (hereinafter simply expressed as %), preferably 0.1 to 1.0%. In addition, component (B) of the present invention is a compound selected from the group consisting of glycosides and polyphenol compounds, and examples of preferable glycosides include alcohol glycosides, resin glycosides, and terpene glycosides. Glycosides, phenolic glycosides, mustard oil glycosides, coumarin glycosides, nitrile glycosides, indocyl glycosides, saponins, etc.
Examples of preferred polyphenol compounds include phloroglucinol, aspidin, phloroglucinol derivatives such as aspidinol; for example, mimosa,
Examples include tannin crude drugs obtained from quebrachiyo, kushichi, asenyaku, gobaiko, gallic, etc., tannins, tannin derivatives such as pyrogallol tannin, and catechol tannin. Among these glycosides and polyphenol compounds, particularly desirable ones include saponin as the glycoside and tannin derivatives as the polyphenol compound. Component (B) is contained in the hair treatment agent composition by combining one or more of them in an amount of 0.001 to 5.0%, preferably
Contains 0.005-0.1%. The hair treatment agent of the present invention is prepared by adding component (A) and
It is produced by dissolving component (B) in a suitable solvent or by using a surfactant to form an emulsion, suspension or gel. Examples of these solvents include water, carbon atoms of 1 to
Examples include lower alcohol No. 3, propylene glycol, glycerin, and the like. Furthermore, the hair treatment agent of the present invention may contain optional ingredients depending on the purpose of use, such as anionic activators, cationic activators,
Nonionic surfactants and amphoteric surfactants; fatty acid higher alcohols, lanolin oils, esters,
Fats and oils such as liquid paraffin; thickeners such as hydroxyethyl cellulose, methyl cellulose, and hydroxypropyl methyl cellulose; preservatives, fragrances, etc. are blended. The hair treatment agent thus obtained can be in the form of an aqueous solution, an ethanol solution, an emulsion, a suspension, or a gel;
Hair rinse agents, hair treatment agents, pre-shampoo agents, hair sprays, hair brushing agents,
It can be in the form of a known hair treatment agent such as a hair setting agent, hair liquid, or hair tonic. Next, the present invention will be explained with reference to synthesis examples and examples, but the present invention is not limited to these examples. Synthesis Example 1 Synthesis of oxidatively decomposed keratin derivative: (a) 10 g of wool fiber was immersed in 700 g of an 8% aqueous peracetic acid solution at room temperature for one day to carry out an oxidation reaction. The obtained oxidized wool is filtered, washed with water,
When the wool was immersed in 700 g of 0.1N ammonia water at room temperature for one day, about 90% of the wool was solubilized in the ammonia water. Approximately 1 g of insoluble portion was removed by filtration, and 2N hydrochloric acid was added to the ammonia aqueous solution of keratose, which is an oxidative decomposition product of wool keratin, to pH 4.0.
Then, α-keratose precipitated out. This was washed with acetone and dried to obtain 5.4 g of α-keratose. Synthesis Example 2 Synthesis of keratin reductive decomposition derivative: (a) 10 g of wool fiber was immersed in 600 ml of an aqueous solution containing 8 M urea and 0.01 M Tris buffer, and after adding 6 ml of 2-mercaptoethanol as a reducing agent, 5 N caustic potassium was added. The pH was adjusted to 10 with an aqueous solution, and the reduction reaction was carried out at room temperature under a nitrogen stream. After about 3 hours, the wool was about 85% solubilized in the reaction solution. Then, while adjusting the pH of the system with a 5N caustic potassium aqueous solution so that it does not fall below 7, 16.5 g of iodoacetic acid is added.
was gradually added, the pH of the system was finally adjusted to 8.5, and the carboxymethylation reaction was carried out at room temperature for 2 hours.
The reaction solution was filtered to remove the lower solvent, and the resulting solution was placed in a cellulose tube and dialyzed against ion-exchanged water to remove low-molecular impurities including urea. As urea is dialyzed,
Inside the cellulose tube is a water-insoluble component
HGT (components with high glycine and tyrosine content)
precipitates and becomes cloudy. After the dialysis, HGT was removed by centrifugation, and SCMKA was obtained from the resulting neutral transparent aqueous solution of S-carboxymethylkeratin (SCMKA) by isoelectric focusing. That is, by adjusting the pH of the system to 4.4 with 1N hydrochloric acid, SCMKA becomes insoluble and precipitates out. This was separated, washed with ethanol, and dried to obtain 4.2 g of SCMKA. (b) In Synthesis Example 2 (a), a porous material obtained by heating feathers instead of wool fibers in a high-pressure container with 6 kg/cm ² of superheated steam at 240°C for 6 minutes and then rapidly releasing them into the atmosphere. Synthesis Example 2 except that 17.5 g of maleic acid was used instead of iodoacetic acid.
By the same operation as in (a), 5.3 g of S-(1,2-
Dicarboxyethyl)-keratin was obtained. Example 1 A hair treatment agent (hair conditioner) having the composition shown below was prepared, and its style formation and retention effects and occurrence of hair breakage were investigated. The results are shown in Table 1. Composition: Glycosides or polyphenol compounds (Table 1) 0.01 (%) Keratin decomposition derivatives (Table 1) 0.1 Distilled water balance Test method: (1) Style formation and retention effect Hair of a Japanese woman measuring 5 g in length, 20 g in length, and about 40 to 50 μ in thickness was soaked for 10 minutes, then rinsed with running water, wrapped around a 1 cm diameter glass tube, and heated indoors (20°C, 65% RH). It was dried for 8 hours. After drying, it was removed from the glass and the length of the curl was measured over time to determine the degree of curl. The degree of curl was determined by the following formula. Curl degree (%) = 100 - Curl length immediately after uncurling - Curl length after 7 hours / Curl length immediately after uncurling x 100 (2) Amount of hair cut 20g of hair Add 1 bundle to each hair treatment agent (5% solution)
Soak for 5 minutes, then rinse under running water for 5 minutes and thoroughly dry with a hair dryer. Next, comb it through 100 times using a commercially available nylon brush. The cut hairs generated during this time were collected and weighed. result:

[Table] As is clear from Table 1, improvements in style formation, retention, and combability are almost always observed when oxidative decomposition products of keratin, derivatives of reducing substances, glycosides, or polyphenols are used alone. However, when both are used together, remarkable improvements in style formation, retention, and combing performance are observed, which is a unique effect of using both together. Example 2 Shampoo composition: (Composition) A Lauryl sulfate triethanol amine salt 15.0 (%) B Lauric acid diethanolamide 5.0 C Hydroxyethyl cellulose 0.5 D Ethanol 3.0 E Keratin decomposition derivative (Synthesis example 2 (b)) 0.2 F Saponin 0.1 G Water Balance H Triethanolamine Amount to make PH=7.0 (manufacturing method) E and F were added to G, and the pH was adjusted to 7.0 with H and dissolved. Next, add A, B, C, and D and heat to 70°C. After the whole is uniformly dissolved, it is cooled to obtain a shampoo composition. Example 3 Hair conditioner: (Composition) A Keratin decomposition derivative (Synthesis example 2 (a)) 0.1 (%) B Tannin (pharmacopoeia) 0.02 C Methylparaben 0.1 D Ethanol 10.0 E Water Balance F Arginine PH7.0 Amount (manufacturing method) Add A, B, C, and D to E, add F while stirring, and adjust the pH to 7.0 to obtain a hair conditioner. Example 4 Hair setting agent: (Composition) A Keratin decomposition derivative (Synthesis Example 1 (a)) 0.7 (%) B Saponin 0.3 C Ethanol 10.0 D Hydroxyethyl cellulose 0.5 E Water Balance F Triethanolamine Amount to give PH7.0 (Production method ) Add A, B, C, and D to E, adjust the pH to 7.0 with F, and then add B to obtain a hair setting agent. Example 5 Hair brushing agent: (Composition) A Keratin decomposition derivative (Synthesis Example 2 (B)) 2.0 (%) B Tannin (pharmacopoeia) 0.1 C Ethanol 10.0 D Polyethylene glycol 6000 5.0 E Water Balance F Arginine PH6.5 Amount (manufacturing method) Disperse A to D in E, then adjust the pH with arginine.
Dissolve each component in Step 6.5 to obtain a hair brushing agent.

Claims (1)

[Scope of Claims] 1. From the group consisting of the following two components (A) and (B): (A) an alkali salt of an oxidative decomposition product of a keratin substance and an alkali salt of a derivative in a thiol group of a reductive decomposition product of a keratin substance; 0.05 to 10.0% by weight of one or a mixture of two or more selected keratin substance decomposition derivatives; (B) 0.001 to 5.0 of a mixture of one or two or more compounds selected from the group consisting of glycosides and polyphenol compounds; A hair treatment agent containing % by weight.