JP7094661B2 - Hair treatment method - Google Patents

Description

The present invention relates to a hair treatment method.

Conventionally, when it is desired to alleviate curly hair or to straighten hair, it is common to perform a treatment called straight perm treatment or relaxer treatment. In the straight perm treatment, the disulfide bond of the keratin protein inside the hair is cleaved with a reducing agent such as thioglycolic acid, and if necessary, the curly hair is forcibly transformed into a straight shape by using a high-temperature hair iron or the like. , Hydrogen peroxide, potassium bromine and other oxidizing agents to re-bond the disulfide bonds. In the relaxer treatment, a strong alkaline hair treatment agent having a pH of 12 to 14 cleaves the disulfide bond of the hair protein and replaces it with a lanthionine bond, thereby forcibly deforming and fixing the hair to a straight shape.

However, it is known that these methods may cause serious damage to hair because they use strong chemical reactions and high temperature heat. For this reason, various methods for straightening curly hair and giving hair cohesion without heating have been studied without performing straight perm treatment or relaxer treatment.

In Patent Document 1, a hair deformation composition containing a benzene derivative having two groups selected from a hydroxy group and an amino group on a benzene ring and a gallic acid-based glycoside is applied to curly hair and left for 4 hours. It is disclosed that it can be straightened without damaging the curly hair and has excellent moisture resistance.

In Patent Document 2, a composition containing a specific carboxylic acid, a specific sulfonic acid, and an organic solvent and exhibiting acidity is applied to the frizz and heated at 40 ° C. for 1 hour to make it simple without damaging the frizz. It is disclosed that the hair can be straightened and the deformation effect is not lost even by humidity and washing.

On the other hand, in order to finish the desired hairstyle, it is necessary to use a hair styling agent (wax, mist, foam, etc.), that is, to break / rebond the hydrogen bonds inside the hair or to bond the hairs together. It is common. However, this operation is complicated and not sufficient from the viewpoint of facilitating shaping. For this reason, various methods have been studied for improving the shapeability of hair by a simple method and simultaneously giving the hair cohesiveness and smoothness. For example, Patent Documents 3 to 5 describe aromatic sulfones such as naphthalene sulfonic acid. A technique for enhancing the shapeability of hair by using an acid-containing hair treatment agent is described.

Japanese Unexamined Patent Publication No. 2005-154348 Japanese Unexamined Patent Publication No. 8-92043 Japanese Unexamined Patent Publication No. 2010-65022 Japanese Unexamined Patent Publication No. 6-305942 Japanese Patent Application Laid-Open No. 6-298625

However, in the methods of Patent Documents 1 and 2, the curly hair may not be sufficiently relieved, or the curly hair may return to the state before the treatment by repeatedly washing the hair. There was a problem that the effect could not be obtained when trying to adopt such a method.

Further, the shapeability by the techniques of Patent Documents 3 to 5 is evaluated by shaping the hair in a wet state with water and observing the sustainability of the shape after drying. From this, it can be said that the shapeability in these techniques is due to the breakage / recombination of hydrogen bonds inside the hair, that is, the so-called water set, which occurs when the hair dries from a wet state. Therefore, these techniques did not improve the shapeability of the hair "after drying" after being treated with a hair treatment agent. In particular, the technique described in Patent Document 3 also has an effect of making it difficult for the hair to fall asleep, and thus can be said to be a technique for reducing the shapeability of the hair after drying.

It is also known that aromatic sulfonic acids such as naphthalene sulfonic acid are compounds that give hair firmness and elasticity (for example, JP-A-05-229919, JP-A-8-198732, etc.). In fact, when the hair is treated by the methods of Patent Documents 2 to 5, it is insufficient in terms of the softness of the treated hair. Further, even when the hair is treated by the method of Patent Document 1, it is insufficient in terms of the softness of the hair after the treatment. Further, when the treatments described in Patent Documents 1 to 5 are applied to fine hair such as Caucasian hair, there is a problem that the hair is easily entangled and the hair is difficult to handle.

The present invention has been made in view of such circumstances, and it is possible to relieve curly hair, the hair flow of the relieved curly hair is uniform, the hair is well organized, and the hair shape after hair treatment is almost the same even after repeated shampooing. Regarding hair treatment methods that can be maintained. In addition, the hair treatment method of the present invention can soften the hair when wet, impart natural lightness and resistance to entanglement to the dried hair, and further enhance the shapeability of the dried hair.

As a result of diligent studies, the present inventors have found that by treating hair with a specific phenolic compound and aromatic sulfonic acid in a predetermined order, the effect of alleviating curly hair is dramatically improved even when the hair treatment time is short. It was found that the hair flow was improved, the hair flow was uniform, and the easing effect was almost the same even after repeated washing of hair. Even more surprisingly, treating the hair in a predetermined order not only feels lighter, but also makes the treated hair less entangled and softer to the touch when wet, resulting in easier hair styling during the drying process. Furthermore, he found that it was possible to impart shapeability to dry hair, and completed the invention.

That is, the present invention provides a hair treatment method including the following steps (i) to (iii).
Step (i): A step of applying the first composition containing the following component (A) to hair.
(A) An aromatic compound or a salt thereof having a molecular weight of 350 or less and having 1 or more and 4 or less phenolic hydroxyl groups Step (ii): After step (i), the hair is kept at 15 ° C or higher and 100 ° C or lower for 15 seconds or longer. Step of leaving for 60 minutes or less Step (iii): After step (ii), a step of applying a second composition containing the following component (B) to hair.
(B) Aromatic sulfonic acid having a molecular weight of 300 or less or a salt thereof

The hair treatment method of the present invention can relieve curly hair, the relaxed curly hair flow is uniform, and the hair is well organized, and the hair shape after hair treatment can be substantially maintained even after repeated shampooing. Further, it softens the hair when it is wet after treatment, has a natural lightness even when it is dried, is less likely to be entangled, and can enhance the shapeability of the hair after drying.

● First composition [Component (A): Aromatic compound having a phenolic hydroxyl group or a salt thereof]
The first composition used in the step (i) contains an aromatic compound or a salt thereof having a molecular weight of 350 or less and having a phenolic hydroxyl group of 1 or more and 4 or less as the component (A).

As such an aromatic compound, those having an inorganic value of 100 or more and 500 or less and an organic value of 120 or more and 300 or less are preferable. The inorganic value and the organic value in the component (A) refer to the inorganic value and the organic value of the aromatic compound which is not a salt. That is, when the component (A) is a salt of an aromatic compound, it means an inorganic value and an organic value of the aromatic compound that does not form a salt. From the viewpoints of the strength of the frizz-relieving effect, the softness of the treated hair, the difficulty of entanglement of the hair, and the ease of shaping, the inorganic value is preferably 115 or more, more preferably 135 or more, still more preferably. It is 165 or more, preferably 495 or less, more preferably 315 or less, and further preferably 230 or less. From the same viewpoint, the organic value is preferably 140 or more, preferably 280 or less, more preferably 270 or less, still more preferably 230 or less, still more preferably 200 or less.

Specifically, 3,4-methylenedioxyphenol (conventional name: sesamole, inorganic value: 165, organic value: 140), resorcin (inorganic value: 215, organic value: 120), 4-n -Butyl resorcinol (conventional name: lucinol, inorganic value: 215, organic value: 200), 4- (1-phenylethyl) resorcin (conventional name: Simwhite 377, inorganic value: 230, organic value: 270) ), O-Hydroxybenzyl alcohol (inorganic value: 215, organic value: 140), acetaminophen (inorganic value: 315, organic value: 160), 2-naphthol (inorganic value: 160, organic value) Value: 200), o-methoxyphenol (inorganic value: 135, organic value: 140), oxybenzone-3 (inorganic value: 215, organic value: 280), oxybenzone-1 (inorganic value: 295,) Organic value: 260), Floroglucinol (Inorganic value: 315, Organic value: 120), p-hydroxybenzoic acid (Inorganic value: 265, Organic value: 140), Isopropylmethylphenol (Inorganic value: 140) : 115, organic value: 190), oxybenzone-6 (inorganic value: 335, organic value: 300), gallic acid (inorganic value: 465, organic value: 140), oxybenzone-2 (inorganic value: 140) : 495, organic value: 260), phenol (inorganic value: 115, organic value: 120). Among these, 3,4-methylenedioxyphenol, resorcinol, 4-n-butylresorcinol, 4- (1-phenylethyl) resorcinol, o-hydroxybenzyl alcohol, acetaminophen, 2-naphthol, o-methoxyphenol , Oxybenzon-3, Oxybenzon-1, Fluoroglucinol, p-hydroxybenzoic acid, preferably at least one selected from 3,4-methylenedioxyphenol, resorcinol, 4-n-butylresorcinol, 4- (1- (1-) At least one selected from phenylethyl) resorcin and o-hydroxybenzyl alcohol is more preferred.

The content of the component (A) in the first composition is preferably 0.5% by mass or more, more preferably, from the viewpoints of habit-relieving effect, hair wash resistance, resistance to entanglement of hair after treatment, and ease of shaping. It is preferably 0.8% by mass or more, more preferably 1.0% by mass or more, still more preferably 3% by mass or more, and preferably 12% by mass or less from the viewpoint of achieving both a habit-relieving effect and softness after hair treatment. It is more preferably 8% by mass or less, still more preferably 6% by mass or less.

[Ingredient (C): Thickener]
The first composition used in the step (i) preferably further contains a thickener as the component (C) from the viewpoint of more strongly relaxing the curly hair and improving the softness and entanglement resistance of the hair. .. Examples of the thickener include anionic thickeners, cationic thickeners, nonionic thickeners and the like.

Specific examples of the anionic thickener include polyacrylic acid (for example, Noveon: Carbopol 941 and 981), acrylic acid / alkyl methacrylate copolymer (for example, Noveon: Carbopol ETD2020), and lower alkyl. Hydrolyzate of partially cross-linked polymer with terminal unsaturated diene compound of vinyl ether / maleic anhydride copolymer or monoalkyl ester thereof (ASHLAND: Stabilize 06, QM), carrageenan (for example, Mitsubishi Rayon: Soagina) LX22, ML210), Xanthan gum (for example, Dainippon Sumitomo Pharmaceutical Co., Ltd .: Echo Gum T), Welan gum (for example, Sansho Co., Ltd .: K1C376, K1A96), Hydroxypropyl xantan gum (for example, Dainippon Sumitomo Pharmaceutical Co., Ltd .: Laborgum EX), Tearoxy Examples thereof include PG hydroxyethyl cellulose sulfonate sodium, hydroxyethyl acrylate / acryloyldimethyltaurine Na) copolymer (for example, Sepic: Simulgel NS, Sepinob EMT10).

Examples of the cationic thickener include natural or semi-synthetic cationic polysaccharides, synthetic polymers containing an amino group or an ammonium group in the side chain of the polymer chain, or a synthetic polymer containing a diallyl quaternary ammonium salt as a constituent unit. Be done.

Specific examples of cationic polysaccharides include cationized cellulose derivatives (for example, Lion: Leogard G, GP, Dow Chemical: Ucare Polymers JR-125, JR-400, JR-30M, LR-400). , LR-30M, Axonobel: Cellulose H-100, L-200), Catylated guar gum derivative (for example, Solvay: Jaguar C-13S, C-17, DSP Gokyo Food & Chemicals: Labol gum CG-M, CG-M7, CG-M8M), hydroxypropyl chitosan (for example, Ichimaru Falcos: Chitofilmer HV-10), chitosan dl-pyrrolidone carboxylate (for example, Union Carbide: Kytomer PC) ) Etc. can be mentioned.

As the synthetic cationic polymer containing an amino group or an ammonium group in the side chain of the polymer chain, trialkylaminoalkyl (meth) acrylate, trialkylaminoalkyl (meth) acrylamide, (meth) acrylamide, vinylamine and the like are used as constituent units. Examples thereof include synthetic cationic polymers containing, and specific examples thereof include polymers of methacryloyloxyethylene trimonium chloride (INCI name: Polyquaternium-37, for example, BASF: Cosmedia Ultragel 300, SALCARE SC95, Sigma 3V: Synthalen. CR), (acrylic acid / methyl acrylate / 3-methacryloylaminopropyltrimethylammonium chloride) polymer (INCI name: polyquaternium-47, for example, Lubrizol: Marcourt 2201), (acrylic acid / acrylamide / methylmethacrylatepropyltrimethylammonium chloride), Chloride) Polymers (INCI name: Polyquaternium-53, eg Lubrizol: Marcourt 2003), (Dimethylacrylamide / Ethyltrimonium methacrylate trimonium chloride) copolymers (eg, BASF: Tinobis CD), (Vinylamine / Vinyl alcohol) copolymers (Vinylamine / Vinyl alcohol) For example, Sekisui Specialty Chemical Co., Ltd .: SEVOL ULTALUX AD, Mitsubishi Chemical Co., Ltd .: Diafix C-601) and the like can be mentioned.

Specific examples of the synthetic cationic polymer containing diallyl quaternary ammonium salt as a constituent unit include a polymer of diallyldimethylammonium chloride (INCI name: polyquaternium-6, for example, Lubrizol: Marcourt 100), (dimethyldiallylammonium chloride). / Acryl) Polymers (INCI Polyquaternium-7, eg Lubrizol: Marcourt 550, 740), (Acrylic Acid / Dialyldimethylammonium Chloride) Polymers (INCI Name: Polyquaternium-22, eg Lubrizol: Marcourt 280, 295) ), (acrylamide / acrylic acid / diallyldimethylammonium chloride) polymer (INCI name: polyquaternium-39, for example, Lubrizol: Marcourt Plus 3330, 3331) and the like.

Examples of the nonionic thickening polymer include a synthetic nonionic polymer containing a natural or semi-synthetic nonionic polysaccharide, vinyl alcohol or oxyalkylene as a constituent unit.

Specific examples of natural or semi-synthetic nonionic polysaccharides include water-soluble natural polysaccharides such as starch, guar gum, locust bean gum and glucomannan, and alkylene oxides reacted with cellulose, starch, guar gum, locust bean gum and the like. Examples thereof include water-soluble hydroxyalkylated polysaccharides. Specific examples include guar gum (for example, DSP Gokyo Food & Chemical: Pullulan S), pullulan (for example, Hayashibara Co., Ltd .: Pullulan PI-20) and the like. Hydroxyethyl cellulose (eg, Daicel FineChem: SE-850, Dow Chemical: Cellosize HEC QP-52000-H), Methyl hydroxyethyl cellulose (Axonobel: STRUCTURE CELL 12000M), Hydroxypropyl cellulose (eg, Nippon Soda: HPC) -H, HPC-M, HPC-L), hydroxypropylmethyl cellulose (for example, Shin-Etsu Chemical Co., Ltd .: Metrose 60SH-10000) and the like.

Specific examples of the synthetic nonionic thickening polymer containing vinyl alcohol or oxyalkylene as a constituent unit include polyvinyl alcohol (for example, Nippon Synthetic Chemical Co., Ltd .: Gosenol EG-40, GH-05, KH-20, NH). -26), Highly Polymerizable Polyethylene Glycol (eg Dow Chemical: Polyox WSR N-60K, WSR301, WSR303), (PEG-240 / Decyltetradeceth-20 / HDI) Copolymer (eg ADEKA: Adecanol) GT-700) and the like.

Among these thickeners, the viewpoint of suppressing the rate of water volatilization after application, promoting the penetration of the component (A) into the hair, and sufficiently exerting the effect of alleviating curly hair, as well as the softness and shape of the hair. From the viewpoint of improving ease of attachment, natural or semi-synthetic polysaccharides are preferable, at least one selected from xanthan gum, hydroxyxanthan gum and hydroxyethyl cellulose is more preferable, and at least one selected from xanthan gum and hydroxyxanthan gum is more preferable. ..

Thickeners can be used alone or in combination of two or more. The content of the component (C) in the first composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, and preferably 5% by mass or less. It is more preferably 3% by mass or less, still more preferably 2% by mass or less.

[Component (D): Organic solvent]
The first composition may further contain an organic solvent represented by the following general formula (D-1) as the component (D).
R ^2- (OCH ₂ CH ₂ ) _q -R ³ (D-1)
[In the formula, R ² indicates a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, R ³ indicates a hydrogen atom or a hydroxyl group, and q indicates an integer of 0 or more and 5 or less. However, when q is 0, R ² and R ³ do not become hydrogen atoms at the same time, and when q is not 0, when R ² is a hydrogen atom, R ³ is a hydrogen atom and R ² is an alkyl group. If so, R ³ is a hydroxyl group. ]

Examples of such a component (D) include a monohydric alcohol having 1 or more and 4 or less carbon atoms, and ethylene having R ² having 1 or more and 5 or less carbon atoms and having a linear or branched alkyl having q of 1 or more and 5 or less. Glycol monoalkyl ethers can be mentioned. Specific examples thereof include ethanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. Of these, ethanol, propanol, and isopropanol were selected from the viewpoint of obtaining the desired prohydrophobicity for the uniformity and stability of the composition and promoting the penetration of the component (A) contained in the composition into the hair. At least one of them is preferable, and ethanol is more preferable.

Any of these organic solvents can be used alone or in combination of two or more. The content of the component (D) in the first composition obtains the desired prohydrophobicity for the uniformity and stability of the composition, and the component (A) contained in the composition penetrates into the hair. From the viewpoint of promotion, it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 3% by mass or more, and preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably. It is 10% by mass or less.

[Ingredient (E): Aromatic alcohol]
The first composition can further contain an aromatic alcohol as the component (E) from the viewpoint of achieving both the strength of the effect of alleviating curly hair and the difficulty of entanglement of hair. Examples of such aromatic alcohols include benzyl alcohol, cinnamyl alcohol, phenethyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, phenoxyethanol, 2-benzyloxyethanol and the like. Of these, at least one selected from benzyl alcohol and 2-benzyloxyethanol is preferable, and benzyl alcohol is more preferable, from the viewpoint of compatibility with aromatic sulfonic acid.

Any of these aromatic alcohols can be used alone or in combination of two or more. The content of the component (E) in the first composition is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably, from the viewpoint of improving the hair habit alleviating effect and the hair entanglement resistance. Is 4% by mass or more, and from the same viewpoint, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less.

〔solvent〕
The first composition preferably uses water as a solvent from the viewpoint of sufficiently permeating the component (A) into the hair.

[Conditions in the first composition]
The first composition does not contain the aromatic sulfonic acid of the component (B) contained in the second composition used in the step (iii) described later or a salt thereof, that is, the content is 0% by mass. Is preferable. Further, even when the composition contains the component (B) (for example, 0.0001% by mass or more in the composition), the content of the component (B) in the composition is preferably less than 3% by mass. It is preferably less than 1% by mass, more preferably less than 0.5% by mass.

Further, the first composition may further contain a surfactant. However, the content of the surfactant in the composition is preferably 2% by mass or less, from the viewpoint of achieving both a sufficient effect of alleviating curly hair and a uniform formulation of the composition. It is preferably 1% by mass or less, more preferably 0.1% by mass or less, still more preferably 0.01% by mass or less, still more preferably 0% by mass.

The pH of the first composition is a viewpoint of promoting the penetration of the aromatic sulfonic acid or a salt thereof of the component (B) applied to the hair in the step (iii) into the hair, and a viewpoint of further relaxing the curly hair. , And from the viewpoint of improving the softness and ease of shaping of the hair, it is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and preferably 10 or less, more preferably 8 or less, further. It is preferably 7 or less. From the viewpoint of further reducing damage to the hair and scalp while fully exerting the effect of alleviating curly hair, and from the viewpoint of improving the feel when the above composition is applied to the hair and making it easier to apply the composition to the hair. In the above range, the pH of the composition is more preferably 5 or more, and further preferably 6 or more. On the other hand, from the viewpoint of further alleviating the curly hair, the above composition is preferably acidic. When the effect of alleviating the curly hair is preferentially considered, the pH of the composition is preferably 7 or less, more preferably 5 or less, and preferably 2 or more, more preferably 3 or more. The pH of the first composition is 10-fold diluted with ion-exchanged water and measured with a pH meter under a temperature condition of 25 ° C.

● Second composition [Component (B): aromatic sulfonic acid having a molecular weight of 300 or less or a salt thereof]
The second composition used in the step (iii) contains an aromatic sulfonic acid having a molecular weight of 300 or less or a salt thereof as the component (B). Examples of the aromatic sulfonic acid of the component (B) or a salt thereof include naphthalene sulfonic acids, azulene sulfonic acids, benzophenone sulfonic acids, benzene sulfonic acids and the like.

Examples of naphthalene sulfonic acids include compounds represented by the following general formula (1).

[In the formula, one or more of A ¹ to A ⁸ indicate a sulfo group or a salt thereof, and the remainder represents a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a carboxy group, a lower alkoxycarbonyl group, an alkyl group, an alkenyl group, or a lower group. An alkoxy group, a formyl group, an acyl group, a phenylazo group which may have a substituent or -N (R') (R'') (R'and R'' are hydrogen atoms, lower alkyl groups and lower alkenyl groups. , A phenyl group, a benzyl group or an acyl group). ]

Specific examples of these naphthalene sulfonic acids include 1- or 2-naphthalene sulfonic acid (α- or β-naphthalene sulfonic acid), 2,7-naphthalenedisulfonic acid, 1,5-naphthalenedisulfonic acid, and 2,6-naphthalene. Disulfonic acid, 1-naphthol-2-sulfonic acid, 1-naphthol-4-sulfonic acid, 2-naphthol-6-sulfonic acid, 2-naphthol-7-sulfonic acid ,, 2,3-dihydroxynaphthalene-6-sulfon Acid, 1,7-dihydroxynaphthalene-3-sulfonic acid, chromotropic acid (4,5-dihydroxynaphthalene-2,7-disulfonic acid), 3,6-dihydroxynaphthalene-2,7-disulfonic acid, S acid ( 1-Amino-8-naphthol-4-sulfonic acid), gamma acid (2-amino-8-naphthol-6-sulfonic acid), J acid (2-amino-5-naphthol-7-sulfonic acid), 1 -Amino-2-naphthol-4-sulfonic acid, 1-naphthylamine-4-sulfonic acid, Broener's acid (2-naphthylamine-6-sulfonic acid), Clave's acid (1-naphthylamine-7-sulfonic acid), 2-naphthylamine -1-sulfonic acid, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 2,7-diamino-1-naphthol-3-sulfonic acid, 7,8-diamino-1-naphthol- 3-sulfonic acid, naphthalenesulfonic acid formarin polycondensate with a molecular weight of 300 or less, 6-methyl-2-naphthalenesulfonic acid, 4-ethyl-1-naphthalenesulfonic acid, 5-isopropyl-1-naphthalenesulfonic acid, 5-butyl -2-Naphthalene sulfonic acid and salts thereof and the like can be mentioned.

Specific examples of azulene sulfonic acids include guaiazulene sulfonic acid, 1-azulene sulfonic acid, 3-acetyl-7-isopropyl-1-azulene sulfonic acid, 3- (2-hydroxyethyl) -7-isopropyl-1-azulene. Sulfonic acid, 3-methyl-7-isopropyl-1-azulene sulfonic acid, 7-isopropyl-1-azulene sulfonic acid, 3-phenyl-6-isopropyl-1-azulene sulfonic acid, 1,4-dimethyl-7-isopropyl -2-azulene sulfonic acid, 4-ethoxy-3-ethyl-6-isopropyl-1-azulene sulfonic acid, 1,3-azurange sulfonic acid, 4,6,8-trimethyl-1,3-azurange sulfonic acid, 3 -Formyl-4,6,8-trimethyl-1-azulene sulfonic acid and salts thereof can be mentioned.

Examples of the benzophenone sulfonic acid group include a compound represented by the following general formula (2).

[In the formula, one or more of A ¹¹ to A ²⁰ indicate a sulfo group or a salt thereof, and the remainder represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, an amino group, a lower alkyl group, a lower alkenyl group, a lower alkoxy group or Shows an acyl group. ]

Specific examples of these benzophenone sulfonic acids include oxybenzene sulfonic acid, o-chlorobenzophenone sulfonic acid, p-chlorobenzophenone sulfonic acid, 2-hydroxybenzophenone sulfonic acid, 4-hydroxybenzophenone sulfonic acid, and 2-aminobenzophenone sulfonic acid. , 4-Aminobenzophenone sulfonic acid, 2-methylbenzophenone sulfonic acid, 4-methoxybenzophenone sulfonic acid, 4,4'-dimethylbenzophenone sulfonic acid, 4,4'-dimethoxybenzophenone sulfonic acid, salts thereof and the like. ..

Examples of the benzenesulfonic acid include a compound represented by the following general formula (3).

[In the formula, one or more of A ²¹ to A ²⁶ indicate a sulfo group or a salt thereof, and the remainder indicates a hydrogen atom or a lower alkyl group. ]

Specific examples of benzene sulfonic acids include benzene sulfonic acid, o-toluene sulfonic acid, p-toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, ethylbenzene sulfonic acid, 2,4,6-trimethylbenzene sulfonic acid and their respective. Examples include salt.

Examples of the above aromatic sulfonic acid salt include sodium salt, potassium salt, lithium salt, aluminum salt, ammonium salt (NH ⁴⁺ ), organic ammonium salt and the like.

As the aromatic sulfonic acid of the component (B) or a salt thereof, naphthalene sulfonic acid represented by the general formula (1), in general, from the viewpoint of alleviating curly hair more strongly, giving a soft feel, and making it difficult for the hair to get entangled. At least one selected from benzophenone sulfonic acids represented by the formula (2) and benzene sulfonic acids represented by the general formula (3) is preferable, and 2-naphthalene sulfonic acid (β-naphthalene sulfonic acid), 1- At least one selected from naphthalene sulfonic acid (α-naphthalene sulfonic acid), p-toluene sulfonic acid, xylene sulfonic acid, hydroxymethoxybenzophenone sulfonic acid (oxybenzon-5) and salts thereof is more preferable. Among them, 1- or 2-naphthalene sulfonic acid (α- or β-naphthalene sulfonic acid) or a salt thereof is more preferable from the above viewpoint.

These aromatic sulfonic acids or salts thereof can be used alone or in combination of two or more. The content of the component (B) in the second composition is preferably 1 % by mass or more, more preferably, from the viewpoint of improving the curly hair easing effect, the hair wash resistance of the curly hair easing effect, and the lightness of the touch after the hair treatment. It is preferably 2.5% by mass or more, more preferably 4% by mass or more, further preferably 5% by mass or more, still more preferably 6% by mass or more, and to have a light touch after hair treatment and resistance to entanglement of hair. From the viewpoint of improvement, it is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less.

[Ingredient (C): Thickener]
The second composition preferably further contains the thickener of the above-mentioned component (C) from the viewpoint of more strongly relaxing the curly hair and improving the softness and ease of shaping of the hair. Thickeners can be used alone or in combination of two or more. The content of the component (C) in the second composition is preferably 0.1% by mass or more, more preferably, from the viewpoint of promoting the penetration of the component (B) into the hair and sufficiently exerting the effect of alleviating the curly hair. It is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less.

[Ingredient (E): Aromatic alcohol]
The second composition can further contain the aromatic alcohol of the above-mentioned component (E) from the viewpoint of achieving both the strength of the easing effect of curly hair and the difficulty of entanglement of hair. Aromatic alcohols can be used alone or in combination of two or more. The content of the component (E) in the second composition improves the hair habit-relieving effect and the hair entanglement resistance, preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass. From the same viewpoint as above, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, still more preferably 10% by mass or less.

In the second composition, the mass ratio (B) / (E) of the component (B) to the component (E) is preferably 0.25 or more, more preferably 0.30 or more, and further, from the viewpoint of making the frizz relaxing effect remarkable. It is preferably 0.35 or more, more preferably 0.5 or more, and from the same viewpoint, preferably 2.5 or less, more preferably 2.3 or less, still more preferably 2.0 or less, still more preferably 1.8 or less.

[Component (D): Organic solvent]
The second composition may further contain an organic solvent represented by the above-mentioned general formula (D-1) as the component (D), but from the viewpoint of sufficiently exerting the effect of alleviating curly hair, the second composition may further contain an organic solvent represented by the above-mentioned general formula (D-1). The content of the component (D) in the second composition is preferably small, preferably 1% by mass or less, more preferably 0.1% by mass or less, and does not contain the component (D). That is, the content is more preferably 0% by mass. If a large amount of the component (D) coexists in the system, the effect of relaxing the curly hair improved by the interaction between the component (B) aromatic sulfonic acid and the component (E) aromatic alcohol may be impaired, so that this is not inhibited. It is preferable to suppress it within the concentration range. Specifically, for the component (D), the mass ratio (D) / [(B) + (E)] of the component (D) to the total of the component (B) and the component (E) is preferably 0.3 or less. It can be contained in a range. The mass ratio (D) / [(B) + (E)] is more preferably 0.2 or less, still more preferably 0.1 or less. Furthermore, it is preferable that the mass ratio (D) / [(B) + (E)] is 0, that is, the component (D) is not contained.

Further, the content of the component (D) in the second composition is preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, still more preferably, from the same viewpoint as above. Is 0% by mass.

[Ingredient (F): Multivalent alcohol]
The second composition can further contain a polyhydric alcohol as a component (F). Polyhydric alcohols have 2 to 20 carbon atoms, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,2-butylene glycol, 1, Alkylene glycols such as 3-butylene glycol, pentylene glycol and hexylene glycol; glycerins such as glycerin and polyglycerin; sugar alcohols such as xylit, mannit, galactit and sorbit; other trimethylolethane, trimethylolpropane, etc. Examples include pentaerythritol. Among these, alkylene glycols are preferable from the viewpoint of alleviating curly hair, improving the feel of hair after hair treatment, and improving the softness, resistance to entanglement, and ease of shaping of hair, and propylene glycol and di. At least one selected from propylene glycol and polypropylene glycol is preferred.

These polyhydric alcohols can be used alone or in combination of two or more. The content of the component (F) in the second composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass or less. It is more preferably 25% by mass or less, still more preferably 22% by mass or less.

[Other ingredients]
The second composition may further contain a glycylglycine derivative and a polymer surfactant from the viewpoint of making the effect of alleviating curly hair more remarkable. The glycylglycine derivative is preferably glycylglycine, glycylglycylglycine or the like or a salt thereof, and the polymer surfactant is an oxazoline-modified silicone such as Polysilicone-9, a polyether-modified silicone, an aminopolyether. Silicone-type surfactants such as modified silicones are preferred.

〔solvent〕
The second composition also preferably uses water as a solvent from the viewpoint of sufficiently permeating the component (B) into the hair.

[PH]
The pH of the second composition may be any range as long as it can be generally used as a hair cosmetic, but the pH may be 3 or more and 10 or less from the viewpoint of not damaging the hair or scalp. It is preferably 3.5 or more and 8 or less, more preferably. The pH of the second composition is 3 or more from the viewpoint of improving the feel when applying the second composition to the hair and making it easier to apply the composition to the hair while fully exerting the effect of alleviating curly hair. 8 or less is more preferable. The pH of the second composition shall be a value measured 10-fold with ion-exchanged water and measured with a pH meter under a temperature condition of 25 ° C.

From the viewpoint of suppressing chemical damage to the hair, it is preferable that none of the first and second compositions further contains a hair reducing agent. The present invention is characterized in that the hair can be deformed without breaking the SS bond of the protein in the hair, and by using a reducing agent to break the SS bond of the protein in the hair. This is a completely different technique from the perm agent that deforms hair. Examples of the hair reducing agent include thiols such as thioglycolic acid, dithioglycolic acid, cysteine and acetylcysteine, hydrogen sulfite and salts thereof.

In the present invention, "substantially free" means that the content of the target compound in the composition is preferably less than 0.1% by mass, more preferably less than 0.01% by mass, and even more preferably. , It means that the target compound is not contained in the composition.

● Hair Treatment Method The hair treatment of the present invention can be performed by a hair treatment method including the following steps (i) to (iii).
Step (i): Applying the first composition containing the component (A) to the hair Step (ii): After the step (i), the hair is heated at 15 ° C. or higher and 100 ° C. or lower for 15 seconds or longer and 60 minutes or shorter. Step of leaving Step (iii): After step (ii), a step of applying the second composition containing the component (B) to the hair.

Before the step (i), from the viewpoint of preventing hair damage, it is preferable to untangle the hair using a tool such as a hand, a comb, or a brush. Further, the hair may or may not be washed before the step (i), but if the step of washing the hair is included, a commercially available shampoo or the like can be used for washing.

[Step (i): Step of applying the first composition containing the component (A) to the hair]
Step (i) is a step of applying the first composition containing the component (A) to the hair, and when this composition contains the component (A), the habit alleviating effect is sufficiently exhibited and repeated. Shampooing can help maintain the shape of the hair with alleviated habits, and make the treated hair softer, more natural and lighter, less entangled and easier to shape. Can be done.

The first composition may be applied to dry hair or wet hair, but is preferably applied to dry hair. The hair to be treated may be all or a part of the hair.

The amount of the first composition applied to the hair in the step (i) is a bath ratio (mass of the first composition / mass of the hair) to the mass of the hair, preferably 0.05 or more, more preferably 0.1 or more. It is more preferably 0.25 or more, preferably 1.5 or less, more preferably 1.25 or less, still more preferably 1.0 or less.

After applying the first composition to the hair, in order to apply it to the entire hair, use a hand method such as rubbing the composition into the hair or passing a hand gush through the hair, or using a tool such as a brush, comb, or brush. The method and a combination thereof may be used.

[Step (ii): After step (i), leave the hair at 15 ° C or higher and 100 ° C or lower for 15 seconds or longer and 60 minutes or shorter]
The temperature when left in the step (ii) is 15 ° C. or higher and 100 ° C. or lower, preferably 60 ° C. or lower, and more preferably 30 ° C. or lower. From the viewpoint of simple treatment without the need for a special device for hair treatment, it is preferable that the temperature is 15 ° C or higher and lower than 30 ° C, that is, room temperature. On the other hand, from the viewpoint of shortening the leaving time, it can be left while being heated by a heater or the like, and the temperature in this case is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and 100 ° C. Below, it is more preferably 60 ° C. or lower.

The time left in the step (ii) is 15 seconds or more, preferably 30 seconds or more, more preferably, from the viewpoint of alleviating the curly hair, giving the hair a softer feel, and making it difficult for the treated hair to get entangled. Is 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and 60 minutes or less, preferably 45 minutes or less, more preferably 30 minutes or less. When left while heating with a heater or the like as described above, the leaving time can be further shortened, and the leaving time in this case is 15 seconds or more, preferably 30 seconds or more, more preferably. It is 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and preferably 30 minutes or less, more preferably 15 minutes or less, still more preferably 10 minutes or less.

In general, it is advantageous to leave the component in the hair for a long time under heating conditions, but the present invention is excellent in that the effect of the invention can be obtained even if it is left for a short time at room temperature. ing.

Step (ii) is preferably performed in an environment where evaporation of water is suppressed. Specific means for suppressing the evaporation of water include a method of covering the hair to which the first composition is applied in step (i) with a plastic film, a cap, etc., and continuously spraying steam such as superheated steam onto the hair. How to do it, etc.

After step (ii) and before step (iii), the first composition may or may not be rinsed from the hair. Further, when the first composition is rinsed from the hair after the step (ii) and before the step (iii), the hair may be dried after the rinse and before the step (iii). It does not have to be dried. It may also have a step of washing before rinsing. Further, after rinsing and before performing step (iii), the entanglement of the hair may or may not be untangled using a tool such as a hand, a comb, or a brush.

[Step (iii): After step (ii), a step of applying the second composition containing the component (B) to the hair]
In step (iii), the amount of the second composition applied to the hair is a bath ratio to the mass of the hair (mass of the second composition / mass of the hair) from the viewpoint of improving the habit-relieving effect after the hair treatment. ), It is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, and preferably 1.5 or less, more preferably 1.25 or less, still more preferably 1.0 or less. The hair to be treated may be all or a part of the hair, but it is preferable to apply the second composition to the portion to which the first composition is applied in the step (i).

After applying the second composition to the hair, in order to apply it to the entire hair, a method of rubbing the hair and the agent, a method of using a hand such as passing a hand gush, a method of using a tool such as a brush, a comb, a brush, and a method of using a tool such as a brush, a comb, and a brush, and The combination of the two may be used.

In the hair treatment method of the present invention, not only the method of performing the steps (i), the step (ii), and the step (iii) in order, but also the two steps (i), the step (ii), and the step (iii) or It also includes an embodiment in which three steps are performed at the same time.

That is, the step (i) may be performed on a part of the hair, the step (ii) may be left at this portion, and the step (i) may be performed on the portion of the hair that has not been subjected to the step (i). After that, when the step (i) is further performed on the hair portion where the step (i) has not been performed, the step (iii) is performed on the hair portion where the step (ii) has been completed, and the step (i) is performed. Step (ii) is performed on the finished hair. In this case, the step (i), the step (ii), and the step (iii) are performed at the same time. In short, each step may be performed in the order of step (i) → step (ii) → step (iii) for each part of the hair to be treated.

[Step (iv): Step of leaving hair after step (iii)]
After the step (iii), the hair may or may not be rinsed, but it is preferable to rinse the hair from the viewpoint of improving the lightness of the touch and the resistance to entanglement of the treated hair. Further, the present invention may include a step of washing the hair after the step (iii).

When the hair is rinsed after the step (iii), a step (iii) is further performed between the step (iii) and the step of rinsing the hair from the viewpoint of sufficiently obtaining the effect of the present invention. ), It is preferable to include a step of leaving the hair to which the second composition is applied at 15 ° C. or higher and 100 ° C. or lower for 1 minute or longer and 60 minutes or shorter.

The temperature when left in the step (iv) is 15 ° C. or higher and 100 ° C. or lower, preferably 60 ° C. or lower, more preferably 30 ° C. or lower. From the viewpoint of simple treatment without the need for a special device for hair treatment, it is preferable that the temperature is 15 ° C or higher and lower than 30 ° C, that is, room temperature. On the other hand, from the viewpoint of shortening the leaving time, it can be left while being heated by a heater or the like, and the temperature in this case is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and 100 ° C. Below, it is more preferably 60 ° C. or lower.

After applying the second composition in step (iii), the time left in step (iv) is from the viewpoint of alleviating frizz, giving the hair a soft feel, aligning the flow of hair, and giving cohesion. It is 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and 60 minutes or less, preferably 45 minutes or less, more preferably 30 minutes or less. When left while heating with a heater or the like as described above, the leaving time can be further shortened, and the leaving time in this case is 1 minute or more, preferably 3 minutes or more, more preferably. It is 5 minutes or more, preferably 30 minutes or less, more preferably 15 minutes or less, and further preferably 10 minutes or less.
In the present invention, the leaving time in the step (iv) means the time from applying the second composition to the hair in the step (iii) to starting a step other than the step of leaving the step (iv). ..

In general, it is advantageous to leave the component in the hair for a long time under heating conditions, but the present invention is excellent in that the effect of the invention can be obtained even if it is left for a short time at room temperature. ing. In the hair treatment method of the present invention, the characteristics of the hair are changed by applying the first composition containing the component (A) in advance to the hair in the step (i), and the inside of the hair of the component (B). It is presumed that such an effect can be obtained by promoting the penetration into the hair.

Step (iv) is preferably performed in an environment where evaporation of water is suppressed. Specific means for suppressing the evaporation of water include a method of covering the hair to which the second composition is applied with a plastic film, a cap, etc., a method of continuously spraying steam such as superheated steam onto the hair, and the like. Be done.

Further, when the step of rinsing the hair is performed after the step (iv), the step of washing the hair can be included after that. When the step of washing the hair is included, a commercially available shampoo or the like can be used for washing. Further, after washing the hair, a step of treating with a commercially available conditioner, treatment or the like can be included.

The hair may or may not be dried after the step of rinsing the hair, but it is more preferable to dry the hair from the viewpoint of preventing damage to the hair. Drying can be performed by natural drying, heat drying with a dryer or the like, but heat drying is preferable from the viewpoint of shortening the treatment time. In addition, from the viewpoint of further improving the cohesiveness and preventing hair damage, it is possible to untangle the hair by using a tool such as a hand, a comb, or a brush as appropriate before and / or after the drying step. preferable.

[Step (v): Heating step]
When it is desired to obtain a straight hairstyle with almost no spread from the root to the tip of the hair, it is preferable to perform a step of heating the hair as a step (v) after the step (iv). The heating temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and preferably 230 ° C. or lower, more preferably 200 ° C. or lower, still more preferably 180 ° C. or lower. The heating temperature means the temperature of the equipment used for the heat treatment or the environment in which the heat treatment is performed. Examples of the heating method include a method using a hair iron, an electric heating rod, a hot curler, and the like, and a method of using a hair iron to slide the hair from the root to the tip of the hair to straighten the hair is more preferable.

Further, the hair may or may not be rinsed between the steps (iv) and the step (v), but it is preferable not to rinse the hair from the viewpoint of correcting the curly hair and shortening the treatment time. .. Further, the hair may or may not be dried between the steps (iv) and the step (v), but from the viewpoint of suppressing damage to the hair, the water content is reduced by a dryer or the like, and then the step (v). It is preferable to do. Further, from the viewpoint of preventing hair damage, it is preferable to disentangle the hair by using a tool such as a hand, a comb, or a brush before performing the step (v). When the treatments from the step (i) to the step (iv) are performed and then the shaping is performed in the step (v), the shape of the hair is almost the same as the shaping performed in the step (v) even if the hair is repeatedly washed. Can be maintained.
If there is no hair rinsing step between steps (iv) and step (v), it is preferred to have a hair rinsing step after step (v).

On the other hand, from the viewpoint of further reducing the damage to the hair, easily alleviating the curly hair without a special device, and making the hair flow uniform and having a natural cohesive hairstyle, step (v). It is preferable not to contain. After the step (iv), even if the step (v) is not included, there is almost no change in the hair shape due to the subsequent washing of the hair, and even after repeated washing, the curly hair is alleviated, and the hair flow is naturally aligned. It has the advantage of remaining cohesive and soft hair.

In the hair treatment method of the present invention, after applying the first composition to the hair in the step (i) or after applying the second composition to the hair in the step (iii), these compositions are applied on the hair. It is possible to obtain a sufficient effect of alleviating curly hair without applying tension to the hair by an external force such as a comb or a brush during the period until the hair is removed from the hair.

The curly hair is spontaneously relieved and the effect of the present invention can be obtained without heating or forcibly deforming the hair shape by an external force, that is, without performing an advantageous operation for deforming the hair. In that respect, the hair treatment method of the present invention is excellent.

On the other hand, after the first composition is applied to the hair in step (i), or after the second composition is applied to the hair in step (iii), until these compositions are removed from the hair. In addition, by applying tension to the hair by an external force such as a comb or a brush, it is possible to further alleviate the curly hair.

The hair treatment method of the present invention is a technique that makes it possible to relieve the shape of curly hair by a principle completely different from the perm treatment using a reducing agent and the so-called relaxer treatment using a strongly alkaline hair treatment agent. Therefore, it does not include the step of applying a hair treatment agent containing a reducing agent or a hair treatment agent having a pH of 12 to 14 to the hair. Therefore, the hair treatment method of the present invention can deform the hair without damaging the hair.

[Hair bundle for evaluation]
Using Caucasian curly hair having no history of chemical treatment, a hair bundle having a length of 24 cm and a weight of 0.5 g when the hair was straightened was prepared. The hair bundle was washed with the model shampoo shown below, and then the model rinse shown below was applied. Then, after rinsing, excess water was wiped off with a towel, and the hair bundles after being air-dried for 2 hours under laboratory conditions were used for evaluation.

(Composition of model shampoo)
Ingredient (% by mass)
Polyoxyethylene (2.5) Lauryl Ether Sodium Sulfate 15.5
Lauric acid diethanolamide 2.28
Disodium edetate 0.1
Sodium benzoate 0.5
Oxybenzone 0.03
Phosphoric acid 0.075
Dibutylhydroxytoluene 0.01
Sodium chloride 0.8
Red No. 106 0.00012
Fragrance 0.26
Purified water balance 100 in total

(Composition of model rinse)
Ingredient (% by mass)
Cetearyl alcohol 2.0
Stealtrimonium chloride 0.76
Distearyldimonium chloride 2.7
Propylene glycol 5.0
Isopropanol 0.6
Ethylparaben 0.1
Ion-exchanged water balance 100 in total

[Example 1, Comparative Examples 1 and 2]
The hair treatment agent for step (i) (first composition) and the hair treatment agent for step (iii) (second composition) shown in Table 1 below were prepared. Using these hair treatment agents, the hair bundles for evaluation are treated according to the procedure shown below, and the "habit mitigation effect", "hair wash resistance of the curl mitigation effect (3 times)", and "treatment" are performed in each procedure. "Lightness of the dry hair after treatment", "Softness of the hair after treatment when moistened", "Difficulty of entanglement of dry hair after treatment", "Shaping when stress is applied to the dry hair after treatment" The results of evaluating "sex" are shown in Table 2.
The pH of each hair treatment agent was measured at room temperature (25 ° C.) by diluting it 10-fold with ion-exchanged water with a pH meter (pH meter F-21 manufactured by HORIBA, Ltd.). Hereinafter, in this example and comparative example, room temperature means 25 ° C.

(Processing procedure)
Example 1
After 0.5 g of the hair treatment agent for step (i) was applied to the dried hair bundle for evaluation and spread evenly on the hair, the entire hair bundle was covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes. Next, remove the wrap, apply 0.5 g of the hair treatment agent for step (iii) without rinsing the hair bundle, and let it blend in. Then, cover the entire hair bundle with the wrap again to seal it, and leave it at room temperature for 15 minutes. did.
Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, it was rinsed for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

Comparative Example 1
After 0.5 g of the hair treatment agent for step (i) was applied to the dried hair for evaluation and spread evenly on the hair, the entire hair bundle was covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes. Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, it was rinsed for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

Comparative Example 2
After applying 0.5 g of the hair treatment agent for step (iii) to the dried hair for evaluation and spreading it evenly on the hair, the entire hair bundle was covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes. Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, it was rinsed for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

(Evaluation item)
<Bad habit mitigation effect>
The length of the hair bundle (24 cm) when the hair before the hair treatment is straightened is L, the length of the evaluation hair bundle after the natural drying is L ₀ , and the hair after the natural drying after the treatment is L 0. The length of the bundle was L ₁ , and the degree of habit relaxation (%) was determined according to the following formula 1. Note that L ₀ and L ₁ are lengths measured by suspending the hair bundle from above and not pulling it. The larger the value, the better the habit mitigation effect.
(Equation 1) Degree of relaxation of habit = (L ₁ -L ₀ ) / (L-L ₀ ) x 100

<Hair wash resistance with habit-relieving effect (after washing hair 3 times)>
The treated hair was moistened with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, whipped for 30 seconds, and then rinsed for 30 seconds. Then, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. Then, after towel drying, it was dried for 2 minutes using a dryer (National, EH646). This treatment flow is defined as one hair wash.
The hair after repeating this treatment three times was immersed in water for 3 minutes, towel-dried, and naturally dried at room temperature for 2 hours.
The length of the hair bundle after being naturally dried after the hair washing treatment was L ₂ , and the habit relaxation duration (%) was determined according to the following formula 2. L ₂ is the length measured by suspending the hair bundle from above and not pulling it. The larger the value, the better the habit mitigation and sustaining effect.
(Equation 2) Sustainability of habit relaxation = (L ₂ -L ₀ ) / (L ₁ -L ₀ ) x 100

<Lightness of dry hair after treatment>
Regarding the lightness of the dry hair after treatment, using the model treatment treated hair shown below as the standard hair, 7 panelists were asked to say "lighter than the standard hair" / "neither can be said" / "heavier than the standard hair". I was asked to choose which one. The number of panelists who answered "lighter than standard hair" / "neither can be said" / "heavier than standard hair" is shown in order.

For the standard model treatment-treated hair, the evaluation hair bundle was washed with a model shampoo, and then 1 g of the model treatment shown in the formulation below was applied. After standing for 30 minutes, rinsing with tap water at 40 ° C. for 30 seconds, wiping off excess water with a towel, and air-drying at room temperature for 2 hours, the hair bundle was used for evaluation.

(Composition of model treatment)
Ingredient (% by mass)
Stearyl alcohol 6.9
Stearoxypropyl dimethylamine (* 1) 2.0
Sunflower seed oil 1.5
Hydroxy stearic acid hydrogenated castor oil (* 2) 0.1
Hexa (hydroxystearic acid / stearic acid / rosin acid)
Dipentaerythrityl (* 3) 0.4
Lanolin fatty acid 0.18
Dimethicone 3.2
Amodimethicone 0.3
Bisisobutyl PEG-15 / Amodimethicone) Copolymer 0.08
Lactic acid 1.3
Dipropylene glycol 3.5
Benzyl alcohol 0.4
Fragrance 0.45
Ion-exchanged water balance 100 in total

* 1: Farmin DM E-80 (manufactured by Kao Corporation)
* 2: Technol MH (manufactured by Yokoseki Oil & Fat Industry Co., Ltd.)
* 3: Cosmall 168ARV (manufactured by Nisshin Oillio)

<Softness of hair after treatment when wet>
The state in which the treated hair is moistened with tap water at 40 ° C for 1 minute is referred to as "wet", and the softness of the treated hair when wet is "softer than the untreated hair" / "which". It cannot be said that it is "harder than the hair before treatment" or "it is harder than the hair before treatment". The number of panelists who answered "softer than untreated hair" / "neither can be said" / "harder than untreated hair" is shown in order.

<Difficulty of entanglement of dried hair after treatment>
Regarding the difficulty of entanglement of dried hair after treatment, 7 panelists were asked to selectively select whether it was "difficult to entangle than before treatment" / "neither can be said" / "easier to entangle than before treatment". rice field. The number of panelists who answered "harder to get entangled than before processing" / "neither can be said" / "easier to get entangled than before processing" is shown in order.

<Shaping property when stress is applied to dried hair after treatment>
Hold the naturally dried untreated hair and the treated hair bundle between your fingers and slide it from the root to the tip of the hair at 3 cm / sec while applying a load of 600 g, then stop at the tip and let it stand for 1 minute. After that, I let go of my finger. The length of the hair bundle at that time was L ₃ , and the shapeability of the dried hair was determined according to the following formula 3. The larger the value, the better the shapeability of dry hair.
(Equation 3) Shapeability of dried hair = (L ₃ -L ₁ ) / (L-L ₁ ) x 100

[Comparative Example 3]
The one-agent hair treatment agents shown in Table 3 were prepared. The evaluation hair bundle was treated with this hair treatment agent according to the procedure shown below. "Hair relief effect" after these treatments, "Hair wash resistance of habit relief effect (3 times)", "Lightness of dry hair after treatment", "Softness of hair after treatment when moistened" The "difficulty of entanglement of dried hair after treatment" and "shapeability when stress is applied to the dried hair after treatment" were evaluated according to the above-mentioned methods and criteria. The evaluation results are shown in Table 3.

(Processing procedure)
After applying 0.5 g of a one-agent hair treatment agent to the dried evaluation hair and spreading it evenly on the hair, the entire hair bundle was covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes. Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, it was rinsed for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

[Examples 2 to 14]
The hair treatment agent for step (i) and the hair treatment agent for step (iii) shown in Table 4 below were prepared. Using these hair treatment agents, the hair bundles for evaluation are treated according to the procedure shown below, and "the habit-relieving effect", "the habit-relieving effect of hair wash resistance (3 times)", and "the feel of dried hair after treatment". The above-mentioned methods for "lightness", "softness of treated hair when moistened", "difficulty in entanglement of dried hair after treatment", and "shapeability when stress is applied to dried hair after treatment". And evaluated according to the criteria. The evaluation results are shown in Table 4 .

(Processing procedure)
After 0.5 g of the hair treatment agent for step (i) was applied to the dried hair bundle for evaluation and spread evenly on the hair, the entire hair bundle was covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes. Next, remove the wrap, apply 0.5 g of the hair treatment agent for step (iii) without rinsing the hair bundle, and let it blend in. Then, cover the entire hair bundle with the wrap again to seal it, and leave it at room temperature for 15 minutes. did.
Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, it was rinsed for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

[Examples 15 and 16]
The evaluation hair bundle was treated with the hair treatment agent for step (i) and the hair treatment agent for step (iii) shown in Table 1 according to the procedure shown below. "Hair relief effect" after these treatments, "Hair wash resistance of habit relief effect (3 times)", "Lightness of dry hair after treatment", "Softness of hair after treatment when moistened" The "difficulty of entanglement of dried hair after treatment" and "shapeability when stress is applied to the dried hair after treatment" were evaluated according to the above-mentioned methods and criteria. The evaluation results are shown in Table 5.

(Processing procedure)
Example 15
After applying 0.5 g of the hair treatment agent for step (i) shown in Table 1 to the dried hair bundle for evaluation and spreading it evenly on the hair, the entire hair bundle is covered with a wrap and sealed, and the hair bundle is sealed at room temperature for 15 minutes. It was left still. Next, the wrap is removed, and after further applying 0.5 g of the hair treatment agent for step (iii) shown in Table 1 without rinsing the hair bundle and letting it blend in, the entire hair bundle is covered with the wrap again and sealed at room temperature. It was allowed to stand for 15 minutes.
Then, the wrap was removed, the hair treatment agent on the hair bundle was scraped off with a comb, and the hair bundle was heated using a straight iron (manufactured by Taiff, model number TITANIUM450) heated to 200 ° C.
Then, it was rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and it was whipped for 30 seconds. Then, after rinsing for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

(Processing procedure)
Example 16
After applying 0.5 g of the hair treatment agent for step (i) shown in Table 1 to the dried hair bundle for evaluation and spreading it evenly on the hair, the entire hair bundle is covered with a wrap and sealed, and the hair bundle is sealed at room temperature for 15 minutes. It was left still. Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, after rinsing for 30 seconds, the hair was towel-dried.
Then, after further applying 0.5 g of the hair treatment agent for step (iii) shown in Table 1 and letting it blend in, the entire hair bundle was again covered with a wrap to seal it, and the hair was allowed to stand at room temperature for 15 minutes.
Then, the wrap was removed, rinsed with tap water at 40 ° C. for 30 seconds, 1 g of model shampoo was applied, and the mixture was whipped for 30 seconds. Then, after rinsing for 30 seconds, 1 g of model rinse was applied, soaked for 30 seconds, and rinsed with tap water at 40 ° C. for 30 seconds. The hair bundle was then towel-dried and air-dried at room temperature for 2 hours.

Claims (11)

A hair treatment method comprising the following steps (i) to (iii) and not including a step of applying a hair treatment agent containing a reducing agent to the hair.
Step (i): A step of applying the first composition containing the following component (A) to hair.
(A) 3,4-Methylenedioxyphenol, resorcinol, 4-n-butylresorcinol, 4- (1-phenylethyl) resorcinol or phloroglucinol or salts thereof
Step (ii): After step (i), leave the hair at 15 ° C or higher and 100 ° C or lower for 15 seconds or longer and 60 minutes or shorter. Step (iii): After step (ii), the following component (B) is contained. The process of applying the second composition to the hair
(B) Aromatic sulfonic acid having a molecular weight of 300 or less or a salt thereof The hair treatment method according to claim 1, wherein after the step (iii), a step of rinsing the hair is included, and a step (iv) is further included between the step (iii) and the step of rinsing the hair.
Step (iv): A step of leaving the hair coated with the second composition at 15 ° C or higher and 100 ° C or lower for 1 minute or longer and 60 minutes or lower. The hair treatment method according to claim 1 or 2 , wherein the content of the organic solvent represented by the following general formula (D-1) in the first composition is 10% by mass or less.
R ^2- (OCH ₂ CH ₂ ) _q -R ³ (D-1)
[In the formula, R ² indicates a hydrogen atom or an alkyl group having 1 or more and 5 or less carbon atoms, R ³ indicates a hydrogen atom or a hydroxyl group, and q indicates an integer of 0 or more and 5 or less. However, when q is 0, R ² and R ³ do not become hydrogen atoms at the same time, and when q is not 0, when R ² is a hydrogen atom, R ³ is a hydrogen atom and R ² is an alkyl group. If so, R ³ is a hydroxyl group. ] The hair treatment method according to any one of claims 1 to 3 , further comprising a thickener as a component (C) in the first composition. The hair treatment method according to any one of claims 1 to 4 , wherein the pH of the first composition at 25 ° C. is 2 or more and 10 or less. The hair treatment method according to any one of claims 1 to 5 , wherein the pH of the first composition at 25 ° C. is 5 or more and 8 or less. The hair treatment method according to any one of claims 1 to 6 , further comprising a thickener as the component (C) in the second composition. The hair treatment method according to any one of claims 1 to 7, further comprising an aromatic alcohol as the component (E) in the second composition. The hair treatment method according to any one of claims 2 to 8 , wherein the temperature at which the hair is left in the step (iv) is 15 ° C. or higher and lower than 30 ° C. The hair treatment method according to any one of claims 2 to 8 , wherein the temperature at which the hair is left in the step (iv) is 30 ° C. or higher and 100 ° C. or lower, and the leaving time is 1 minute or longer and 30 minutes or shorter. .. The hair treatment method according to any one of claims 1 to 10 , which does not include a step of applying a hair treatment agent having a pH of 12 to 14 to the hair.