JPWO2020021798A1 - Hair protectant, hair treatment agent and hair treatment method - Google Patents

Abstract

Provided are a novel hair protectant capable of suppressing hair damage and improving the feel of the hair, and a hair treatment agent containing the same. The hair protectant according to one aspect of the present invention contains a perfluoropolyether.

Description

The present invention relates to a hair protective agent, a hair treatment agent containing the hair protective agent, and the use of the hair treatment agent.

Hair color treatment (also called "hair dyeing treatment") and permanent wave treatment (also simply called "perm treatment"), which are a type of hairdressing and beauty treatment, involve a chemical reaction to the hair and can damage the hair. Are known. These two types of treatment have different action steps. That is, the hair color treatment decomposes the melanin pigment in the hair with hydrogen peroxide, whereas the permanent wave treatment uses an oxidation / reduction reaction to cleave and recombine the disulfide bond of the hair keratin (Non-Patent Document 1). See). As a result, the hair color treatment deteriorates the surface of the hair, while the permanent wave treatment deteriorates mainly the inside of the hair, and the properties of damage to the hair are different.

Various hair protection components have been proposed as techniques for repairing and improving hair damaged by such treatment and irradiation with ultraviolet rays. For example, Patent Document 1 describes (A) an N-acylamino acid condensate, (B) an amino group-free organopolysiloxane and an amino-modified organopolysiloxane, and (C) a polyoxy having an ethylene oxide addition molar number of 60 or more. Disclosed is an oil-in-water emulsion composition for hair cosmetics containing ethylene ethylene bean oil and / or polyoxyethylene cured bean oil, and (D) water. Patent Document 2 discloses a hair protection component containing a protein having an average molecular weight measurement value of 11,000 measured by gel filtration column chromatography separated and purified from human hair.

Japanese Patent Publication "Japanese Patent Application Laid-Open No. 2015-110538" Japanese Patent Publication "Japanese Patent Laid-Open No. 2004-286738"

"Science of Wave" edited by Japan Permanent Wave Liquid Industry Association, New Beauty Publishing Co., Ltd., April 10, 2002, pp. 13-31

However, with the conventional hair protection component as described above, it has been difficult to suppress damage to the hair and improve the feel of the hair at the same time. That is, in order to improve the feel of hair, a silicone-based hair protectant has been mainly used (see, for example, Patent Document 1). However, although the silicone-based hair protectant has the effect of improving the feel of the hair surface, it cannot restore the strength of the hair. On the other hand, in order to suppress hair damage, keratin-based hair protectants have been mainly used (see, for example, Patent Document 2). Keratin-based hair protectants have the effect of increasing the strength of hair, but the stickiness peculiar to proteins remains on the surface of the hair, and the feel of the hair does not improve, but rather tends to worsen.

One aspect of the present invention is to provide a novel hair protectant and a hair treatment agent containing the novel hair protectant, which can solve the above-mentioned problems.

As a result of diligent studies, the present inventors have found that it is effective to use perfluoropolyether as a hair protective agent, and have completed the present invention.

That is, the present invention includes the following configurations.
<1> A hair protectant containing perfluoropolyether.
<2> The hair protectant according to <1>, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (1).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r- (CF ₂ ) _{s- CF 3} (1)
[In equation (1),
m + s indicates a real number from 0 to 5,
n + o + p + q + r represents a real number from 1 to 50. ]
<3> The hair protectant according to <1>, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (2).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r- (CF ₂ ) _s- CH ₂ O-R1 (2)
[In equation (2),
R1 indicates H,-[CH _2- CH (OH) CH ₂ O] _x- R3, or-(CH ₂ ) _y OH.
x indicates a real number from 1 to 5, y indicates a real number from 1 to 6,
R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB.
B is an alkoxy group, an amide group, or an amino group of C1 to C4.
m + s represents a real number from 1 to 5,
n + o + p + q + r represents a real number from 1 to 50. ]
<4> The hair protectant according to <1>, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (3).
R2-OCH _2- (CF ₂ ) _m −O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − (CF ₂ CF ₂ CF ₂ O) _r − (CF ₂ ) _s −CH ₂ O—R1 (3)
[In equation (3),
R1 and R2 independently represent H,-[CH _2- CH (OH) CH ₂ O] _x- R3, or-(CH ₂ ) _y OH, respectively.
x indicates a real number from 1 to 5, y indicates a real number from 1 to 6,
R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB.
B is an alkoxy group, an amide group, or an amino group of C1 to C4.
m + s represents a real number from 1 to 5,
n + o + p + q + r represents a real number from 1 to 50. ]
<5> The hair protectant according to any one of <1> to <4>, wherein the perfluoropolyether has a number average molecular weight of 100 to 10,000.
<6> A hair treatment agent containing the hair protective agent according to any one of <1> to <6>.
<7> The hair treatment agent according to claim 6, wherein the content of perfluoropolyether is 0.005 to 20% by mass.
<8> A hair treatment method using the hair treatment agent according to <6> or <7>.

According to one aspect of the present invention, there is provided a novel hair protectant capable of suppressing damage to hair and improving the feel of the hair, and a hair treatment agent containing the same.

(A) is an SEM image showing the surface of healthy hair that has not been subjected to hair coloring treatment. (B) is an SEM image showing the surface of a hair sample treated with a hair coloring agent to which D2N is added as a hair protective agent. (C) is an SEM image showing the surface of the hair sample treated with the hair coloring agent to which D2N is not added. It is a graph which shows the sulfur content of the hair sample treated with the hair coloring agent containing perfluoropolyether.

Hereinafter, examples of embodiments of the present invention will be described in detail, but the present invention is not limited thereto. Unless otherwise specified in the present specification, "A to B" representing a numerical range means "A or more and B or less".

[1. Perfluoropolyether]
[Structure and physical properties of perfluoropolyether]
The hair protectant according to one aspect of the present invention contains a perfluoropolyether.

As used herein, the term "perfluoropolyether" refers to-(CF ₂ O)-,-(C ₂ F ₄ O)-,-(C ₃ F ₆ O)-,-(C ₄ F ₈ O)-. ,-(C ₅ F ₁₀ O)-, and-(C ₆ F ₁₂ O)-represents a compound having one or more repeating units of one or more types selected from. The repeating unit preferably contains 1 to 50 units, and more preferably 1 to 20 units.

The repeating unit may be linear or may have branches. It is preferably linear. For example,-(C ₃ F ₆ O)-is- (CF ₂ CF ₂ CF ₂ O)-,-(CF (CF ₃ ) CF ₂ O)-,-(CF ₂ CF (CF ₃ ) O)- However, it is preferably − (CF ₂ CF ₂ CF ₂ O) −. The same applies to other repeating units.

The end of the perfluoropolyether may or may not be modified with a functional group. Here, "not modified with a functional group" means that the terminal is a perfluoroalkyl group. Examples of the functional group modifying the terminal include a hydroxyl group, a phosphazene group, an amino group, a carboxyl group, a phenyl group, a phenoxy group, a thiol group, an amide group and an alkoxy group. In addition, the options of R1 and R2 in the formulas (2) and (3) described later are also examples of functional groups that modify the ends.

As long as the effect of the present invention is exhibited, the perfluoropolyether may have a substituent or may contain an atom other than a carbon atom, a fluorine atom and an oxygen atom. Examples of such a substituent include a hydroxyl group, a phosphazene group, an amino group, a carboxyl group, a phenyl group, a phenoxy group, a thiol group, an amide group and an alkoxy group. Examples of such atoms other than carbon atom, fluorine atom and oxygen atom include hydrogen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom and halogen atom other than fluorine atom.

In one embodiment, the perfluoropolyether has the structure of the following formula (1).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r − (CF ₂ ) _{s − CF 3} (1).

In the formula (1), m + s is a real number from 0 to 5, preferably a real number from 0 to 4. n + o + p + q + r is a real number of 1 to 50, preferably a real number of 1 to 20.

Formula (1) represents a perfluoropolyether whose both ends are not modified with a functional group. Such perfluoropolyethers can be prepared, for example, using Demnum (manufactured by Daikin Industries, Ltd.), Krytox (manufactured by DuPont Specialty Chemicals) and Fomblin (manufactured by Solvay) as starting materials (for example, a desired structure by chromatography). By separating the perfluoropolyether having.). For example, when Demnum is used as a starting material, a perfluoropolyether in which Demnum is the main chain and both ends are not modified with a functional group can be prepared. Such perfluoropolyethers are referred to herein as "D2N". Similarly, a perfluoropolyether having Krytox or Fomblin as the main chain and having both ends not modified with functional groups can be prepared. Of these, the latter is referred to as "Formlin X" in the present specification. Further, as another example of a perfluoropolyether having Fomblin as the main chain and both ends not modified with functional groups, Fomblin HC / R (manufactured by Nikko Chemicals Co., Ltd.) can be mentioned.

The structure of D2N is as follows.
CF ₃ CF ₂ CF ₂ (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CF ₃ (m is a real number of 1 to 50, preferably a real number of 1 to 10).

The structure of Krytox is as follows.
CF ₃ CF ₂ CF ₂ O- (CF (CF ₃ ) CF ₂ O) _z- CF _{2 CF 3} (z is a real number from 1 to 50, preferably a real number from 1 to 10).

The structure of Formlin X is as follows.
CF ₃ CF ₂ O (CF ₂ CF ₂ O) _x (CF ₂ O) _y CF ₂ CF ₃ (x + y is a real number of 1 to 50, preferably a real number of 1 to 10).

The structure of Fomblin HC / R is as follows.
CF ₃ O (CF ₂ O) _x (CF ₂ CF (CF ₃ ) O) _y CF ₃ (x + y is a real number of 1 to 50, preferably a real number of 1 to 10).

In one embodiment, the perfluoropolyether has the structure of the following formula (2).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r- (CF ₂ ) _s- CH ₂ O-R1 (2).

In formula (2), R1 represents H,-[CH _2- CH (OH) CH ₂ O] _x- R3 or-(CH ₂ ) _y OH. Here, x is a real number from 1 to 5. y is a real number from 1 to 6. R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB, and B is an alkoxy group, an amide group, or an amino group of C1 to C4.

Here, C ₆ H ₅ and C ₆ H ₄ in R3 are benzene rings. When R3 is C ₆ H ₄ OB, the positional relationship between the perfluoropolyether group and OB may be any of the ortho-position, the meta-position, and the para-position.

Preferably, R1 is H, CH ₂ CH (OH) CH ₂ OH, CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OH, CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH). Selected from CH ₂ OCH ₂ CH (OH) CH ₂ OH or CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH _{2 OH} ..

In the formula (2), m + s is a real number of 1 to 5, preferably a real number of 2 to 4. n + o + p + q + r is a real number of 1 to 50, preferably a real number of 1 to 20.

Formula (2) represents a perfluoropolyether whose one end is not modified with a functional group. Such perfluoropolyethers can be prepared, for example, using Demnum (manufactured by Daikin Industries, Ltd.) and Fomblin (manufactured by Solvay) as starting materials (for example, separating perfluoropolyethers having a desired structure by chromatography). according to.). For example, when Demnum is used as a starting material, a perfluoropolyether having Demnum as the main chain and one end of which is not modified with a functional group can be prepared. Such perfluoropolyethers are referred to herein as "D2M". Similarly, a perfluoropolyether having Fomblin as the main chain and one end of which is not modified with a functional group can be prepared. Such perfluoropolyethers are referred to herein as "Fomblin Y".

The structure of D2M is as follows.
CF ₃ CF ₂ CF ₂ (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OH (m is a real number of 1 to 50, preferably a real number of 1 to 20).

The structure of Formlin Y is as follows.
CF ₃ CF ₂ O (CF ₂ CF ₂ O) _x (CF ₂ O) _y CF ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ OH (x + y is a real number from 1 to 50, and a real number from 10 to 30. Is preferable).

In one embodiment, the perfluoropolyether has the structure of the following formula (3).
R2-OCH _2- (CF ₂ ) _m −O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − (CF ₂ CF ₂ CF ₂ O) _r − (CF ₂ ) _s −CH ₂ O—R1 (3).

In formula (3), R1 and R2 independently represent H,-[CH _2- CH (OH) CH ₂ O] _x- R3 or-(CH ₂ ) _y OH, respectively. Here, x is a real number from 1 to 5. y is a real number from 1 to 6. R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB, and B is an alkoxy group, an amide group, or an amino group of C1 to C4. _{Regarding C 6} H ₅ and C ₆ H _{4 in} R3, the same as the description of the equation (2).

Preferably, R1 and R2 are independently H, CH ₂ CH (OH) CH ₂ OH, CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OH, CH ₂ CH (OH) CH _{2 respectively.} OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OH or CH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH ₂ OCH ₂ CH (OH) CH Selected from _{2 OH.}

In the formula (3), m + s is a real number of 1 to 5, preferably a real number of 2 to 5, and more preferably a real number of 3 to 5. n + o + p + q + r is a real number of 1 to 50, preferably a real number of 1 to 20.

Formula (3) represents a perfluoropolyether having both ends modified with a functional group. Such a perfluoropolyether can be prepared, for example, using Demnum (manufactured by Daikin Industries, Ltd.) as a starting material (for example, by separating the perfluoropolyether having a desired structure by chromatography). In this case, it is possible to prepare a perfluoropolyether in which Demnum is the main chain and both ends are modified with functional groups. Such perfluoropolyethers are referred to herein as "D-4OH".

The structure of D-4OH is as follows.
HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OCH ₂ CH (OH) CH ₂ OH (m is 1 to 50, 1 ~ 20 is preferable).

Among the perfluoropolyethers represented by the formulas (1) to (3), those having a Demnum main chain are more preferably used because they have a flat molecular chain and easily adhere to hair. That is, among the above-mentioned perfluoropolyethers, D2N, D2M and D-4OH are more preferably used.

In the hair protective agent according to the embodiment of the present invention, the number average molecular weight of the perfluoropolyether is preferably 100 to 10000, more preferably 1000 to 5000, and further preferably 1000 to 3000. Here, the number average molecular weight can be measured by ^{, for example, 19 F-NMR.} Perfluoropolyethers having a number average molecular weight of 100 to 10,000 are by-products of perfluoropolyethers for lubricants. Therefore, it can be said that it is preferable because a by-product which has been scarcely used in the past can be used and a perfluoropolyether for a hair protectant can be provided at a low cost.

[Manufacturing method of perfluoropolyether]
A method for producing a perfluoropolyether is a known technique (see, for example, WO01 / 021630, WO2009 / 066784, WO2016 / 092900, etc.).

[2. Hair protectant and hair treatment agent]
The hair protectant according to one embodiment of the present invention contains a perfluoropolyether. The hair protectant may contain only one type of perfluoropolyether described in Section [1], or may contain two or more types of the perfluoropolyether. The hair protectant may contain only perfluoropolyether, or may be a mixture of other substances and perfluoropolyether. Examples of other substances include non-polar substances (silicones, olefins, halogenated alkanes, etc.). When other substances and perfluoropolyether are mixed, the content of the perfluoropolyether is, for example, 20% by mass or more, 50% by mass or more, 70% by mass or more, or 90% or more. May be good.

The hair treatment agent according to one embodiment of the present invention contains the hair protective agent according to one embodiment of the present invention. Here, the "hair treatment agent" means an agent used to apply various treatments to hair. Specific examples of the hair treatment agent include, for example, a hair coloring agent for performing hair coloring treatment; a perm agent for performing permanent wave treatment; a hair styling agent for performing hair styling (hair wax, gel, foam, etc.); Shampoos to be performed; rinses, conditioners, treatments, etc. to maintain good hair condition; hair oils to further improve hair condition, non-rinse type treatments, etc.;

The content of the perfluoropolyether in the hair treatment agent according to the embodiment of the present invention is not particularly limited, but is preferably 0.005 to 20% by mass, more preferably 0.01 to 15% by mass. , 0.1 to 10% by mass is more preferable.

The hair treatment agent according to the embodiment of the present invention may contain ordinary components and / or additives contained in the hair treatment agent in addition to the perfluoropolyether. Such components and / or additives include moisturizers, fats and oils, lanolins, higher alcohols, fluorine compounds, silicones, cationized polymers, surfactants (cationic surfactants, etc.). Anionic surfactants / nonionic surfactants / amphoteric surfactants), thickening / gelling agents, preservatives, chelating agents, pH regulators / acids / alkalis, solvents, anti Examples include inflammatory agents, fragrances, pigments, antioxidants and the like.

Moisturizers include polyhydric alcohols (1,3-butylene glycol, propylene glycol, glycerin, etc.), proteins / peptides (collagen, gelatin, elastin, collagen-degrading peptide, elastin-degrading peptide, keratin-degrading peptide, etc.) Silk proteolytic peptide, soybean proteolytic peptide, wheat proteolytic peptide, casein-degrading peptide, etc.) and their derivatives, amino acids (arginine, serine, glycine, glutamic acid, trimethylglycine, etc.), plant extract components (aloe extract, hamamelis) Water, Hechima water, chamomile extract, kanzo extract, etc.), citrate, chondroitin sulfate, sodium lactate, sodium 2-pyrrolidone-5-carboxylate, and the like.

Oils and fats include vegetable oils and fats (sunflower oil, palm oil, palm oil, palm kernel oil, safflower oil, olive, avocado oil, sesame oil, evening primrose oil, wheat germ oil, macadamia nut oil, hazelnut oil, rose hip oil, Meadowfoam oil, tea tree oil, peppermint oil, corn oil, rapeseed oil, sunflower oil, cottonseed oil, soybean oil, peanut oil, rice bran oil, liquid shea butter, jojoba oil, etc.), hydrocarbons (liquid paraffin, squalane, light) Liquid isoparaffin, ceresin, paraffin wax, polyethylene, microcrystallin wax, vaseline, etc.), esters (di2-ethylhexyl succinate, isopropyl palmitate, etc.), waxes (mitsurou, candelilla wax, carnauba wax, rice wax, whale wax, etc.) , Celac, cotton wax, mokuro, hydrogenated jojoba oil, etc.).

Examples of lanolins include liquid lanolin, reduced lanolin, and adsorption-purified lanolin.

Higher alcohols include linear alcohols (lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, etc.), branched alcohols (monostearyl glycerin ether (bacyl alcohol), 2- Decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol, etc.) and the like.

Examples of the fluorine-based compounds include fluorine-based compounds and their derivatives (polyperfluoroethoxymethoxydifluorohydroxyethyl, polyperfluoroethoxymethoxydifluoromethyl distearylamide, polyperfluoroethoxymethoxydifluoroethyl polyethylene glycol phosphoric acid, etc.). Be done.

Silicones include low-viscosity dimethylpolysiloxane, high-viscosity dimethylpolysiloxane, cyclic dimethylsiloxane (decamethylcyclopentasiloxane), methylphenylpolysiloxane, diphenylpolysiloxane, silicone resin, silicone rubber, amino-modified polysiloxane, and cationic modification. Examples thereof include polysiloxane, polyether-modified polysiloxane, and fluorine-modified polysiloxane.

Examples of the cationized polymers include cationized cellulose derivatives, cationized starches, cationized guar gum, polymers or copolymers of diallyl quaternary ammonium, and quaternized polyvinylpyrrolidone derivatives.

Examples of the cationic surfactants include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid ethylsulfate aminopropylethyldimethylammonium.

Anionic surfactants include fatty acid salts, alkyl sulfates, polyoxyethylene alkyl sulfates, polyoxyethylene fatty amine sulfates, acyl N-methyltaurine salts, alkyl ether phosphate salts, and N-acyl amino acids. Examples include salt.

Examples of nonionic surfactants include polyhydric alcohol fatty acid partial esters, polyglycerin fatty acid esters, alkyldimethylamine oxides, alkyl polyglycosides, and alkyl glucosides.

Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaine, alkylamide dimethylaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaine and the like.

Examples of thickening / gelling agents include cetostearyl glucoside, guar gum, xanthan gum, carrageenan, alginic acid, tragant gum, starch derivatives, sodium carboxymethyl cellulose, carboxyvinyl polymer, meadowfoam oil fatty acid dimethicone copolypoly, and acrylic acid / methacrylic acid ester. Examples thereof include polymers, N, N-dimethylaminoethyl methacrylate diethylsulfate, N, N-dimethylacrylamide / dimethacrylate, acrylic acid / alkyl methacrylate copolymer, polyvinyl alcohol, acrylic resin alkanolamine solution, and the like. ..

Examples of preservatives include p-hydroxybenzoic acid esters, benzoates, phenoxyethanol, quaternary ammonium salts and the like.

Examples of the chelating agent include edetates, phosphonic acids, polyamino acids and the like.

Acids / acids / alkalis include phosphoric acid, malic acid, tartaric acid, carbonic acid, fumaric acid, citric acid, lactic acid, glycolic acid, succinic acid, hydrochloric acid, sulfuric acid, nitrate, hydroxyethanediphosphonic acid and their salts. , Sodium hydroxide, potassium hydroxide, disodium hydrogen phosphate, monoethanolamine, diethanolamine, triethanolamine, arginine, aqueous ammonia, aminomethylpropanol and salts thereof.

Examples of the solvent include water, ethanol, decamethylcyclopentasiloxane, lower alcohols (2-propanol, etc.) and the like.

Examples of anti-inflammatory agents include licorice derivatives (glycyrrhizic acid, carbenoxolone disodium, etc.), allantoin, guaiazulene, aloe, α-bisabolol and the like.

Examples of the antioxidant include sodium ascorbate, sodium sulfite and the like.

The hair treatment agent according to one embodiment of the present invention may contain components used for permanent wave treatment or hair straightening treatment. Examples of such a component include a reducing agent, an oxidizing agent, an alkaline agent, a reaction modifier, and the like.

Reducing agents include ammonium thioglycolate, monoethanolamine thioglycolate, L-cysteine, DL-cysteine, L-cysteine hydrochloride, DL-cysteine hydrochloride, acetylcysteine, cysteamine, cysteamine hydrochloride, thiolactic acid, and thioapple. Examples thereof include acid, glycerylthioglycolate, thioglycerin, butyrolactone thiol and the like. The reducing agent can be contained in the hair treatment agent within an acceptable range (for example, the total content of all reducing agents converted to thioglycolic acid, which is equivalent to less than 2% by mass).

Examples of the oxidizing agent include sodium bromate and hydrogen peroxide.

Examples of the alkaline agent include aqueous ammonia, monoethanolamine, triethanolamine, ammonium carbonate, sodium carbonate, sodium bicarbonate, sodium hydroxide, arginine and the like.

Examples of the reaction modifier include dithiodiglycolic acid and dithiodiglycolate.

Using the above-mentioned components, a hair treatment agent can be prepared according to a conventional method.

Examples of the dosage form of the hair treatment agent according to the embodiment of the present invention include creams, gels, emulsions, solutions, mists, foams and the like.

[3. Use of hair treatment agent]
One aspect of the present invention also includes a method of treating the hair of a subject (hair treatment method) using the hair treatment agent according to the above-mentioned aspect of the present invention.

As used herein, the "subject" is not limited to humans. The hair treatment agent according to one embodiment of the present invention can also treat the hair of non-human mammals. Examples of non-human mammals include cloven-hoofed animals (boars, wild boars, pigs, sheep, goats, etc.), cloven-hoofed animals (horses, etc.), rodents (mouse, rats, hamsters, squirrels, etc.), rabbits (rabbits). Etc.), meats (dogs, cats, ferrets, etc.) and the like. The non-human mammals described above include wild animals in addition to livestock or companion animals (pets).

As used herein, the term "hair" means "hair that grows on a subject". When the subject is a human, examples of hair include hair, beard, eyebrows, eyelashes, nose hair, ear hair, armpit hair, pubic hair, and body hair. When the subject is a human, it is preferable to use the hair treatment agent according to one embodiment of the present invention for hair.

In the present specification, "treating hair" means performing hair coloring treatment, permanent wave treatment, hair styling, hair care treatment (hair washing, treatment, etc.) and the like. The hair treatment method according to one embodiment of the present invention uses the hair treatment agent according to one embodiment of the present invention. That is, a hair treatment agent containing a hair protective agent according to an embodiment of the present invention is used. Therefore, according to the hair treatment agent according to the embodiment of the present invention, damage to the hair is suppressed (damage to the surface of the hair is suppressed, damage to the inside of the hair is suppressed, etc.), and the feel is improved (suppression of dryness, cohesiveness). (Improvement, etc.), effects such as suppression of static electricity generation can be obtained at the same time or by the same treatment.

[4. Advantages of Hair Protective Agent According to One Embodiment of the Present Invention]
The advantages that the hair protectant according to the embodiment of the present invention may have will be described below. However, certain embodiments of the present invention do not have to meet some or all of the advantages described below.

[Both suppression of damage and improvement of feel]
As described in the problem column and the effect column, the hair protective agent according to the embodiment of the present invention is a novel hair protective agent capable of both suppressing hair damage and improving the feel of the hair.

[Suppression of external and internal damage to hair]
Hair color treatment and permanent wave treatment are the main causes of hair damage. In the hair coloring treatment, the melanin pigment in the hair is decomposed by the hydrogen peroxide solution, and at the same time, the oxidative dye acts with hydrogen peroxide to develop the color. Therefore, the hair coloring treatment deteriorates the surface of the hair. On the other hand, in the permanent wave treatment, the disulfide bond of the hair is cleaved by an alkaline solution containing a reducing agent, and a new disulfide bond is formed by an oxidizing agent. Therefore, the permanent wave treatment mainly deteriorates the inside of the hair.

The hair protective agent according to one embodiment of the present invention has the effect of suppressing hair damage and improving the feel of the hair against both hair damage caused by hair coloring treatment and hair damage caused by permanent wave treatment. Play. That is, the hair protective agent according to the embodiment of the present invention reduces external damage and internal damage of hair.

[Effective use of by-products]
Perfluoropolyethers having a specific structure are industrially used as lubricating oils. However, in the manufacturing process of perfluoropolyether for lubricating oil, perfluoropolyether, which is a by-product different from the desired structure, is generated. At present, such by-products perfluoropolyether are disposed of at a high cost.

In one embodiment of the present invention, the above-mentioned by-product, perfluoropolyether, can be used in the hair protectant and hair treatment agent of the present invention. Therefore, it is possible to reduce industrial waste, and it can be said that the present invention is also useful from the viewpoint of utilizing by-products. In addition, the cost of producing a fluorine-containing compound such as perfluoropolyether is usually high, but if a by-product perfluoropolyether is used as in one embodiment of the present invention, the cost is relatively low. , It can be said that it is possible to provide a hair protective agent and a hair treatment agent containing perfluoropolyether.

Examples of the perfluoropolyether which is a by-product of the perfluoropolyether for lubricating oil include the perfluoropolyether represented by the above formulas (1) to (3) and a number average molecular weight of 100. Perfluoropolyether which is 10000 to 10000 can be mentioned. In particular, for perfluoropolyethers whose both ends are not modified with functional groups (perfluoropolyethers represented by the above formula (1), etc.), no notable industrial use has been found. The effect of using it as a by-product is great.

[Example 1]
The effect of the hair protective agent according to the embodiment of the present invention on the damage caused by the hair coloring agent to the hair was examined. Specifically, a hair sample treated with a hair coloring agent was prepared, and the breaking strength and friction coefficient of the hair sample were measured.

[How to make a hair sample]
The method for preparing the hair sample is as follows.
1. 1. We prepared a hair piece that had not undergone any chemical treatment.
2. The first agent and the second agent were mixed at a weight ratio of 1: 2 to prepare a hair coloring agent. The composition of the first agent and the second agent will be described later.
The hair coloring agent prepared in 3.2 was applied to the hair piece. The amount applied was such that hair piece: hair coloring agent = 1: 1 (weight ratio).
4. The hairpiece was allowed to stand at 30 ° C. for 30 minutes.
5. The hairpiece was washed with a 10 mass% SDS aqueous solution (sodium dodecyl sulfate aqueous solution) and then dried.

(Composition of 1st agent and 2nd agent)
The basic compositions of the first agent and the second agent are as follows. When the content of the hair protectant was changed, it was adjusted by changing the amount of water (see Examples 1-9 to 1-13 and Comparative Example 1-1). The purpose of this embodiment is to compare the damage to the hair caused by the hair coloring treatment. Therefore, the dye for hair dyeing, which is usually contained in the hair coloring agent, was not contained in the first agent used in this example.
● First agent, cetyl alcohol (higher alcohol): 10% by mass
-Polyoxyethylene cetyl ether (surfactant): 4% by mass
-Sodium cetostearyl sulfate (surfactant): 1% by mass
-Sodium ascorbate (antioxidant): 0.5% by mass
-Sodium sulfite (antioxidant): 0.5% by mass
25% ammonium water: 10% by mass
・ Sodium hydrogen carbonate: 2% by mass
・ Hair protectant: 0.5% by mass
・ Water: 71.5% by mass
● Second agent, cetyl alcohol (higher alcohol): 3% by mass
-Isopropyl palmitate (oil): 0.3%
-Polyoxyethylene cetyl ether (surfactant): 1% by mass
-Phosphoric acid (pH adjuster): 0.1% by mass
-Hydroxyethanediphosphonic acid (pH adjuster): 0.3% by mass
-Disodium hydrogen phosphate (pH adjuster): 0.1% by mass
・ 35% hydrogen peroxide: 17% by mass
-Water: 78.2% by mass.

[Measuring method of breaking strength]
Twelve hairs were arbitrarily selected from the hair pieces treated with the hair coloring agent as described above. The major axis and the minor axis of the hair were measured by a hair diameter measuring system (manufactured by Kato Tech Co., Ltd.). From the obtained values, the cross-sectional area was calculated by the following formula.
Cross-sectional area (mm ² ) = (π / 4) x major axis (mm) x minor axis (mm).

Next, the tensile breakage value (cN) of the hair was measured using a desktop material tester Tensilon STA-1150 (manufactured by Orientec Co., Ltd.). Measurements were taken in water to prevent the effects of hydrogen bonds.

Finally, the breaking strength per cross-sectional area was calculated based on the following formula.
Breaking strength (cN / mm ² ) = tensile breaking value (cN) / cross-sectional area (mm ² ).

[Measurement method of friction coefficient]
The hair piece treated with the hair coloring agent as described above was humidity-controlled for 24 hours or more under the conditions of 20 ° C. and 60% humidity. Hair samples having the same ellipticity were attached to the slide glass (12 or more per slide glass) except for the hair samples having an extreme cross-sectional area ellipticity. A friction tester KES-SE (manufactured by Kato Tech Co., Ltd.) was used to measure the coefficient of friction. The measurement sensitivity was H, the static friction load was 50 gf, and the sensor used was a silicon type. The scanning direction of the sensor was the direction from the root side of the hair to the tip side of the hair. The average value of five slide glasses 10 times per sample was defined as the average coefficient of friction (MIU), and the value obtained by multiplying the average coefficient of friction by 0.1 was defined as the coefficient of friction (μ).

[Example 1-1]
As a hair protectant, D2N (PFPE having no functional group modification at both ends) was used. The structure of D2N is as follows. The measurement results of the hair sample are shown in Table 1.
CF ₃ CF ₂ CF ₂ (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CF ₃ (m = 4.28).

[Example 1-2]
As a hair protectant, D2M (PFPE having one end not modified with a functional group) was used. The structure of D2M is as follows. The measurement results of the hair sample are shown in Table 1.
CF ₃ CF ₂ CF ₂ (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OH (m = 12).

[Example 1-3]
A mixture of D2N and D2M was used as the hair protectant (same as that used in Examples 1-1 and 1-2). The 1-2 mixing ratio was D2N: D2M = 1: 1 (mass ratio). The measurement results of the hair sample are shown in Table 1.

[Example 1-4]
As a hair protectant, Krytox (PFPE having both ends not modified with functional groups) was used. The structure of Krytox is as follows. The measurement results of the hair sample are shown in Table 1.
CF ₃ CF ₂ CF ₂ O- (CF (CF ₃ ) CF ₂ O) _z- CF _{2 CF 3} (z = 6.5).

[Example 1-5]
As a hair protectant, D-4OH (polar PFPE with both ends modified with functional groups) was used. The structure of D-4OH is as follows. The measurement results of the hair sample are shown in Table 1.
HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) _m CF ₂ CF ₂ CH ₂ OCH ₂ CH (OH) CH ₂ OH (m = 11).

[Example 1-6]
As a hair protectant, Fomblin X (PFPE having no functional group modification at both ends) was used. The structure of Formlin X is as follows. The measurement results of the hair sample are shown in Table 1.
CF ₃ CF ₂ O (CF ₂ CF ₂ O) _x (CF ₂ O) _y CF ₂ CF ₃ (x = 4.10, y = 4.18).

[Example 1-7]
As a hair protectant, Fomblin Y (PFPE having one end not modified with a functional group) was used. The structure of Formlin Y is as follows. The measurement results of the hair sample are shown in Table 1.
CF ₃ CF ₂ O (CF ₂ CF ₂ O) _x (CF ₂ O) _y CF ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ OH (x = 10, y = 10).

[Example 1-8]
Fomblin HC / R was used as a hair protectant. The structure of Fomblin HC / R is as follows, and the average molecular weight is 6,250. The measurement results of the hair sample are shown in Table 1.
CF ₃ O (CF ₂ O) _x (CF ₂ CF (CF ₃ ) O) _y CF ₃ (y / x = 20-40).

[Comparative Example 1-1]
The experiment was conducted by changing the water content to 71.5% by mass without adding a hair protectant. The measurement results of the hair sample are shown in Table 1.

[Comparative Example 1-2]
As a hair protectant, KF-8015 (dimethylpolysiloxane to which an aminopropyl group was added; manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone-based raw material, was used. The measurement results of the hair sample are shown in Table 1.

[Comparative Example 1-3]
As a hair protectant, a silicone-based raw material KF-9021 (a mixture of 50% trimethylsiloxysilicic acid and 50% cyclopentasiloxane; manufactured by Shin-Etsu Chemical Co., Ltd.) was used. The measurement results of the hair sample are shown in Table 1.

[Comparative Example 1-4]
As a hair protectant, Promois WK (a hydrolyzed peptide derived from wool; manufactured by Seiwa Kasei Co., Ltd.), which is a protein-based raw material, was used. The measurement results of the hair sample are shown in Table 1.

[Comparative Example 1-5]
As a hair protectant, Proticute H Gamma (wool-derived hydrolyzed peptide; manufactured by Ichimaru Falcos Co., Ltd.), which is a protein-based raw material, was used. The measurement results of the hair sample are shown in Table 1.

[Example 1-9]
Experiments were conducted using D2N as the hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 0.01% by mass and the water content to 71.9% by mass. went. The measurement results of the hair sample are shown in Table 2.

[Example 1-10]
Experiments were conducted using D2N as the hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 0.1% by mass and the water content to 71.9% by mass. went. The measurement results of the hair sample are shown in Table 2.

[Example 1-11]
An experiment was conducted using D2N as a hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 1.0% by mass and the water content to 71% by mass. .. The measurement results of the hair sample are shown in Table 2.

[Example 1-12]
An experiment was conducted using D2N as a hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 5.0% by mass and the water content to 67% by mass. .. The measurement results of the hair sample are shown in Table 2.

[Example 1-13]
An experiment was conducted using D2N as a hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 10.0% by mass and the water content to 62% by mass. .. The measurement results of the hair sample are shown in Table 2.

（結果）
表１によると、パーフルオロポリエーテルを毛髪保護剤として用いたヘアカラー剤においては、毛髪破断強度の向上及び摩擦係数の減少がみられる（実施例と比較例１−１とを比較して参照）。一方、シリコーン系毛髪保護剤を用いた場合、摩擦係数は減少しているが、毛髪破断強度は向上しなかった（比較例１−２、１−３を参照）。また、タンパク質系毛髪保護剤を用いた場合、毛髪破断強度は向上しているが、摩擦係数はむしろ増加した（比較例１−４、１−５を参照）。

(result)
According to Table 1, in the hair coloring agent using perfluoropolyether as the hair protective agent, the hair breaking strength is improved and the friction coefficient is decreased (see by comparing Example and Comparative Example 1-1). ). On the other hand, when the silicone-based hair protectant was used, the coefficient of friction was reduced, but the hair breaking strength was not improved (see Comparative Examples 1-2 and 1-3). In addition, when a protein-based hair protectant was used, the hair breaking strength was improved, but the coefficient of friction was rather increased (see Comparative Examples 1-4 and 1-5).

Further, according to Table 2, in the range where the D2N content was 0.01 to 10.00% by mass, the hair breaking strength was improved and the friction coefficient was decreased. Of these, the hair breaking strength was maximum when the D2N content was 1.00% by mass, and the friction coefficient was minimum when the D2N content was 0.5% by mass. there were.

From this result, it can be said that the hair protective agent according to the embodiment of the present invention is effective in suppressing damage to the hair by the hair coloring treatment and improving the feel. That is, it is suggested that the hair protective agent according to the embodiment of the present invention can suppress damage to the hair surface and further improve the feel.

[Example 2]
The effect of the hair protective agent according to the embodiment of the present invention on the damage caused by the perm agent to the hair was examined. Specifically, a hair sample treated with a perm agent was prepared, and the breaking strength and friction coefficient of the hair sample were measured.

[How to make a hair sample]
The method for preparing the hair sample is as follows.
1. 1. We prepared a hair piece that had not undergone any chemical treatment.
2. The first agent was applied to the hair piece. Hairpiece: Perm agent = 1: 1 (weight ratio). The composition of the first agent will be described later.
3. The hairpiece was allowed to stand at 30 ° C. for 30 minutes and then washed with water.
4. The second agent was applied to the hair piece. The amount applied was such that hair piece: hair coloring agent = 1: 1 (weight ratio). The composition of the second agent will be described later.
The hairpiece was allowed to stand at 5.30 ° C. for 30 minutes.
6. The hairpiece was washed with a 10 mass% SDS aqueous solution (sodium dodecyl sulfate aqueous solution) and then dried.

In this embodiment, in order to measure only the effect of the perm agent on the hair, the treatment of wrapping the hair piece around the hair rod is not performed.

(Composition of 1st agent and 2nd agent)
The basic compositions of the first agent and the second agent are as follows. When the content of the hair protectant was changed, it was adjusted by changing the amount of water (see Examples 2-3 to 2-6 and Comparative Example 2-5).
● 1st agent ・ 50% ammonium thioglycolate (reducing agent): 12% by mass
-Monoethanolamine (alkaline agent): 2% by mass
-Triethanolamine (alkaline agent): 3% by mass
-Sodium ascorbate (antioxidant): 0.5% by mass
・ Hair protectant: 0.5% by mass
・ Water: 82% by mass
● Second agent, sodium bromate (oxidizing agent): 8% by mass
-Water: 92% by mass.

Since the method for measuring the breaking strength and the method for measuring the friction coefficient are the same as those in the first embodiment, the description thereof will be omitted again.

[Example 2-1]
D2N was used as the hair protectant (same as that used in Example 1-1). The measurement results of the hair sample are shown in Table 3.

[Example 2-2]
D2M was used as the hair protectant (same as that used in Example 1-2). The measurement results of the hair sample are shown in Table 3.

[Comparative Example 2-1]
As a hair protectant, KF-8015, a silicone-based raw material, was used (the same as that used in Comparative Example 1-2). The measurement results of the hair sample are shown in Table 3.

[Comparative Example 2-2]
As a hair protectant, a silicone-based raw material KF-9021 was used (the same as that used in Comparative Example 1-3). The measurement results of the hair sample are shown in Table 3.

[Comparative Example 2-3]
As a hair protectant, Promois WK, a protein-based raw material, was used (same as that used in Comparative Examples 1-4). The measurement results of the hair sample are shown in Table 3.

[Comparative Example 2-4]
As a hair protectant, Proticute H gamma, a protein-based raw material, was used (same as that used in Comparative Example 1-5). The measurement results of the hair sample are shown in Table 3.

[Comparative Example 2-5]
The experiment was conducted by changing the water content to 82.5% by mass without adding a hair protectant. The measurement results of the hair sample are shown in Table 3.

[Example 2-3]
An experiment was conducted using D2N as a hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 0.01% by mass and the water content to 82.49% by mass. It was. The measurement results of the hair sample are shown in Table 4.

[Example 2-4]
Experiments were conducted using D2N as the hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 0.1% by mass and the water content to 82.4% by mass. went. The measurement results of the hair sample are shown in Table 4.

[Example 2-5]
Experiments were conducted using D2N as the hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 5.0% by mass and the water content to 77.5% by mass. went. The measurement results of the hair sample are shown in Table 4.

[Example 2-6]
Experiments were conducted using D2N as the hair protectant (same as that used in Example 1-1), changing the content of the hair protectant to 10.0% by mass and the water content to 72.5% by mass. went. The measurement results of the hair sample are shown in Table 4.

（結果）
表３によると、パーフルオロポリエーテルを毛髪保護剤として用いたパーマネントウェーブ剤においては、毛髪破断強度の向上及び摩擦係数の減少がみられる（実施例と比較例２−５とを比較して参照）。一方、シリコーン系毛髪保護剤を用いた場合、摩擦係数は減少しているが、毛髪破断強度は向上しなかった（比較例２−１、２−２を参照）。また、タンパク質系毛髪保護剤を用いた場合、毛髪破断強度は向上しているが、摩擦係数は減少しなかった（比較例２−３、２−４を参照）。

(result)
According to Table 3, in the permanent wave agent using the perfluoropolyether as the hair protective agent, the hair breaking strength is improved and the friction coefficient is decreased (see comparing Examples and Comparative Examples 2-5). ). On the other hand, when the silicone-based hair protectant was used, the coefficient of friction was reduced, but the hair breaking strength was not improved (see Comparative Examples 2-1 and 2-2). Further, when the protein-based hair protectant was used, the hair breaking strength was improved, but the friction coefficient was not decreased (see Comparative Examples 2-3 and 2-4).

Further, according to Table 4, in the range where the D2N content was 0.01 to 10.00% by mass, the hair breaking strength was improved and the friction coefficient was decreased. Of these, the hair breaking strength was maximum when the D2N content was 5.00%, and the friction coefficient was minimum when the D2N content was 10.00%. ..

From this result, it can be said that the hair protective agent according to one embodiment is effective in suppressing damage to the hair by the permanent wave treatment and improving the feel. That is, it is suggested that the hair protective agent according to the embodiment of the present invention can suppress damage inside the hair and further improve the feel.

[Example 3]
The effect of the hair protective agent according to the embodiment of the present invention on the damage caused by the hair coloring agent to the hair surface was confirmed. Specifically, a hair sample treated with a hair coloring agent was prepared, and the surface of the hair sample was observed using a scanning electron microscope (SEM). The method for preparing the hair sample and the composition of the hair coloring agent were the same as in Example 1-1, and D2N was used as the hair protective agent (the same as that used in Example 1-1). The results are as shown in FIG.

(result)
FIG. 1A is a surface of healthy hair that has not been subjected to hair coloring treatment. (B) is the surface of the hair treated with a hair coloring agent to which D2N is added as a hair protective agent. (C) is the surface of the hair treated with a hair coloring agent to which D2N is not added. When D2N was not added to the hair coloring agent, peeling was observed on the cuticle on the hair surface ((c) in FIG. 1). On the other hand, when D2N was added to the hair coloring agent, the cuticle peeling was suppressed.

From this result, it was shown that the hair protective agent according to the embodiment of the present invention has an effect of suppressing damage to the hair surface in the hair coloring treatment. Therefore, since the surface of the hair can be kept smooth, the effect of improving the feel of the hair is also expected.

[Example 4]
The effect of the hair protectant according to the embodiment of the present invention on the outflow of proteins in the hair due to the hair coloring treatment was examined. Specifically, a hair sample that had been color-treated once or three times was prepared, and the sulfur content of the hair sample was measured by SEM-EDX. For comparison, the sulfur content of hair treated with a hair coloring agent to which D2N was not added was also measured. The method for preparing the hair sample and the composition of the hair coloring agent are the same as those in Example 1 (for the hair sample subjected to the hair coloring treatment three times, steps 3 to 5 in Example 1 were repeated a total of three times). The method for measuring the sulfur content is as shown below.

[Measurement of sulfur content]
The tips of 12 of the prepared hair samples were cut out. The reason why the hair tips are cut out is that the hair tips are the parts where the damage to the hair due to the hair coloring treatment is greater. Next, the sulfur content of the cut hair sample was measured by SEM-EDX. The proportion (atomic%) of sulfur atoms in the hair was calculated from the average value of the K-line (SK) intensity of sulfur atoms detected in 12 samples. The results are shown in FIG.

(result)
According to FIG. 2, when D2N was added to the hair coloring agent, the decrease in sulfur content associated with the hair coloring treatment of the hair was suppressed as compared with the case where D2N was not added. In particular, in the hair sample subjected to the hair coloring treatment once, the decrease in the sulfur content of the hair was strongly suppressed.

From this result, it is considered that the hair protective agent according to the embodiment of the present invention suppresses the outflow of protein from the hair. Therefore, it is suggested that the hair protective agent according to the embodiment of the present invention has an effect of suppressing damage to the hair due to the hair coloring treatment.

[Example 5]
The effect of the hair protective agent according to one embodiment of the present invention on the dryness of hair was examined. Specifically, a sample obtained by adding D2N to a commercially available non-rinse type treatment was applied to a hair piece having a length of 30 cm. Then, the amount of static electricity of the hair piece was measured. Specifically, it is as follows.
1. 1. Glamorous curl cream essence (manufactured by Nakano Seiyaku Co., Ltd.) was used as a commercially available non-rinse type treatment. The amount of D2N added was 1.0% by mass. 2. A hair styling product was applied to the hair piece. The amount of application was such that hairpiece: non-rinse type treatment = 1: 1 (weight ratio).
3. 3. The hairpiece was rubbed 30 times with a vinyl gloved hand to generate static electricity.
4. The amount of static electricity generated was measured using an electrostatic measuring instrument (Digital Electro Static Meter Model [KDS-0303]: manufactured by Kasuga Electric Works Ltd.). The results are shown in Table 5. For comparison, the amount of static electricity in the hair sample treated with the non-rinse type treatment without adding D2N was also measured.

（結果）
Ｄ２Ｎを添加した洗い流さないタイプのトリートメントを塗布することにより、静電気量の減少が見られた。この結果から、本発明の一実施形態に係る毛髪保護剤には、毛髪の静電気発生を抑制する効果が認められる。つまり、本発明の一実施形態に係る毛髪保護剤には、毛髪のパサツキを抑制する効果があると言える。

(result)
A reduction in the amount of static electricity was observed by applying a non-rinse type treatment containing D2N. From this result, the hair protective agent according to the embodiment of the present invention has an effect of suppressing the generation of static electricity in the hair. That is, it can be said that the hair protective agent according to the embodiment of the present invention has an effect of suppressing the dryness of hair.

[Example 6]
The effect of the hair protective agent according to one embodiment of the present invention on the feel of hair was sensory-evaluated. Specifically, the wig was treated with a non-rinse type treatment to which D2N was added, and nine panelists were allowed to evaluate the feel (moistness and cohesiveness). More specifically, the procedure was as follows.
1. 1. 2.1 g of a commercially available non-rinse type treatment (same as in Example 5) to which D2N was added was applied to a wig (manufactured by Bulux Co., Ltd.). After application, it was well blended with a comb.
2. The wig was washed with water, towel-dried and dried in sequence. The feel of the wig after completion of each step was compared to the wig treated with a D2N-free, non-rinse type treatment. The results are shown in Table 6.

（結果）
Ｄ２Ｎを添加した洗い流さないタイプのトリートメント試料を塗布した場合、水洗後、タオルドライ後及び乾燥後のすべてにおいて、手触りが向上する傾向にある。特に乾燥後においては、すべてのパネラーが手触りの向上を報告し、９名中４名は手触りが更に向上したと評価した。

(result)
When a non-rinse type treatment sample to which D2N is added is applied, the feel tends to be improved after washing with water, towel-drying, and drying. Especially after drying, all panelists reported improvement in texture, and 4 out of 9 evaluated that the texture was further improved.

From this result, it is considered that the hair protective agent according to the embodiment of the present invention has an effect of improving the feel of hair.

The present invention can be used in industries dealing with various hair treatment agents such as hair color treatment and permanent wave treatment.

Claims (8)

A hair protectant containing perfluoropolyether. The hair protectant according to claim 1, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (1).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r- (CF ₂ ) _{s- CF 3} (1)
[In equation (1),
m + s indicates a real number from 0 to 5,
n + o + p + q + r represents a real number from 1 to 50. ] The hair protectant according to claim 1, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (2).
CF ₃ − (CF ₂ ) _{m −} O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − ( CF ₂ CF ₂ CF ₂ O) _r- (CF ₂ ) _s- CH ₂ O-R1 (2)
[In equation (2),
R1 indicates H,-[CH _2- CH (OH) CH ₂ O] _x- R3, or-(CH ₂ ) _y OH.
x indicates a real number from 1 to 5, y indicates a real number from 1 to 6,
R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB.
B is an alkoxy group, an amide group, or an amino group of C1 to C4.
m + s represents a real number from 1 to 5,
n + o + p + q + r represents a real number from 1 to 50. ] The hair protectant according to claim 1, wherein the perfluoropolyether contains a perfluoropolyether represented by the following formula (3).
R2-OCH _2- (CF ₂ ) _m −O − (CF ₂ CF ₂ O) _n − (CF ₂ O) _o − (CF (CF ₃ ) CF ₂ O) _p − (CF (CF ₃ ) O) _q − (CF ₂ CF ₂ CF ₂ O) _r − (CF ₂ ) _s −CH ₂ O—R1 (3)
[In equation (3),
R1 and R2 independently represent H,-[CH _2- CH (OH) CH ₂ O] _x- R3, or-(CH ₂ ) _y OH, respectively.
x indicates a real number from 1 to 5, y indicates a real number from 1 to 6,
R3 is H, OH, CH ₃ , C ₆ H ₅ or C ₆ H ₄ OB.
B is an alkoxy group, an amide group, or an amino group of C1 to C4.
m + s represents a real number from 1 to 5,
n + o + p + q + r represents a real number from 1 to 50. ] The hair protectant according to any one of claims 1 to 4, wherein the perfluoropolyether has a number average molecular weight of 100 to 10,000. A hair treatment agent containing the hair protective agent according to any one of claims 1 to 5. The hair treatment agent according to claim 6, wherein the content of perfluoropolyether is 0.005 to 20% by mass. A hair treatment method using the hair treatment agent according to claim 6 or 7.

Images