JP2012121831A - Multi-agent type hair treating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-agent type hair treating agent for efficient adhesion of silicone to the hair.SOLUTION: The multi-agent type hair treating agent comprises a hair treating agent (a) mixed with a modified peptide containing one or more of side-chain groups having a unit selected from structures represented by formulas (I): -S-S-(CH)-COOH (wherein n is 1 or 2), (II): -S-S-CH(CH)-COOH and (III): -S-S-CH(COOH)-CH-COOH, and salts of these structures and a silicone-mixed hair treating agent (b).

Description

  The present invention relates to a multi-component hair treatment agent comprising a hair treatment agent in which a predetermined peptide having a carboxymethyl disulfide group or the like is blended.

  The hair is damaged by physical or chemical treatments such as brushing on the hair, hand dryer, thermal iron, hair color, permanent wave, etc., resulting in deterioration of the feel of the hair, loss of gloss, reduction of elasticity. For the purpose of repairing such hair, it is known that protein derivatives are incorporated into various hair treatment agents.

  Patent Document 1 discloses a kind of protein derivative. The protein derivative reduces a disulfide bond of a protein insoluble in water to a mercapto group (-SH), and a part or all of the reduced mercapto group is reduced. This is converted to a carboxymethyl disulfide group. And patent document 2 discloses the hair treatment agent which mix | blended the modified peptide which has a carboxymethyl disulfide group etc., and is the hair treatment agent of the said modified peptide combination to the hair processed with the agent which mix | blended the cationic compound. Disclose the application.

JP 07-126296 A JP 2010-155823 A

  By the way, silicones such as dimethyl silicone and amino-modified silicone are general-purpose components blended in hair treatment agents and are known as hair conditioning components. In order to produce an effect as a conditioning component, silicone must be attached to the hair and it is desired that the attachment be efficient.

  In view of the above circumstances, an object of the present invention is to provide a multi-component hair treatment agent that efficiently attaches silicone to hair.

  As a result of intensive studies by the inventors, if the hair is treated with a hair treatment agent containing a predetermined modified peptide and then treated with a hair treatment agent containing silicone, the silicone adheres to the hair. As a result, the present invention has been completed.

That is, the present invention is a multi-component hair treatment agent comprising a hair treatment agent (a) and a hair treatment agent (b) used after use of the hair treatment agent (a), wherein the hair treatment agent (a ) Is a combination of a modified peptide comprising one or more side chain groups having units selected from the structures represented by the following formulas (I) to (III) and salts of these structures: The hair treatment agent (b) is characterized in that it contains silicone.
_{-S-S- (CH 2) n} -COOH (I)
(In the formula (I), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (II)
_{-S-S-CH (COOH)} -CH 2 -COOH (III)

  Here, the “modified peptide” in the present invention includes one or more side chain groups having units selected from the structures represented by the above formulas (I) to (III) and salts of these structures. A peptide is a peptide in which two or more amino acids are linked by peptide bonds, and a protein such as a keratin protein also corresponds to a peptide.

  The silicone blended in the hair treatment agent (b) of the present invention is one or more selected from, for example, amino-modified silicone and dimethyl silicone.

  According to the multi-component hair treatment agent of the present invention, before using the hair treatment agent (b) containing silicone, the hair using the hair treatment agent (a) containing a predetermined modified peptide is used. As a result of the treatment, the adhesion of silicone to the hair becomes efficient.

It is a flowchart which shows the example of the manufacturing method of the modified | denatured peptide in this invention.

  Based on the multi-component hair treatment agent of this embodiment provided with a hair treatment agent (a) and a hair treatment agent (b), this invention is demonstrated below.

(Hair treatment agent (a))
A modified peptide is blended in the hair treatment agent (a) in the multi-component hair treatment agent according to this embodiment.

  The modified peptide blended in the hair treatment agent (a) includes a main chain formed by peptide bonds of a plurality of amino acids and a side chain group bonded to the main chain.

  The main chain of the modified peptide is not particularly limited. Examples of this main chain include the same main chain of peptides having cysteine as one of the constituent amino acids. Examples of peptides having cysteine as one of the constituent amino acids include keratin and casein. Keratin is known to have a high cysteine ratio among peptides derived from natural products, and is a raw material from which the modified peptide can be efficiently obtained. From this viewpoint, the main chain of the modified peptide is preferably the same as the main chain of keratin.

The modified peptide has one or more side chain groups having units selected from the structures represented by the following formulas (I) to (III) and salts of these structures.
_{-S-S- (CH 2) n} -COOH (I)
(In the formula (I), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (II)
_{-S-S-CH (COOH)} -CH 2 -COOH (III)

The salt having the structure represented by the above (I) to (III) is an ionic conjugate of a carboxylate anion and a cation. Examples of the unit serving as the cation include ammonium such as NH ₄ and metal atoms such as Na and K.

  The smaller the denatured peptide molecule, the easier it is to dissolve in the hair treatment agent (a), and the smaller the effect on the solubility when the pH of the treatment agent (a) is lowered. Therefore, the molecular weight of the modified peptide from the viewpoint of solubility of the modified peptide in water is preferably 70,000 or less, preferably 50,000 or less, more preferably 10,000 or less, and even more preferably 7,000 or less. Although the minimum of the molecular weight is not specifically limited, For example, it is 1000. Here, regarding the molecular weight of the modified peptide, the molecular weight calculated from the relative distance between the band of the modified peptide and the band of the molecular weight marker by Sodium Dodecyl Sulfate-polyacrylamide gel electrophoresis (SDS-PAGE method) is the molecular weight of the modified peptide. Adopted by assuming that.

  The lower limit of the amount of the modified peptide in the hair treatment agent (a) is, for example, 0.001% by mass or more, preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. On the other hand, the upper limit of the modified peptide blending amount is preferably 3% by mass or less, preferably 2% by mass or less, and more preferably 1% by mass or less from the viewpoint of suppressing an increase in cost due to a large amount of formulation. As described above, the smaller the molecular weight of the modified peptide, the easier it is to dissolve in the hair treatment agent (a). However, the blending amount of the modified peptide in the hair treatment agent (a) depends on the molecular weight of the modified peptide. To set as appropriate.

  Next, as an example of a method for producing a modified peptide, a method for producing a modified peptide using keratin as a raw material will be described. As shown in FIG. 1, the modified peptide production method includes a reduction step (STP1), an oxidizing agent mixing step (STP2), a solid-liquid separation step (STP3), and a recovery step L (STP4). In the method including all the steps shown in FIG. 1, denatured peptides (denatured peptides dissolved in the liquid part L shown in FIG. 1 and denatured peptides contained in the solid part S) are generated in the oxidizing agent mixing step (STP2). Therefore, the modified peptide can be produced without providing the solid-liquid separation step (STP3) and the recovery step L (STP4).

Reduction process (STP1)
Examples of keratin as a raw material include wool (merino wool, Lincoln wool, etc.), human hair, animal hair, feathers, nails and the like containing this as a constituent protein. Among them, it is preferable to use wool as a raw material in order to obtain a modified peptide inexpensively and stably. About raw materials, such as this wool, it is good to process beforehand, combining sterilization, degreasing, washing, cutting, crushing, and drying suitably.

  The reduction step (STP1) is a step of mixing the reducing agent, keratin, and water. In this reduction step (STP1), the disulfide group (—S—S—) of keratin is reduced to a mercapto group (—SH HS—).

  The reducing agent used in the reduction step (STP1) is one or two selected from thioglycolic acid, thioglycolate, mercaptopropionic acid, mercaptopropionic acid, thiolactic acid, thiolactate, thiomalic acid, and thiomalate. More than a seed. The combination of reducing agents when two or more reducing agents are used may be any combination, for example, a combination of thioglycolic acid and one thioglycolate, a combination of two thioglycolates, mercaptopropionic acid And a combination of one mercaptopropionate, a combination of two mercaptopropionates, a combination of thiolactic acid and one thiolactate, a combination of two thiolactates, a combination of thiomalic acid and one thiomalate, thioapple Combination of two acid salts, combination of one thioglycolate and one mercaptopropionate, combination of one thioglycolate and one thiolactate, combination of one thioglycolate and one thiomalate, mercaptopropion A combination of a single salt and a thiolactate, a single mercaptopropionate and a thiomalate Allowed, thiolactic acid salt type and thiomalate kind, and a combination of thioglycolate kind and thiosulfate lactate species as thiomalate kind.

  Examples of the thioglycolate include sodium thioglycolate, potassium thioglycolate, lithium thioglycolate, and ammonium thioglycolate. Examples of mercaptopropionate include sodium mercaptopropionate, potassium mercaptopropionate, lithium mercaptopropionate, and ammonium mercaptopropionate. Examples of the thiolactate include sodium thiolactate, potassium thiolactate, lithium thiolactate, and ammonium thiolactate. Examples of the thiomalate include sodium thiomalate, potassium thiomalate, lithium thiomalate, and ammonium thiomalate.

  The amount of the predetermined reducing agent used is preferably 0.005 mol or more and 0.02 mol or less based on 1 g of raw materials such as wool. In addition, the amount of the reducing agent used is 0.1 mol based on the volume of the liquid to be treated (including keratin or a keratin-derived treatment product and a reaction system in each step; the same shall apply hereinafter). / L or more and 0.4 mol / L or less.

  The amount of water in the reduction step (STP1) is not particularly limited, but may be, for example, 20 parts by volume or more and 200 parts by volume or less with respect to 1 part by mass of raw materials such as wool.

  In the reduction step (STP1), one or more alkaline compounds may be mixed with the liquid to be treated. An alkaline compound is a compound that can be made alkaline by adding it to water. Examples of the alkaline compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like.

  The mixing amount of the alkaline compound is not particularly limited, but is an amount for adjusting the pH of the liquid to be treated in the reduction step (STP1) to the following range. As a minimum of pH in a reduction process (STP1), 9 is preferred and 10 is more preferred. On the other hand, the upper limit of the pH in the reduction step (STP1) is preferably 13, and more preferably 12. By setting the pH in the reduction step (STP1) to the above lower limit or higher, keratin can be reduced efficiently. Further, by making the pH below the above upper limit, the cleavage of the keratin main chain can be suppressed (for the purpose of promoting the cleavage of the keratin main chain, the pH of the liquid to be treated should be adjusted to exceed 13. Just do it.)

  Although the temperature conditions of a reduction process (STP1) are not specifically limited, 35 degreeC or more and 60 degrees C or less are good, and 40 degreeC or more and 50 degrees C or less are preferable. When the temperature condition is less than 35 ° C., the reduction reaction rate for converting the disulfide group into a mercapto group is lowered, and keratin may not be sufficiently reduced. On the other hand, when it exceeds 60 ° C., the keratin main chain tends to be cleaved. Moreover, the time of the reduction process (STP1) becomes longer as the set temperature is lower, and becomes shorter as the set temperature is higher.

Oxidant mixing step (STP2)
The oxidizing agent mixing step (STP2) is a step of mixing the processed product (keratin-derived product) that has undergone the reducing step (STP1) and an oxidizing agent to generate a modified peptide. The mixing of the oxidizing agent is performed to promote an oxidation reaction that modifies the mercapto group of the processed product. Usually, an oxidizing agent is mixed with the liquid to be processed containing the processed product that has undergone the reduction step (STP1).

  Examples of the oxidizing agent include sodium bromate, potassium bromate, sodium perborate, potassium perborate, hydrogen peroxide, and the like. The oxidizing agent to be used is 1 type, or 2 or more types.

  The amount of the oxidizing agent used in the oxidizing agent mixing step (STP2) is not particularly limited, but may be 0.001 mol or more and 0.02 mol or less based on 1 g of raw materials such as wool, and the oxidizing agent mixing step ( STP2) is preferably 0.02 mol / L or more and 1 mol / L or less based on the volume of the liquid to be treated.

  When mixing the oxidant with the liquid to be treated, an oxidant solution of about 1 mol / L or more and 5 mol / L or less is used, for example, in order to avoid local concentration of the oxidant in the liquid to be treated. It is good to mix gradually regardless of continuous and intermittent over 6 minutes to 6 hours.

  It is preferable that the amount of oxidizing agent (A) mixed with the liquid to be treated having a pH of 9 or more is larger than the amount of oxidizing agent (B) mixed with the liquid to be processed having a pH of 7 or more and less than 9. This shortens the modified peptide production time. The ratio of the oxidizing agent amount (B) to the total of the oxidizing agent amounts (A) and (B) is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and particularly preferably 0 mol%.

  The pH of the liquid to be treated in the oxidizing agent mixing step (STP2) is adjusted according to the progress of this step. The pH at the start of mixing of the oxidizing agent is preferably 9 or more, and more preferably 10 or more. The pH is preferably 13 or less, preferably 12 or less, and more preferably 11 or less. When the pH is 9 or more, the generation efficiency of the modified peptide is good, and when the pH is 13 or less, the cleavage of the main chain of the keratin-derived processed product can be suppressed. The pH at the end of the oxidizing agent mixing step (STP2) is not particularly limited, but may be about 7.

  In the oxidant mixing step (STP2), the time of pH 9 or more is preferably longer than the time of pH 7 or more and less than 9, more preferably the time of pH 9 or more and 12 or less is longer than the time of pH 7 or more and less than 9, and pH 10 or more and 11 More preferably, the following time is longer than the time of pH 7 or more and less than 9. When such a procedure is adopted, the generation efficiency of the modified peptide is increased.

  As the acid for adjusting the pH of the liquid to be treated, one or more selected from organic acids and inorganic acids may be used. Examples of the organic acid include citric acid, lactic acid, succinic acid, and acetic acid, and examples of the inorganic acid include hydrochloric acid and phosphoric acid. The mixing amount of the acid may be appropriately set while monitoring the pH of the liquid to be treated. When mixing the acid with the liquid to be treated, if the pH is locally lowered in the liquid to be treated, the mercapto groups of the treated product may become disulfide groups, so the acid is gradually mixed with the liquid to be treated. It is preferable.

  The temperature condition in the oxidizing agent mixing step (STP2) is preferably 10 ° C. or more and 60 ° C. or less, and preferably 40 ° C. or less. By controlling the temperature within the above range, the production of by-products such as cystine monoxide can be suppressed.

The reaction formula in the oxidizing agent mixing step (STP2) is the thioglycolic acid or salt thereof, mercaptopropionic acid or salt thereof, thiolactic acid or salt thereof, or thiomalic acid or salt thereof as the reducing agent in the reduction step (STP1). When used, the reducing agents are listed in the order listed below.

Solid-liquid separation process (STP3)
The solid-liquid separation step (STP3) is a step of separating the liquid to be processed after the oxidizing agent mixing step (STP2) into the liquid part L and the solid part S. In the solid-liquid separation step (STP3), known solid-liquid separation means such as filtration, centrifugation, squeezing separation, sedimentation separation, and flotation separation can be employed, and desalting by ion exchange, electrodialysis, etc., if necessary. Etc.

Recovery process L (STP4)
The recovery step L (STP4) is a step of recovering the modified peptide L dissolved in the liquid part L obtained in the solid-liquid separation step (STP3) as a solid product. As a method for recovering the solid modified peptide L in the recovery step L (STP4), (1) recovery by freeze-drying the liquid part L, (2) recovery by spray-drying the liquid part L, (3) Examples thereof include recovery of a denatured peptide L precipitate generated by adding an acid such as hydrochloric acid to the liquid part L and lowering the pH of the liquid part L from about 2.5 to about 4.0. About the collect | recovered solid modified | denatured peptide L, washing | cleaning with water or acidic aqueous solution, drying, etc. are performed as needed.

  As described above, by finishing the treatment in the oxidizing agent mixing step (STP2), a denatured peptide dissolved in the solution to be treated and a denatured peptide not dissolved in the same solution are obtained. If these modified peptides are reduced in molecular weight, the solubility in water increases. As modes for reducing the molecular weight, (1) a mode in which the solid part S obtained in the solid-liquid separation step (STP3) is hydrolyzed, and (2) a solution in the liquid part L obtained in the solid-liquid separation step (STP3). The modified peptide L is hydrolyzed, (3) the modified peptide L recovered in the recovery step L is hydrolyzed, and (4) the modified peptide L and the solid part S are hydrolyzed together. Can be mentioned. In addition, as a method for reducing the molecular weight by hydrolysis, before the reduction step (STP1), simultaneously with the reduction step (STP1), between the reduction step (STP1) and the oxidizing agent mixing step (STP2), One example is hydrolysis for lowering the molecular weight.

  Examples of the method for hydrolyzing the modified peptide include (1) enzyme hydrolysis, (2) acid hydrolysis, and (3) alkali hydrolysis, which are known as peptide hydrolysis.

Hydrolysis by enzymes Examples of enzymes for hydrolysis include pepsin, protease A, protease B and other acidic proteolytic enzymes; papain, promelain, thermolysin, pronase, trypsin, chymotrypsin and other neutral or alkaline proteolytic enzymes Etc.

  The pH at the time of hydrolysis by the enzyme is preferably adjusted to 1 or more and 3 or less in the case of an acidic proteolytic enzyme, and is adjusted to 5 or more and 11 or less in the case of a neutral or alkaline proteolytic enzyme. Enzyme activity improves by making this pH into the said range.

  The reaction temperature at the time of hydrolysis with the enzyme is appropriately set within a range of 30 ° C. to 60 ° C., and the reaction time is 10 minutes to 24 hours. In order to stop the hydrolysis by the enzyme, it is preferable to deactivate the enzyme at a temperature of 70 ° C. or higher.

Hydrolysis with acid Examples of acids used for hydrolysis include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrobromic acid, and organic acids such as formic acid and oxalic acid. Is appropriately selected. The hydrolysis conditions are, for example, pH 4 or less, reaction temperature 40 ° C. or more and 100 ° C. or less, and reaction time 2 hours or more and 24 hours or less.

Hydrolysis with alkali Examples of the alkali used for hydrolysis include sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, sodium borate and the like. Can be mentioned. The hydrolysis conditions are, for example, pH 8.0 or more, reaction temperature 50 ° C. or more and 100 ° C. or less, and reaction time 20 minutes or more and 24 hours or less.

  In order to recover the hydrolyzed modified peptide, the same method as in the recovery step L (STP4) can be employed. However, in the recovery method in which an acid is added so that the pH is about 2.5 to 4.0, the denatured peptide is reduced in molecular weight by hydrolysis, so that it may be difficult or impossible to recover.

  The hair treatment agent (a) is preferably one in which the modified peptide is blended in water (the blending concentration of water in the hair treatment agent (a) is, for example, 60% by mass or more).

  Moreover, raw materials other than the modified peptide optionally blended in the hair treatment agent (a) are appropriately selected from known hair treatment agent raw materials according to the use of the treatment agent (a). The known hair treatment materials include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, higher alcohols, lower alcohols, polyhydric alcohols, sugars, fats and oils, ester oils, fatty acids, carbonized There are hydrogen, wax, synthetic polymer compounds, semi-synthetic polymer compounds, and natural polymer compounds. Other known hair treatment materials include silicone, protein, amino acid, animal and plant extracts, microorganism-derived materials, inorganic compounds, fragrances, preservatives, sequestering agents, and the like.

  Examples of the anionic surfactant include N-acyl amino acid salts, alkyl ether carboxylates, fatty acid amide ether carboxylates, fatty acid amide ether carboxylic acids, acyl lactates, alkane sulfonates, α-olefin sulfonates, alkyls. Examples include sulfosuccinate, alkylsulfoacetate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, alkyl sulfate, alkyl ether sulfate, fatty acid monoglyceride sulfate, alkyl phosphate, and polyoxyethylene alkyl ether phosphate. . One or two or more types of anionic surfactants may be added to the hair treatment agent (a), and the concentration of the anionic surfactant is, for example, from 0.1% by mass to 20% by mass.

  Examples of cationic surfactants include alkylamine salts, fatty acid amide amine salts, ester-containing tertiary amine salts, arkol-type tertiary amine salts, long-chain alkyltrimethylammonium salts, di-long-chain alkyldimethylammonium salts, and tri-long-chain alkylmonomethyls. Examples thereof include ammonium salts, benzalkonium-type quaternary ammonium salts, and monoalkyl ether-type quaternary ammonium salts. One or two or more cationic surfactants may be added to the hair treatment agent (a), and the concentration of the cationic surfactant is, for example, 0.1% by mass or more and 20% by mass or less.

  Examples of amphoteric surfactants include alkyl glycine salts, carboxymethyl glycine salts, N-acylaminoethyl-N-2-hydroxyethyl glycine salts, alkyl polyamino polycarboxy glycine salts, alkyl amino propionates, and alkyl imino dipropionic acids. Salt, N-acylaminoethyl-N-2-hydroxyethylpropionate, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, alkyldihydroxyethylaminoacetic acid betaine, N-alkyl-N, N-dimethylammonium- N-propylsulfonate, N-alkyl-N, N-dimethylammonium-N- (2-hydroxypropyl) sulfonate, N-fatty acid amidopropyl-N, N-dimethylammonium-N- (2-hydride) Kishipuropiru) sulfonate. One or two or more amphoteric surfactants may be blended in the hair treatment agent (a), and the blending concentration of the amphoteric surfactant is, for example, from 0.1% by mass to 10% by mass.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol tetra fatty acid ester, glycerin fatty acid ester, sorbitan Examples include fatty acid esters, polyglycerin fatty acid esters, and sucrose fatty acid esters. One or two or more kinds of nonionic surfactants may be added to the hair treatment agent (a), and the concentration of the nonionic surfactant is, for example, from 0.1% by mass to 20% by mass.

  Examples of the higher alcohol include cetanol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, and myristyl alcohol. One or two or more higher alcohols may be blended in the hair treatment agent (a), and the blending concentration of the higher alcohol is, for example, 3% by mass or more and 15% by mass or less.

  Examples of the lower alcohol include ethanol and isopropyl alcohol. One or two or more lower alcohols may be added to the hair treatment agent (a). The concentration of the lower alcohol is, for example, 0.5% by mass or more and 3% by mass or less.

  Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, and butylene glycol. One or two or more polyhydric alcohols may be blended in the hair treatment agent (a), and the blending concentration of the polyhydric alcohol is, for example, 1% by mass or more and 50% by mass or less.

  Examples of the saccharide include sorbitol, mannitol, glucose, fructose, xylitol, lactose, maltose, maltitol, and trehalose. One or two or more saccharides may be added to the hair treatment agent (a), and the concentration of the saccharide is, for example, from 0.1% by mass to 10% by mass.

  Examples of the fat include almond oil, avocado oil, olive oil, shea fat oil, evening primrose oil, camellia oil, peanut oil, and rosehip oil. One or two or more types of fats and oils may be blended in the hair treatment agent (a). The blending concentration of the fats and oils is, for example, 0.1% by mass or more and 10% by mass or less.

  Examples of ester oils include ethyl oleate, isopropyl myristate, isopropyl palmitate, butyl stearate, cetyl palmitate, myristyl myristate, octyldodecyl myristate, isopropyl isostearate, ethyl isostearate, cetyl 2-ethylhexanoate Hexyl isostearate, ethylene glycol di-2-ethylhexanoate, ethylene glycol dioleate, di (capryl / capric acid) propylene glycol, propylene glycol dioleate, trimethylolpropane triisostearate, pentaerythritol tetra2-ethylhexanoate Isocetyl isostearate, 2-octyldodecyl dimethyloctanoate, myristyl lactate, trioctyldodecyl citrate, phosphorus Diisostearyl, succinate di-2-ethylhexyl, diisobutyl adipate, stearic acid cholesteryl. One or more ester oils may be blended in the hair treatment agent (a), and the blending concentration of the ester oil is, for example, 0.1% by mass or more and 10% by mass or less.

  Examples of the fatty acid include isostearic acid, oleic acid, capric acid, stearic acid, palmitic acid, hydroxystearic acid, behenic acid, myristic acid, lauric acid, lanolin fatty acid, and linoleic acid. One or two or more fatty acids may be blended in the hair treatment agent (a), and the blending concentration of the fatty acid is, for example, 0.1% by mass or more and 10% by mass or less.

  Examples of the hydrocarbon include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, petrolatum, and microcrystalline wax. One or two or more hydrocarbons may be blended in the hair treatment agent (a), and the blending concentration of the hydrocarbon is, for example, 0.1% by mass or more and 20% by mass or less.

  Examples of the wax include beeswax, mole, candelilla wax, and carnauba wax. One or more waxes may be added to the hair treatment agent (a). The wax concentration is, for example, 0.1% by mass or more and 20% by mass or less.

  Examples of the synthetic polymer compound include carboxyvinyl polymer, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, methacryloylethylbetaine / methacrylic acid ester copolymer. Examples of the semi-synthetic polymer compound include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, and soluble starch. Examples of natural polymers include sodium alginate, guar gum, glucan, cellulose, and sodium hyaluronate. One or two or more synthetic polymer compounds may be blended in the hair treatment agent (a). The total blending concentration of the synthetic polymer compound, semi-synthetic polymer compound and natural polymer compound is, for example, 0.1% by mass. The content is 15% by mass or less.

  The pH of the hair treatment agent (a) is not particularly limited, but is preferably 5.0 or more and 11.0 or less, preferably 6.0 or more and 10.0 or less, more preferably 6.5 or more and 9.0 or less, More preferably, it is 5 or more and 8.0 or less. If the pH is less than 5.0, the modified peptide tends to precipitate, and if the pH is 11.0 or more, hydrolysis of the modified peptide may progress. In order to adjust pH, an organic acid, an inorganic acid, an alkali metal hydroxide, or the like may be used.

  The dosage form at the time of using the hair treatment agent (a) is not particularly limited, and for example, liquid, emulsion, lotion, cream, wax, gel, solid, foam (foam), or mist Can be mentioned.

(Hair treatment agent (b))
In the hair treatment agent (b) in the multi-component hair treatment agent according to this embodiment, one or more selected from known silicones are blended.

  Examples of the silicone compounded in the hair treatment agent (b) include amino-modified silicones such as aminoethylaminopropylsiloxane / dimethylsiloxane copolymer and aminoethylaminopropylmethylsiloxane / dimethylsiloxane copolymer; silanol-modified silicones; Alcohol-modified silicones such as dimethylsiloxane / methylcetyloxysiloxane copolymer, dimethylsiloxane / methylstearoxysiloxane copolymer; alkyl-modified silicone; aralkyl-modified silicone; polyoxyethylene / methylpolysiloxane copolymer, polyoxypropylene / Polyether-modified silicone such as methylpolysiloxane copolymer; dimethylpolysiloxane having an average degree of polymerization of 3 or more and less than 650; high polymerization methyl having an average degree of polymerization of 650 or more Dimethylsilicone polysiloxane; octamethylcyclotetrasiloxane, cyclic dimethyl silicones such as decamethylcyclopentasiloxane; methylhydrogenpolysiloxane; and the like. One or two or more types of silicone may be added to the hair treatment agent (b), and the concentration of the silicone is, for example, 0.1% by mass or more and 20% by mass or less.

The higher the kinematic viscosity of the silicone, the easier the adhesion to the hair lasts. Therefore, as the silicone for the maintenance, the kinematic viscosity at 25 ° C. confirmed by the first method of the cosmetic raw material standard general test method is 10 mm ^2. / S or more is good, and 500 mm ² / s or more is preferable.

  The amino-modified silicone and dimethyl silicone are highly versatile in the hair treatment agent (b) as well as in the known hair treatment agent. When the amino-modified silicone is blended in the hair treatment agent (b), the blending concentration of the amino-modified silicone in the treatment agent (b) is not particularly limited, but is, for example, 7% by mass or less, and usually 0.1% by mass or more. 5% by mass or less. Moreover, when mix | blending dimethyl silicone with a hair treatment agent (b), the compounding density | concentration of the dimethyl silicone in the said treatment agent (b) is although it does not specifically limit, For example, it is 7 mass% or less, and is 0.1 mass% or more normally. 3% by mass or less.

  The hair treatment agent (b) may be either water-based or non-aqueous, but is typically a mixture of silicone in water (the concentration of water in the hair treatment agent (b) is, for example, 60 % By mass or more.)

  Moreover, raw materials other than silicone optionally blended in the hair treatment agent (b) are appropriately selected from known hair treatment agent raw materials according to the use of the treatment agent (b). The known hair treatment materials include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, higher alcohols, lower alcohols, polyhydric alcohols, sugars, fats and oils, ester oils, fatty acids, carbonized Examples include hydrogen, waxes, synthetic polymer compounds, semi-synthetic polymer compounds, natural polymer compounds, proteins, amino acids, animal and plant derived substances, microorganism derived substances, inorganic compounds, fragrances, preservatives, and sequestering agents.

  Among the optional raw materials blended in the hair treatment agent (b), quaternary ammonium salts and higher alcohols have high versatility as well as known hair treatment agents. The lower alcohol is versatile when it is desired to increase the solubility of the surfactant in water.

  When a quaternary ammonium salt is added to the hair treatment agent (b), examples of the quaternary ammonium salt include lauryltrimethylammonium chloride, cetyltrimethylammonium bromide, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, and behenyltrimethylammonium chloride. Mono-long chain alkyltrimethylammonium salts such as behenyltrimethylammonium methosulfate; dilong-chain alkyldimethylammonium salts such as dicetyldimethylammonium chloride, distearyldimethylammonium chloride, dicocoyldimethylammonium chloride; stearoxypropyltrimethylammonium chloride, etc. Long-chain alkoxyalkyltrimethylammonium salts thereof. One or two or more quaternary ammonium salts may be blended in the hair treatment agent (b), and the blending concentration of the quaternary ammonium salt is appropriately set. It is as follows.

  When a higher alcohol is blended in the hair treatment agent (b), examples of the higher alcohol include cetanol, isocetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, and myristyl alcohol. One or two or more higher alcohols may be blended in the hair treatment agent (b), and the blending concentration of the higher alcohol is appropriately set, and is, for example, 2% by mass or more and 10% by mass or less.

  When a lower alcohol is blended in the hair treatment agent (b), examples of the lower alcohol include ethanol and isopropyl alcohol. One or two or more lower alcohols may be blended in the hair treatment agent (b). The blending concentration of the lower alcohol is appropriately set, and is, for example, 0.5% by mass or more and 3% by mass or less.

  The dosage form at the time of using the hair treatment agent (b) is not particularly limited, and for example, liquid, emulsion, lotion, cream, wax, gel, solid, foam (foam), or mist Can be mentioned.

(how to use)
The multi-component hair treatment agent of this embodiment applies the hair treatment agent (b) to the hair after the hair treatment agent (a) is applied to the hair. After the use of the hair treatment agent (a) and before the use of the hair treatment agent (b), the hair may be heated, washed with water, dried, or a combination thereof.

  In addition, if the hair treatment agent (b) is used after the hair treatment agent (a) is used on the hair, before using the hair treatment agent (a), after using the hair treatment agent (a) A known hair treatment agent may be applied to the hair before and after using the hair treatment agent (b) and after using the hair treatment agent (b).

  As described above, the multi-component hair treatment agent of the present embodiment uses the hair treatment agent (b) after the use of the hair treatment agent (a). By using this multi-component hair treatment agent, silicone adheres efficiently to the hair. The mechanism for the efficient adhesion of silicone is considered as follows.

First, when the hair treatment agent (a) is used, the modified peptide of the treatment agent (a) adheres to the hair. The attachment of the modified peptide to the hair is considered to involve a reaction between the mercapto group of the hair and the modified peptide. The mechanism of the reaction is as follows.
K _H -SH + K-S-S-R
→ K _H -S-S K + HS-R
[In the above reaction formula, K _H represents a keratin residue of hair, K—S—S—R represents a denatured peptide, R represents —CH ₂ —COOH, —CH ₂ —COOH salt, — (CH ₂ ) ₂ —COOH, — (CH ₂ ) ₂ —COOH salt, —CH (CH ₃ ) —COOH, —CH (CH ₃ ) —COOH salt, —CH (COOH) —CH ₂ —COOH, —CH ( COOH) —CH ₂ —COOH salt and any of these anions. ]

  Next, when the hair treatment agent (b) is used, the silicone of the treatment agent (b) adheres to the hair. Since the modified peptide adheres to the hair after using the hair treatment agent (a), and this modified peptide is thought to increase the physical adhesion action such as entanglement with silicone, the silicone adheres efficiently to the hair. It becomes like this.

(Use)
The use of the multi-component hair treatment agent according to the present embodiment is not particularly limited as long as the usage method is followed. Examples of the use of the multi-component hair treatment agent according to this embodiment are as follows: a hair treatment agent (a) is used as a shampoo, and a hair treatment agent (b) is washed away; a hair treatment agent (a) and a hair treatment Use as a treatment for washing off the agent (b); Use as a treatment for washing out the hair treatment agent (a) and use as a treatment without washing out the hair treatment agent (b); and a hair treatment agent (a) and a hair treatment agent (b) Use as a treatment that does not wash away; Use as a treatment to wash away the hair treatment agent (a) and use the hair treatment agent (b) as a styling agent; Use as a hair treatment agent (a) and a hair treatment agent (b) as a styling agent The use of the hair treatment agent (a) and the hair treatment agent (b) as a pretreatment agent for coloring; the hair treatment agent (a) as a pretreatment agent for coloring; Use of agent (b) as coloring agent; Use of hair treatment agent (a) as coloring agent and use of hair treatment agent (b) as post-treatment agent for coloring; Hair treatment agent (a) and hair treatment Use of agent (b) as a post-treatment agent for coloring; Use of hair treatment agent (a) and hair treatment agent (b) as a pre-treatment agent for permanents; Hair treatment agent (a) as a pre-treatment agent for permanents And uses the hair treatment agent (b) as a permanent agent; uses the hair treatment agent (a) as a permanent agent, and uses the hair treatment agent (b) as a permanent post treatment agent; hair treatment agent (a) and hair Use of the treating agent (b) as a permanent post-treating agent.

  In the application example of the multi-component hair treatment agent according to this embodiment, “styling” is to temporarily hold a hairstyle. “Perm” is to change the hair shape into a wave shape, a straight hair shape or the like using a chemical reaction such as a reduction reaction or an oxidation reaction. “Coloring” is to change the hair color by coloring the hair with a dye, decolorizing the hair pigment, or the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist of the present invention.

(Modified peptide)
The modified peptide used in the examples was produced as follows.

Reduction step Merino wool, washed with a neutral detergent and dried, was cut to about 5 mm. 5.0 parts by weight of this wool, 15.4 parts by weight of 30% by weight sodium thioglycolate aqueous solution and 8.5 parts by weight of 6 mol / L sodium hydroxide aqueous solution were mixed, and water was further mixed to give a total amount of 150 parts by weight, pH 11 A liquid to be treated was prepared. This liquid to be treated was stirred at 45 ° C. for 1 hour. Subsequently, water was further mixed to make the total amount 200 parts by mass, left under conditions of 45 ° C. for 2 hours, and then naturally cooled until the liquid temperature reached room temperature.

Oxidant mixing step While stirring the liquid to be treated after the reduction step, 178 parts by mass of an aqueous solution containing 15.26 parts by mass of 35% by mass hydrogen peroxide was mixed with the liquid while stirring over about 30 minutes. (The pH of the liquid to be treated increased with the mixing of the hydrogen peroxide solution, but the increase was adjusted to a range of pH 10 to 11 by mixing an aqueous solution of about 20% by mass acetic acid.) Then, about 20 mass% acetic acid aqueous solution was mixed gradually, and it adjusted so that the pH of a to-be-processed liquid might become 11-7 gradually. Thus, a denatured peptide solution was obtained.

Solid-liquid separation step and recovery step Insoluble matter in the solution was removed by filtering the denatured peptide solution. Thereafter, 160 parts by mass of an aqueous solution containing 97.2 parts by mass of a 36% by mass hydrochloric acid aqueous solution was added to the recovered liquid part (filtrate) to adjust the pH of the denatured peptide solution to 7 to 3.8, thereby denatured peptide. Precipitation occurred. This precipitate was recovered and washed with water to obtain a solid modified peptide.

  An aqueous solution in which the solid modified peptide obtained in the recovery step was 1% by mass and the pH was 8 with 2-amino-2-methyl-1-propanol was heated at 85 ° C. for 5 hours. The heated solution was filtered to obtain a modified peptide aqueous solution used in the examples.

(Example)
Hair treatment agent (a)
The 1 mass% modified peptide aqueous solution obtained above was used as the hair treatment agent (a) in the multi-component hair treatment agent of the examples.

Hair treatment agent (b)
As a hair treatment agent (b) in the multi-component hair treatment agent of Example, a creamy O / W emulsion having the following blending concentrations was produced.
1% by mass of aminoethylaminopropylsiloxane / dimethylsiloxane copolymer
Highly polymerized methylpolysiloxane (1) 2% by mass
Decamethylcyclopentasiloxane 11% by mass
Cetyltrimethylammonium salt 2% by mass
Stearyl trimethyl ammonium salt 0.1% by mass
Dicocoyldimethylammonium salt 0.1% by mass
Polyoxyethylene cetyl ether 0.01% by mass
Cetanol 5% by mass
1% by mass of ethanol
Phenoxyethanol 0.3% by mass
Lactic acid 0.01% by mass
Fragrance 0.3% by mass

(Comparative example)
The hair treatment agent (b) in the examples was used as the hair treatment agent of the comparative example (the hair treatment agent (a) in the examples was not used as a constituent of the hair treatment agent of the comparative example).

(Hair treatment)
A hair bundle containing about 3 g of black hair without coloring and perm history is washed with a commercially available shampoo containing an anionic surfactant, and the multi-component hair treatment agent of the embodiment is used for this hair bundle. The following processing was performed. The hair bundle was immersed in the hair treatment agent (a) of the example for 5 minutes and then washed with water. Next, the hair treatment agent (b) of the example was applied to the hair bundle from which water had been cut, and washed with water. The hair bundle was then dried with warm air. In the hair treatment using the hair treatment agent of the comparative example, the immersion in the hair treatment agent (a) and the subsequent water washing were omitted.

(Quantification of Si)
In order to confirm the difference in the amount of silicone adhering to the hair bundle subjected to the hair treatment, atomic absorption analysis was performed. The conditions and results in this analysis are as follows.

Analysis sample 6 ml of 61% nitric acid aqueous solution was added to about 0.2 g of hair in the hair bundle, and Analytik
The hair was dissolved using a microwave sample decomposition apparatus “TOPwave” manufactured by Jena (the decomposition conditions of the hair for the dissolution are as shown in Table 1 below). Water was added to the hair solution to make a total volume of 20 ml, which was further diluted 100 times with water. This was used as an analysis sample in atomic absorption analysis.

Analysis method
Using a furnace atomic absorption method continuous light source atomic absorption analyzer “contrAA700” manufactured by Analytik Jena, Si in the analysis sample was quantified by the standard addition method (the analysis conditions at this time are as shown in Table 2 below).

Analysis result The analysis result of Si quantification based on the hair treated in the example was 620 mg / kg. On the other hand, the analysis result of the comparative example was 540 mg / kg. Also from this result, it can be understood that the silicone adhesion to the hair was efficient by using the hair treatment agent (a) prior to the treatment with the hair treatment agent (b).

Claims (2)

A multi-agent hair treatment agent comprising a hair treatment agent (a) and a hair treatment agent (b) used after use of the hair treatment agent (a),
The hair treatment agent (a) contains a modified peptide comprising one or more side chain groups having units selected from the structures represented by the following formulas (I) to (III) and salts of these structures: It has been
The multi-treatment hair treatment agent, wherein the hair treatment agent (b) is a blend of silicone.
_{-S-S- (CH 2) n} -COOH (I)
(In the formula (I), n is 1 or 2.)
_{-S-S-CH (CH 3} ) -COOH (II)
_{-S-S-CH (COOH)} -CH 2 -COOH (III) The multi-component hair treatment agent according to claim 1, wherein the hair treatment agent (b) is one in which one or more selected from amino-modified silicone and dimethyl silicone are blended as the silicone.