JP5632150B2 - Hair treatment agent - Google Patents

Description

  The present invention relates to a hair treatment agent. Specifically, the present invention relates to a hair treatment agent used as a hair bleaching agent or an oxidative hair dye.

  In general, since a hair bleaching agent has an excellent bleaching effect, a two-component hair bleaching agent in which a first agent containing an alkaline agent and a second agent containing an oxidizing agent are mixed at the time of use becomes the mainstream. ing. Further, since the effect of the hair dye is continuous, a two-component oxidative hair dye in which a first agent containing an alkaline agent and an oxidative dye and a second agent containing an oxidizer are mixed at the time of use. Has become the mainstream.

  In the two-part hair bleaching agent, an alkaline agent and hydrogen peroxide act to generate oxygen during use, thereby decomposing melanin pigment in the hair and bleaching the hair. In the two-component oxidative hair dye, the generated oxygen oxidizes and decomposes the melanin pigment in the hair, and the hair is dyed by oxidative polymerization of the oxidative dye in the hair.

  In addition to the action of hydrogen peroxide, the alkaline agent in the first agent has an effect of improving the hair dyeing effect by swelling the cuticle on the hair surface and penetrating the dye into the hair.

  However, the keratin protein on the hair surface has problems that the cystine bond is oxidized to cysteic acid by hydrogen peroxide or is easily decomposed by an alkaline agent, so that the hair is damaged and split hairs and hairs are broken. doing.

  In order to solve such problems, it has been proposed to use a hair modifier using cationized hyaluronic acid as a hair color pretreatment liquid (see, for example, Patent Document 1). In addition, it has been reported that when such a cationized hyaluronic acid is blended with a hair treatment agent containing an oxidizing agent, it is possible to prevent the occurrence of a hair bundle feeling while ensuring the moisturizing effect of the hair (for example, Patent Documents). 2-3).

  Although cationized hyaluronic acid has an excellent hair-modifying effect, adding cationized hyaluronic acid to a hair treatment agent containing an oxidizer makes the hair after treatment easy to be stiff and the hair ends to a firm finish. There is a problem of being inferior.

WO08 / 133267 pamphlet (paragraph [0215]) JP 2008-266253 A JP 2008-266239 A (paragraph [0070])

  Therefore, as a result of intensive studies by the present inventors, when a cationized hyaluronic acid is used in combination with hydrocarbons and / or waxes in a hair treatment agent containing an oxidizing agent, the hair feels after treatment. It has been found that the hair ends have a hard finish feeling and are excellent in unity, and that the hair decolorization and dyeing properties are improved, and the present invention has been completed.

で表される繰り返しユニットを有するカチオン化ヒアルロン酸であることを特徴とする前記〔１〕に記載の毛髪処理剤、
〔３〕前記（Ａ）成分の分子量が、重量平均分子量で１０万〜３００万であることを特徴とする前記〔１〕又は〔２〕に記載の毛髪処理剤、
〔４〕前記（Ｂ）成分が、室温で固形の炭化水素類及び／又はロウ類であることを特徴とする前記〔１〕〜〔３〕のいずれかに記載の毛髪処理剤、
〔５〕更に、（Ｃ）両性高分子化合物を含有することを特徴とする前記〔１〕〜〔４〕の何れかに記載の毛髪処理剤、
〔６〕前記（Ｃ）成分が、ジメチルジアリルアンモニウムを構成単位として含む両性高分子化合物であることを特徴とする前記〔５〕に記載の毛髪処理剤、並びに
〔７〕更に、（Ｄ）高級アルコールを含有することを特徴とする前記〔１〕〜〔６〕の何れかに記載の毛髪処理剤
に関する。 That is, the present invention
[1] A hair treatment agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, wherein (A) a cationized hyaluronic acid and (B) a hydrocarbon and / or a wax A hair treatment agent comprising:
[2] The component (A) is represented by the general formula (1):

The hair treatment agent according to the above [1], which is a cationized hyaluronic acid having a repeating unit represented by:
[3] The hair treatment agent according to [1] or [2], wherein the molecular weight of the component (A) is 100,000 to 3 million in terms of weight average molecular weight,
[4] The hair treatment agent according to any one of [1] to [3], wherein the component (B) is a hydrocarbon and / or wax that is solid at room temperature,
[5] The hair treatment agent according to any one of [1] to [4], further comprising (C) an amphoteric polymer compound ,
[ 6] The hair treatment agent according to [5], wherein the component (C) is an amphoteric polymer compound containing dimethyldiallylammonium as a structural unit ;
[7] The hair treatment agent according to any one of [1] to [6], further comprising (D) a higher alcohol .

  The hair treatment agent of the present invention has the effect of suppressing the stiff feeling of the hair after the treatment, and suppressing the hair tip from becoming a hard finish, and being excellent in unity. In addition, when the hair treatment agent of the present invention is used as a hair bleaching agent, it has excellent hair decoloring properties, and when it is used as an oxidative hair coloring agent, the hair dyeing properties are excellent.

  The hair treatment agent of the present invention is a hair treatment agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, and as essential components (A) cationized hyaluronic acid, and (B ) Contains hydrocarbons and / or waxes.

  The cationized hyaluronic acid of component (A) is a hydroxyl group or carboxyl group of hyaluronic acid having a repeating unit of D-glucuronic acid and N-acetyl-D-glucosamine as represented by the following general formula (3). Hyaluronic acid cationized with a cationizing agent.

  The origin of the cationized hyaluronic acid is not particularly limited, and examples thereof include extracts from living tissues such as chicken crowns and cultures by microorganisms such as Streptococcus pyogenes.

  The molecular weight of hyaluronic acid is not particularly limited, and may be a molecular weight of about 100,000 to 3,000,000, hydrolyzed low molecular weight hyaluronic acid of less than about 1,000 to 100,000, and a molecular weight of about 1,000. Less than hyaluronic acid oligo may be used. Among these, from the viewpoint of suppressing the feeling of hair stiffness after the treatment, the hyaluronic acid after cationization preferably has a molecular weight of about 100,000 to 3,000,000, more preferably about 500,000 to 1,500,000. In addition, the average molecular weight in this invention shows a weight average molecular weight.

  The cationizing agent that cationizes hyaluronic acid may be a commonly used cationizing agent, and examples thereof include glycidyltrialkylammonium halides such as glycidyltrimethylammonium halide, glycidyltriethylammonium halide, and glycidyltripropylammonium halide. Moreover, Cl, Br, I, etc. are mentioned as the halogen atom of the halide. Of these, glycidyltrimethylammonium chloride is preferably used because of its good reactivity. In addition, a commercial item can be used for glycidyl trialkyl ammonium halide. For example, a brand name “SY-GTA80” (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) can be mentioned.

次式（５）で表される前記カチオン化剤とを、

通常、水、メタノール、エタノール、又は水とメタノール或いはエタノールの混合液などの溶液中、水酸化ナトリウム、水酸化カリウムなどのアルカリの存在下で、室温〜還流温度にて、０．５〜３日程度反応させることにより、ヒアルロン酸の水酸基又はカルボキシル基がカチオン化された、次式（６）の繰り返し単位を有するカチオン化ヒアルロン酸を得ることができる。

The cationization includes hyaluronic acid having a repeating unit of the following formula (4):

The cationizing agent represented by the following formula (5):

Usually, in a solution such as water, methanol, ethanol, or a mixture of water and methanol or ethanol, in the presence of an alkali such as sodium hydroxide or potassium hydroxide, at room temperature to reflux temperature, 0.5 to 3 days By carrying out the reaction to some extent, a cationized hyaluronic acid having a repeating unit of the following formula (6) in which the hydroxyl group or carboxyl group of hyaluronic acid is cationized can be obtained.

  In the formula (6), when the carboxyl group of hyaluronic acid is cationized, the cationizing agent is added in an amount of 1 to 5 mol with respect to 1 unit of hyaluronic acid of the formula (4) (converted to 1 mol for convenience). Is preferably reacted at a reaction temperature of about 40 to 60 ° C. for about 0.5 to 3 hours. When the hydroxyl group of hyaluronic acid is cationized, it is preferable to react 1 to 8 moles of cationizing agent with 1 unit of hyaluronic acid at a reaction temperature of about 10 to 30 ° C. for about 1 to 3 days. .

  The cationization of hyaluronic acid does not necessarily need to be introduced into every hydroxyl group or carboxyl group per unit of hyaluronic acid represented by formula (4). It is only necessary that about 0.1 to 2 molecules are introduced into the. In the case of cationized hyaluronic acid in which a cation group is introduced into a hydroxyl group, the carboxyl group may be an alkali salt in the hair treatment agent.

  In addition, when a cationic group is introduced into the carboxyl group of hyaluronic acid, it is generally sufficient that about 0.1 to 0.5 molecules are introduced per unit. The introduction ratio of cationization (cationization ratio) can be determined from the nitrogen content of hyaluronic acid before the reaction and the nitrogen content after cationization.

Among these cationized hyaluronic acids, it is preferable to use a cationized hyaluronic acid in which a cationic group is introduced into R ¹ in the formula (6) from the viewpoint of improving dyeability to hair.

  In addition, the above-mentioned cationized hyaluronic acid can use a commercial item as it is. For example, a brand name “HA-QUAT” (manufactured by Engelhard), a brand name “Hyarobe” (manufactured by QP), and the like can be given.

  The content of the cationized hyaluronic acid is not particularly limited as long as the effects of the present invention are exhibited. However, from the viewpoint of improving decolorization / dyeability of hair, 0.005% by mass or more is preferable in the hair treatment agent. 025 mass% or more is more preferable. Moreover, 0.5 mass% or less is preferable from a viewpoint of suppressing a feeling of stickiness, and 0.25 mass% or less is more preferable. For these reasons, the content of the cationized hyaluronic acid in the hair treatment agent is preferably 0.005 to 0.5% by mass, and more preferably 0.025 to 0.25% by mass.

  The hydrocarbons and waxes of component (B) are not particularly limited as long as the effects of the present invention are exhibited. Examples of hydrocarbons include liquid paraffin, liquid isoparaffin, squalane, ozokerite, ceresin, petrolatum, and paraffin wax. , Microcrystalline wax, polyethylene powder and the like. Examples of the waxes include carnauba wax, candelilla wax, jojoba oil, beeswax, lanolin, shellac and the like. Among these, from the viewpoint of improving the decolorization / dyeability of hair, it is preferable to use hydrocarbons that are solid at room temperature, such as ozokerite, ceresin, petrolatum, paraffin wax, microcrystalline wax, and polyethylene powder. Moreover, it is preferable to use waxes that are solid at room temperature, such as carnauba wax, candelilla wax, beeswax, lanolin, shellac, and the like. In the present invention, “room temperature” refers to a temperature range under an atmosphere of 1 to 30 ° C.

  As the component (B), hydrocarbons or waxes may be used singly or in appropriate combination of two or more. The content of the hydrocarbons and / or waxes as the component (B) is not particularly limited as long as the effects of the present invention are exhibited. From the viewpoint of retention in the hair, 0.25% by mass in the hair treatment agent. The above is preferable, and 0.5% by mass or more is more preferable. Moreover, 5 mass% or less is preferable from a viewpoint of the extensibility on hair, and 2.5 mass% or less is more preferable. For these reasons, the content of hydrocarbons and / or waxes in the hair treatment agent is preferably 0.25 to 5% by mass, more preferably 0.5 to 2.5% by mass. Good.

  In addition, the hair treatment agent of the present invention can contain (C) an amphoteric polymer compound from the viewpoint of preventing the component (A) from being excessively adsorbed on the hair. Since hair damaged by an alkali agent or an oxidizing agent is negatively charged, the component (A) having a positive charge is easily adsorbed to the hair. However, when the component (A) is excessively adsorbed on the hair, the fingering property after the description is deteriorated, but the use feeling can be improved by using the amphoteric polymer together.

  The amphoteric polymer compound that can be used is not particularly limited as long as the effects of the present invention are exhibited. For example, dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylamide / acrylic acid copolymer, dimethyldiallyl chloride can be used. Ammonium / methyl acrylate / acrylic acid copolymer, N-methacryloylethyl N, N-dimethylammonium α-N-methylcarboxybetaine / butyl methacrylate copolymer, acrylic acid / methyl acrylate / methacrylamidopropyltrimethylammonium chloride Examples include copolymers, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymers, and the like. Among these, from the viewpoint of improving the cohesiveness of the hair after dyeing, dimethyldiallylammonium chloride / acrylic acid copolymer, dimethyldiallylammonium chloride / acrylamide / acrylic acid copolymer, dimethyldiallylammonium chloride / methyl acrylate, It is preferable to use an amphoteric polymer compound containing dimethyldiallylammonium as a structural unit, such as an acrylic acid copolymer. In addition, these amphoteric polymer compounds may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

  In addition, a commercial item can be used for the above-mentioned amphoteric polymer compound as it is. For example, as the dimethyldiallylammonium chloride / acrylic acid copolymer, the trade name “MARCOAT 280,295” (manufactured by Calgon Co., Ltd.) and the like, and as the dimethyldiallylammonium chloride / acrylamide / acrylic acid copolymer, the trade name “MARCOAT Examples of the dimethyldiallylammonium chloride / methyl acrylate / acrylic acid copolymer such as “plus 3330, 3331” (manufactured by Calgon Co., Ltd.) and the like include the trade name “Marcoat Plus 2001” (manufactured by Calgon Co.).

  The content of the amphoteric polymer compound is not particularly limited as long as the effects of the present invention are exhibited. However, from the viewpoint of improving the decolorization / dyeability and improving the feeling after use, the content of the amphoteric polymer compound is 0.00. 05 mass% or more is preferable and 0.25 mass% or more is more preferable. In addition, from the viewpoint of stability of the preparation, 2.5% by mass or less is preferable, and 1.5% by mass or less is more preferable. From these facts, the content of the amphoteric polymer in the first agent or the second agent is preferably 0.05 to 2.5% by mass, more preferably 0.25 to 1.5% by mass. Good.

  In addition, when using the said (A) component, (B) component, and (C) component, (C) component may also be independently contained in the 1st agent or the 2nd agent, respectively, You may make it contain in both of 2nd agents.

  The alkaline agent in the first agent is not particularly limited as long as it is usually used for a hair treatment agent. For example, organic amines such as monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, 2-amino-2-methyl-1-propanol; sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, bicarbonate Examples thereof include inorganic alkalis such as ammonium and ammonia.

  The content of the alkaline agent in the first agent is not particularly limited as long as the effect of the present invention is exhibited, but it is preferably 1% by mass or more and more preferably 3% by mass or more from the viewpoint of hair decolorization / dyeability. Moreover, from a viewpoint of irritation to the scalp, 15 mass% or less is preferable and 12 mass% or less is more preferable. From these things, content of the alkaline agent in the 1st agent becomes like this. Preferably it is 1-15 mass%, More preferably, it is 3-12 mass%.

  When the hair treatment agent of the present invention is used as a hair bleaching agent, the alkali agent is contained in the first agent, but when used as an oxidation hair dye, an oxidation dye is further contained. The oxidation dye in the present invention means both a dye precursor that develops color by its own oxidative polymerization and a coupler that has various hues by reaction with the dye precursor.

  Examples of the oxidative dye precursor that can be used in the present invention include phenylenediamines, aminophenols, diaminopyridines, and salts thereof such as hydrochlorides and sulfates. Specifically, p-phenylenediamine, toluene-2,5-diamine, toluene-3,4-diamine, 2,5-diaminoanisole, N-phenyl-p-phenylenediamine, N-methyl-p-phenylenediamine N, N-dimethyl-p-phenylenediamine, 6-methoxy-3-methyl-p-phenylenediamine, N, N-diethyl-2-methyl-p-phenylenediamine, N-ethyl-N- (hydroxyethyl) -P-phenylenediamine, N- (2-hydroxypropyl) -p-phenylenediamine, 2-chloro-6-methyl-p-phenylenediamine, 2-chloro-p-phenylenediamine, N, N-bis- (2 -Hydroxyethyl) -p-phenylenediamine, 2,6-dichloro-p-phenylenediamine, 2-chloro-6-butyl Phenylenediamines such as mu-p-phenylenediamine; paraaminophenol, orthoaminophenol, paramethylaminophenol, 2,4-diaminophenol, 5-aminosalicylic acid, 2-methyl-4-aminophenol, 3-methyl-4 -Aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2- Examples thereof include aminophenols such as chloro-4-aminophenol and 3-chloro-4-aminophenol; diaminopyridines such as 2,5-diaminopyridine, and salts thereof.

  Examples of the coupler include resorcin, m-aminophenol, m-phenylenediamine, 2,4-diaminophenoxyethanol, 5-amino-o-cresol, 2-methyl-5-hydroxyethylaminophenol, and 2,6-diaminopyridine. And catechol, pyrogallol, gallic acid, tannic acid and the like and salts thereof.

  The content of the oxidative dye in the first agent is not particularly limited as long as the effect of the present invention is exhibited. However, the content is preferably 0.1% by mass or more, more preferably 1% by mass or more from the viewpoint of dyeability to hair. Moreover, 10 mass% or less is preferable from a viewpoint of irritation to the scalp, and 5 mass% or less is more preferable. From these things, content of the oxidation dye in the 1st agent becomes like this. Preferably it is 0.1-10 mass%, More preferably, it is 1-5 mass%.

  In addition, when the 1st agent concerning this invention contains an oxidation dye, from a viewpoint of preventing the oxidation in the formulation preservation | save, antioxidant can be contained. Antioxidants include sodium ascorbate, potassium ascorbate, calcium ascorbate, ammonium ascorbate, erythorbic acid, sodium erythorbate, magnesium ascorbate phosphate, ascorbyl citrate, ascorbyl acetate, ascorbyl tartrate, ascorbyl palmitate, In addition to ascorbic acid and ascorbic acid derivatives such as ascorbyl stearate and ascorbyl glucoside, sulfites, bisulfites, pyrobisulfites and the like can be mentioned.

  The oxidizing agent in the second agent is not particularly limited as long as it exhibits an oxidizing action. For example, hydrogen peroxide, urea peroxide, alkali metal bromate and the like can be mentioned. Of these, hydrogen peroxide is preferably used, and is usually used as a hydrogen peroxide solution.

  The content of the oxidizing agent in the second agent is not particularly limited as long as the effect of the present invention is exhibited, but from the viewpoint of hair decolorization, 0.01% by mass or more is preferable, and 0.1% by mass or more is more preferable. preferable. Moreover, from a viewpoint of preventing skin irritation and hair damage, 12 mass% or less is preferable and 6 mass% or less is more preferable. From these things, it is preferable that content of the oxidizing agent in a 2nd agent shall be 0.01-12 mass%, More preferably, it is good to set it as 0.1-6 mass%.

  In addition, the 2nd agent of this invention can be made to contain the stabilizer of an oxidizing agent. For example, phenacetin, hydroxyethane diphosphonic acid and the like can be exemplified.

  In addition, the first agent and / or the second agent according to the present invention include, in addition to the above components, lower alcohols such as ethanol and isopropanol; lauryl alcohol, myristyl, as long as the effects of the object of the present invention are not impaired. Higher alcohols such as alcohol, cetyl alcohol, stearyl alcohol; higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid; esters such as myristyl myristate, isostearyl myristate, stearyl stearate; avocado oil, olive oil, sa Animal and vegetable oils such as flower oil and hydrogenated oil; polyhydric alcohols such as polyethylene glycol, glycerin, polyglycerin, 1,3-butylene glycol, 1,2-pentanediol, 1,2-octanediol; sorbitan fatty acid ester, glycerin fatty acid S And non-ionic surfactants such as these alkylene oxide adducts, polyglycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene lanolin; higher fatty acid soaps, Anionic surfactants such as alkyl sulfates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, alkyl ether phosphates, alkyl ether carboxylates, acylmethyl taurates, alkyl sulfosuccinic acids and salts thereof; alkyls Glycine salt, carboxymethylglycine salt, N-acylaminoethyl-N-2-hydroxyethylglycine salt and other glycine-type amphoteric surfactants, alkylaminopropionate, alkyliminodipropio Aminopropionic acid-type amphoteric surfactants such as acid salts, aminoacetic acid betaine-type amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, and sulfobetaine-type amphoteric surfactants such as alkylhydroxysulfobetaine Amphoteric surfactants such as; alkylamine salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride; cationic surfactants such as fatty acid amidoamines such as dimethylaminoethylamide myristate and diethylaminopropylamide stearate An agent; a thickener, an anti-inflammatory agent, an ultraviolet absorber, a colorant, a fragrance, water and the like can be appropriately contained depending on the purpose.

  In addition, as a dosage form of the 1st agent and 2nd agent which concern on the hair treatment agent of this invention, it can use with various dosage forms, such as a liquid form, a gel form, and a cream form, and a 1st agent and 2nd are used at the time of use. The agent is mixed to treat the hair. Mixing of the first agent and the second agent at the time of use may be usually performed at a mass ratio of about 1: 2 to 2: 1.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. The content is mass% unless otherwise specified. “POE” is an abbreviation for polyoxyethylene, and the number in parentheses represents the number of added moles.

(Sample preparation)
According to the composition shown in Tables 1-2, each 1st agent of the hair decoloring agent was prepared by the usual method. Moreover, according to the composition shown to Tables 3-4, each 1st agent of the oxidation hair dye was prepared by the usual method. Each hair treatment agent was prepared by mixing 20 g of the first agent with 20 g of the following second agent to prepare test samples for the examples and comparative examples. Each test sample was subjected to the following evaluation test. The cationized hyaluronic acid used was O- [2-hydroxy-3- (trimethylammonio) propyl] hyaluronic acid [trade name “Hyarobel” (manufactured by QP Corporation)].

(Oxidative hair dye second agent)
Hydrogen peroxide solution (35%) 16.7
Hydroxyethane diphosphonic acid 0.1
Purified water balance part Total 100.0

(Test Example 1: Decolorization evaluation)
Examples 1-6 and Comparative Examples 1-6
4 g of each test sample (drug) prepared in “Preparation of sample” was uniformly applied to a black human hair bundle having a weight of 2 g and a length of 10 cm, and then allowed to stand in an atmosphere at 30 ° C. for 30 minutes. Then, the chemical | medical agent was washed with water using the shampoo, and the hair | bristle bundle was dried using the dryer, and the test hair | bristle bundle of each Example and each comparative example was obtained.

Standard product 1
A test sample (drug) was obtained by mixing 20 g of the first agent of the standard product 1 and 20 g of the second agent. 4 g of the obtained drug was uniformly applied to a black human hair bundle having a weight of 2 g and a length of 10 cm, and then allowed to stand in an atmosphere at 30 ° C. for 30 minutes. Then, the chemical | medical agent was washed with water using the shampoo, and the hair bundle was dried using the dryer, and the test hair bundle of the standard product 1 was obtained.

  The lightness L * value of the L * a * b * color system was measured for each of the obtained test hair bundles using a spectrocolorimeter (manufactured by Minolta Co., Ltd., CM-3610d type), and decolorization was determined according to each evaluation standard. evaluated. The results are shown in Table 5. In addition, L * value shows that decoloring property is so high that a value is high.

<Evaluation criteria for decolorization>
A: The difference in L * value from the test hair bundle of the standard product 1 is +0.5 or more.
(Triangle | delta): The difference of L * value with the test hair | bristle bundle of the standard product 1 is -0.5 or more and less than +0.5.
X: The difference in L * value from the test hair bundle of the standard product 1 is less than −0.5.

(Test Example 2: Evaluation of dyeability)
Examples 7-12 and Comparative Examples 7-12
4 g of each test sample (drug) prepared in “Preparation of sample” was uniformly applied to a white human hair bundle having a weight of 2 g and a length of 10 cm, and then allowed to stand in an atmosphere at 30 ° C. for 30 minutes. Then, the chemical | medical agent was washed with water using the shampoo, and the hair | bristle bundle was dried using the dryer, and the test hair | bristle bundle of each Example and each comparative example was obtained.

Standard product 2
A test sample (drug) was obtained by mixing 20 g of the first preparation of Standard 2 and 20 g of the second preparation. 4 g of the obtained drug was uniformly applied to a black human hair bundle having a weight of 2 g and a length of 10 cm, and then allowed to stand in an atmosphere at 30 ° C. for 30 minutes. Then, the chemical | medical agent was washed with water using the shampoo, and the hair | bristle bundle was dried using the dryer, and the test hair | bristle bundle of the standard product 2 was obtained.

  Each test hair bundle obtained was measured for color difference ΔE * ab in the L * a * b * color system using a spectrocolorimeter (manufactured by Minolta Co., Ltd., CM-3610d type). It evaluated according to. The results are shown in Table 6. ΔE * ab indicates that the higher the value, the higher the dyeability.

<Evaluation criteria for dyeability>
○: The difference in ΔE * ab from the test hair bundle of the standard product 2 is +0.5 or more.
Δ: The difference in ΔE * ab from the test hair bundle of the standard product 2 is −0.5 or more and less than +0.5.
X: The difference in ΔE * ab from the test hair bundle of the standard product 2 is less than −0.5.

(Test Example 3: Evaluation of stiffness)
The test hair bundles of each of Examples 1 and 2 and Comparative Examples were evaluated by 20 professional panelists for the feeling of stiffness after treatment based on the following criteria. The results are shown in Tables 5-8.

<Evaluation criteria for the feeling of stiffness>
○: More than 15 out of 20 responded that they did not feel stiff.
Δ: 8 to 14 out of 20 responded that they did not feel stiff.
×: 7 or less of 20 responded that there was no sense of stiffness.

(Test Example 4: Evaluation of finished feeling and unity feeling)
The test hair bundles of each of Examples 1 and 2 of Test Examples 1 and 2 were evaluated based on the following criteria by 20 professional panelists for the lack of a hard finish feeling on the hair ends after treatment and the feeling of hair unity. . The results are shown in Tables 5-8.

<Evaluation criteria for finished feeling>
○: 15 or more out of 20 responded that the hair tips had no hard finish.
Δ: 8 to 14 out of 20 responded that the hair tips had no hard finish.
X: 7 or less out of 20 responded that the hair ends had no hard finish.

<Evaluation criteria for unity>
○: 15 or more of 20 responded that the hair did not spread and had a sense of unity.
Δ: 8 to 14 out of 20 responded that the hair did not spread and had a sense of unity.
×: 7 or less of 20 responded that the hair did not spread and had a sense of unity.

  From the results of Tables 5 to 6, when the hair treatment agent of the present invention is used as a hair bleaching agent, it is superior to the results of each comparative example, and has excellent decolorization properties, and further suppresses the feeling of hair stiffness after treatment, and the hair ends It turns out that it becomes excellent in unity property by suppressing that it becomes a hard finish feeling.

  In addition, from the results of Tables 7 to 8, when the hair treatment agent of the present invention is used as an oxidative hair dye, it has excellent hair dyeing properties, and further suppresses the stiff feeling of the hair after the treatment, and has a hard finish. It turns out that it is suppressed and becomes excellent in unity property.

  Below, the formulation example of the hair treatment agent of this invention is shown. In addition, a compounding quantity is the mass%.

(Formulation Example 1: Hair bleaching agent)
<First Agent>
Polyoxyethylene (20) stearyl ether 2.0
Polyoxyethylene (40) cetyl ether 2.0
Polyoxyethylene (20) hydrogenated castor oil 0.5
28% stearyltrimethylammonium chloride 5.0
Microcrystalline wax 2.0
Stearyl alcohol 7.0
Cetyl octanoate 1.0
Cationized hyaluronic acid 0.1
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Methyl polysiloxane 1.0
28% ammonia water 6.0
Monoethanolamine 3.0
Ammonium bicarbonate 1.0
Edetate disodium 0.2
Jojoba oil 0.1
Water-soluble collagen 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Polyoxyethylene (40) cetyl ether 0.5
Cetanol 1.0
Dipropylene glycol 1.0
Hydroxyethanediphosphonic acid 0.3
Purified water balance
Total 100.0

(Formulation example 2: hair bleaching agent)
<First Agent>
Dicetyl phosphate 0.8
Polyoxyethylene cetyl ether phosphate 1.6
Polyoxyethylene (40) cetyl ether 2.0
Liquid paraffin 3.0
Microcrystalline wax 1.0
Cetanol 5.0
Cetostearyl alcohol 1.6
Concentrated glycerin 2.0
Cationized hyaluronic acid 0.1
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Methylphenylpolysiloxane 1.0
28% ammonia water 8.0
Ammonium bicarbonate 4.0
Edetate disodium 0.2
Licorice extract powder 0.05
L-Arginine 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Polyoxyethylene (20) cetyl ether 0.05
Absolute ethanol 0.5
Propylene glycol 3.0
Hydroxyethanediphosphonic acid 0.05
Phenoxyethanol 0.05
Diethylenetriaminepentaacetic acid pentasodium 0.2
Purified water balance
Total 100.0

<Third agent>
Potassium persulfate 25.0
Ammonium persulfate 30.0
Anhydrous sodium metasilicate 20.0
Magnesium carbonate 10.0
Sodium chloride 10.0
Sodium silicate 4.0
Silicic anhydride 0.95
Chromium oxide 0.05
Total 100.0

(Formulation Example 3: Oxidative hair dye)
<First Agent>
Polyoxyethylene (20) stearyl ether 2.0
Polyoxyethylene (40) cetyl ether 2.0
28% stearyltrimethylammonium chloride 5.0
Beeswax 2.0
Stearyl alcohol 7.0
Cetyl octanoate 1.0
Cationized hyaluronic acid 0.1
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Dimethyl diallylammonium chloride
-Acrylamide copolymer liquid 2.0
Aminoethylaminopropylmethylsiloxane
・ Dimethylsiloxane copolymer 1.0
28% ammonia water 6.0
Monoethanolamine 3.0
Ammonium bicarbonate 1.0
Paraphenylenediamine 0.4
Resorcin 0.35
2,4-Diaminophenoxyethanol hydrochloride 0.03
Metaaminophenol 0.05
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Camellia oil 0.1
Water-soluble collagen 0.1
Hydrolyzed silk 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Polyoxyethylene (40) cetyl ether 0.5
Cetanol 1.0
Dipropylene glycol 1.0
Hydroxyethanediphosphonic acid 0.3
Purified water balance
Total 100.0

(Formulation Example 4: Oxidative hair dye)
<First Agent>
Polyoxyethylene (20) hydrogenated castor oil 3.0
Polyoxyethylene (20) cetyl ether 2.0
30% stearyltrimethylammonium chloride 3.0
Microcrystalline wax 1.0
Cetyl alcohol 3.0
Oleyl alcohol 2.0
Cationized hyaluronic acid 1.0
Ethanol sulfate lanolin fatty acid aminopropyl
Triethylammonium 1.0
Polyoxyethylene (50)
・ Methylpolysiloxane copolymer 1.0
28% ammonia water 6.0
Monoethanolamine 3.0
Ammonium bicarbonate 1.0
Paraphenylenediamine 0.5
Paraaminophenol 0.5
Resorcin 0.35
5-Aminoorthocresol 0.2
Metaaminophenol 0.1
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Loquat leaf extract 0.1
L-glutamic acid 0.1
Water-soluble collagen 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Sodium lauryl sulfate 0.2
Polyoxyethylene (20) cetyl ether 2.0
Cetanol 6.0
Dipropylene glycol 1.0
Hydroxyethanediphosphonic acid 0.05
Phenoxyethanol 0.05
Diethylenetriaminepentaacetic acid pentasodium 0.2
Phosphoric acid 0.05
Purified water balance
Total 100.0

(Formulation Example 5: Oxidative hair dye)
<First Agent>
Polyoxyethylene (20) stearyl ether 2.0
Polyoxyethylene (40) cetyl ether 2.0
28% stearyltrimethylammonium chloride 5.0
Liquid paraffin 2.0
Microcrystalline wax 1.0
Stearyl alcohol 7.0
Isopropyl palmitate 1.0
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Dimethyl diallylammonium chloride
-Acrylamide copolymer liquid 2.0
Decamethylcyclopentasiloxane 1.0
28% ammonia water 6.0
Monoethanolamine 3.0
Ammonium bicarbonate 1.0
Paraphenylenediamine 0.4
Paraaminophenol 0.2
Resorcin 0.35
5-Aminoorthocresol 0.3
Metaaminophenol 0.2
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Almond oil 0.1
Hydrolyzed collagen 0.1
Pearl calc extract 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Cationized hyaluronic acid 0.1
Polyoxyethylene (40) cetyl ether 0.5
Cetanol 1.0
Dipropylene glycol 1.0
Hydroxyethanediphosphonic acid 0.3
Purified water balance
Total 100.0

(Formulation Example 6: Oxidative hair dye)
<First Agent>
Polyoxyethylene (20) stearyl ether 2.0
Polyoxyethylene (40) cetyl ether 2.0
28% stearyltrimethylammonium chloride 5.0
Vaseline 2.0
Stearyl alcohol 7.0
Cetyl palmitate 1.0
Dimethyl diallylammonium chloride
-Acrylic acid copolymer liquid 1.0
Dimethyl diallylammonium chloride
-Acrylamide copolymer liquid 2.0
Highly polymerized methylpolysiloxane 1.0
28% ammonia water 6.0
Monoethanolamine 3.0
Ammonium bicarbonate 1.0
Paraphenylenediamine 0.3
Paraaminophenol 0.5
Resorcinol 0.1
5-Aminoorthocresol 0.3
Metaaminophenol 0.05
Anhydrous sodium sulfite 0.5
Sodium L-ascorbate 0.5
Edetate disodium 0.2
Squalane 0.1
Purified water balance
Total 100.0

<Second agent>
35% hydrogen peroxide solution 16.5
Sodium lauryl sulfate 0.2
Polyoxyethylene (20) cetyl ether 2.0
Cetanol 6.0
Dipropylene glycol 1.0
Hydroxyethanediphosphonic acid 0.05
Phenoxyethanol 0.05
Diethylenetriaminepentaacetic acid pentasodium 0.2
Phosphoric acid 0.05
Purified water balance
Total 100.0

<Third agent>
Cationized hyaluronic acid 0.5
Water-soluble collagen 0.5
Hydroxyethyl cellulose 0.1
1,3-butylene glycol 10.0
Absolute ethanol 10.0
Purified water balance
Total 100.0

Claims (7)

  A hair treatment agent comprising a first agent containing an alkaline agent and a second agent containing an oxidizing agent, which contains (A) cationized hyaluronic acid, and (B) hydrocarbons and / or waxes. A hair treatment agent characterized by the above. The component (A) is represented by the general formula (1):

The hair treatment agent according to claim 1, which is a cationized hyaluronic acid having a repeating unit represented by:   The hair treatment agent according to claim 1 or 2, wherein the molecular weight of the component (A) is 100,000 to 3,000,000 in terms of weight average molecular weight.   The hair treatment agent according to any one of claims 1 to 3, wherein the component (B) is a hydrocarbon and / or wax solid at room temperature.   The hair treatment agent according to any one of claims 1 to 4, further comprising (C) an amphoteric polymer compound.   The hair treatment agent according to claim 5, wherein the component (C) is an amphoteric polymer compound containing dimethyldiallylammonium as a structural unit. Furthermore, (D) higher alcohol is contained, The hair treatment agent in any one of Claims 1-6 characterized by the above-mentioned.