JP2023088353A - Hair treatment agent and hair treatment method - Google Patents

Abstract

To provide a post-treatment agent and a hair treatment method which can reduce unpleasant odors after perming or hair color treatment.SOLUTION: A hair treatment agent comprises polyalkyleneimine.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a hair post-treatment agent containing a polyalkyleneimine and a hair treatment method using the same. The hair post-treatment agent containing the polyalkyleneimine of the present invention can be suitably used as a hair treatment agent for reducing unpleasant odor after permanent treatment or hair coloring treatment.

Conventionally, permanent waving agents and curly hair straightening agents (hereinafter collectively referred to as permanent treatment agents) Pluronic (registered trademark) have been widely used as means for changing the shape of hair. The first agent of the permanent treatment agent is used for the purpose of cutting disulfide bonds in the hair, and an organic thiol compound is used as a reducing agent.
For example, Patent Document 1 describes a first agent used for permanent wave treatment, which is characterized by containing at least (A) cysteamine as a reducing agent and (B) an anionic polymer. It is described that the first agent for permanent wave treatment can remarkably improve the texture of hair after permanent wave treatment, and that the effect can be sustained.
Further, Patent Document 2 describes a perming agent containing a reducing agent in an amount of 3% by mass or more and 10% by mass or less and having a pH of 7.0 or more and 9.0 or less. It is described that a perm treatment with an excellent balance with restraint can be performed.
Patent Document 3 describes at least one selected from abietic acid or its salts or derivatives, persimmon tannins and fruit polyphenols as a deodorant composition for hair coloring capable of alleviating unpleasant odors derived from ammonia. A deodorant composition for hair coloring is described which is characterized by containing the following ingredients as active ingredients.

JP 2013-95696 JP 2018-162226 JP 2003-231620

However, since a thiol compound is used in Patent Documents 1 and 2, there is a problem that a peculiar unpleasant odor remains for several weeks after permanent wave treatment or curly hair straightening treatment. In addition, along with thiol compounds, it cuts the salt bonds in the hair, swells it, and promotes the penetration of chemicals into the hair. Improvements were also desired.

The present inventors conducted studies in view of the above problems, and found that a polyalkyleneimine-containing hair treatment agent is excellent in reducing unpleasant odors after permanent treatment, hair coloring treatment, etc., and the present invention. perfected the invention.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a hair treatment agent and a hair treatment method capable of reducing an unpleasant odor after permanent treatment, hair coloring treatment, or the like.

A hair treatment agent of the present disclosure comprises a polyalkyleneimine.

<Polyalkyleneimine>
The polyalkyleneimine of the present disclosure is one type of alkyleneimine having 2 to 6 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine. Alternatively, homopolymers and copolymers of these alkyleneimines obtained by polymerizing two or more of them by a conventional method are suitable. These may be used alone or in combination of two or more. More preferably, it is a homopolymer of ethyleneimine (polyethyleneimine; PEI). It may also be obtained by polymerizing ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or the like.

The weight average molecular weight (Mw) of the polyalkyleneimine of the present disclosure is preferably 400 or more, more preferably 1,000 or more, still more preferably 10,000 or more, and 50,000 or more, from the viewpoint of skin safety. is more preferably 300,000 or more, and from the viewpoint of feeling during use, it is preferably 1,000,000 or less, more preferably 800,000 or less, and even more preferably 500,000 or less.
As a method for measuring the weight average molecular weight of the polyalkyleneimine of the present disclosure, it can be measured using a GPC (gel permeation chromatography) method. Specifically, it can be measured by the method described in the Examples.

Specifically, it can be measured by the method described in the Examples, but it is preferable to appropriately adjust the measurement conditions depending on the weight-average molecular weight of the polyalkyleneimine.
For example, when measuring a low-molecular-weight polyalkyleneimine, the measurement may be performed under the following condition 1, and when measuring a high-molecular-weight polyalkyleneimine, the measurement may be performed under the following condition 2. The weight-average molecular weight, which is a measure of the high molecular weight, may be approximately 100,000.

(Condition 1)
Measuring device: manufactured by Shimadzu Corporation Column used: SHODEX Asahipac GF-710HQ + GF-510HQ + GF-310HQ manufactured by Showa Denko K.K.
Eluent: 0.2 mol % - pH adjusted to 5.1 by adding acetic acid to monoethanolamine aqueous solution Standard material: Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.)
Detector; differential refractometer (manufactured by Shimadzu Corporation)
(Condition 2)
Measuring device; manufactured by Shimadzu Corporation Column used; SHODEX OHpak SB-807HQ (2 pieces) + SB-806M/HQ (2 pieces) manufactured by Showa Denko K.K.
Eluent; 0.5 mol%-sodium nitrate, 0.5 mol%-acetic acid Standard substance; Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.)
Detector; differential refractometer (manufactured by Shimadzu Corporation)
The amine value per non-volatile content of the polyalkyleneimine of the present disclosure is preferably 5 or more, more preferably 10 or more, still more preferably 15 or more, preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

The non-volatile content (resin content) of polyalkyleneimine can be measured by the Karl Fischer method or the dry weight method. A specific measuring method is described below.
・ Karl Fischer method measuring instrument; Karl Fischer moisture meter solvent; methanol 20-30 ml
Amine neutralizer; 7 ml of acetic acid
Formula: Resin content (wt%) = 100-V x F/S x 100
V = KF titer (ml)
F = titer of KF (mg/ml)
S = sample amount (mg)
• Dry weight method Approximately 1 g of a sample was placed in an aluminum dish, dried in a hot air circulation dryer at 150±5°C for 1 hour, and then allowed to cool in a desiccator for 10 minutes.
Formula: Resin content (wt%) = W/S x 100
W: residual weight after drying (g)
S: sample weight before drying (g)

The amine value per non-volatile content of polyalkyleneimine is the number of moles (mmol) of amino groups contained in 1 g of non-volatile content of polyalkyleneimine. The amine value of polyethyleneimine can be calculated by potentiometric titration using a 0.5 mol/L p-toluenesulfonic acid standard solution in a methanol solution.
The degree of cationization of the polyalkyleneimine of the present disclosure is preferably 5 meq/g or more, more preferably 10 meq/g or more, still more preferably 15 meq/g or more, preferably 30 meq/g or less, and more preferably 25 meq/g or less. , 22 meq/g or less.

The degree of cationization of the present disclosure can be measured using a known method, but for example, it can be obtained from the measured value of the N content measured by the Kjeldahl method, method 2, Nitrogen determination method, general test method for cosmetic raw material standards. can be done.
Meq/g, which is a unit of degree of cationization, indicates the number of milliequivalents of cationic groups per 1 g of polyalkyleneimine.
Cationization degree (meq/g)
= (number of moles of cationized glucose units in 1 g of polyalkyleneimine) x 1000
Mole number of cationized glucose units in 1 g of polyalkyleneimine = (nitrogen content in polyalkyleneimine) / (atomic weight of N)

The polyalkyleneimines of the present disclosure include primary amines, secondary amines, and/or tertiary amines.
The content of the primary amine in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 25 mol% or more, 27 mol% or more in that order, and 50 mol% or less. is preferred, 45 mol% or less is more preferred, and 40 mol% or less and 37 mol% or less are more preferred in that order.
The content of the secondary amine in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, preferably 60 mol% or less, and 55 mol% or less. is more preferable, and 50 mol % or less is even more preferable.

The content of the tertiary amine in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, preferably 50 mol% or less, and 40 mol% or less. is more preferable, and 35 mol % or less is even more preferable.
The molar ratio of primary amine, secondary amine, and tertiary amine in the polyalkyleneimine of the present disclosure is 10 to 50:10 to 60:10 to 50 for primary amine:secondary amine:and tertiary amine. Preferably, 20-45:20-55:10-40 is more preferable, and 25-40:30-50:20-35 is even more preferable.

The polyalkyleneimine of the present disclosure may be a modified polyalkyleneimine (hereinafter also referred to as modified polyalkyleneimine). The modified polyalkyleneimine is not particularly limited. A compound obtained by adding 1 mol to 300 mol of an oxide and/or glycidyl ether compound to 1 mol of active hydrogen of an amino group, (ii) one of the primary amino groups and/or secondary amino groups contained in the polyalkyleneimine (iii) polyalkylene Some or all of the primary amino groups and/or secondary amino groups contained in the imine are exemplified by isocyanate group-containing compounds, ester group-containing compounds, ketone group-containing compounds, compounds obtained by adding acid anhydrides, and the like. be. When the polyalkyleneimine of the present disclosure contains a polyalkyleneimine to which an alkylene oxide is added, the amount of alkylene oxide added is 10 parts by mass or less per 100 parts by mass of the polyalkyleneimine from the viewpoint of reducing unpleasant odors. Preferably, the amount is 5 parts by mass or less, more preferably 3 parts by mass or less, and alkylene oxide may not be added.

In the polyalkyleneimine of the present disclosure, some or all of the amino groups contained in the polyalkyleneimine may be neutralized with an acid, may be quaternized with an alkyl halide or the like, or may be N-oxidized. It's okay to be.

The polyalkyleneimine of the present disclosure may have a branched structure.
The branching degree of the polyalkyleneimine of the present disclosure exceeds 0%, preferably 1% or more, more preferably 5% or more, further preferably 10% or more, particularly preferably 15% or more, and the upper limit of the branching degree of the polyethyleneimine is preferably 50% or less, more preferably 40% or less, even more preferably 35% or less.
The degree of branching of the polyalkyleneimine is determined from the chart obtained by measuring 13C-NMR of polyethyleneimine, and the intensity ratio between the carbon atoms bonded to the tertiary amine and the carbon atoms bonded to the secondary amine is obtained. Thus, the number a of tertiary amines and the number b of secondary amines are calculated, and from these a and b, the following formula can be used.
Degree of branching (%)=[a/(a+b)]×100
That is, linear polyethyleneimine does not have a tertiary amine, so the degree of branching is 0%, and all nitrogen atoms are tertiary amines. That is, maximally branched polyethylene has a degree of branching of 100%.

<Hair treatment agent>
The hair treatment agent of the present disclosure is not particularly limited as long as it contains polyalkyleneimine.
The content of the polyalkyleneimine in the hair treatment agent of the present disclosure is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and even more preferably 0.05 parts by mass or more per 100 parts by mass of the hair treatment agent. , is preferably 5.0 parts by mass or less, more preferably 4.0 parts by mass or less, and even more preferably 3.0 parts by mass or less.
The hair treatment agent of the present disclosure preferably further contains at least one organic acid or organic acid salt.

Organic acids of the present disclosure include, for example, monocarboxylic acids such as glyoxylic acid, levulinic acid, glycolic acid, lactic acid and salicylic acid; dicarboxylic acids such as maleic acid, fumaric acid, succinic acid, tartaric acid and malic acid; tricarboxylic acid; and more preferred are fumaric acid and succinic acid from the viewpoint of reducing unpleasant odors.
Organic acid salts of the present disclosure include salts of the above organic acids, preferably sodium salts and potassium salts, and more preferably sodium salts.

The total content of the organic acid and organic acid salt per 100 parts by mass of the hair treatment agent of the present disclosure is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and is preferably 0.01 parts by mass or more. It is more preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, and even more preferably 5.0 parts by mass or less.
The total parts by mass of polyalkyleneimine, organic acid and organic acid salt (parts by mass of polyalkyleneimine + parts by mass of organic acid + parts by mass of organic acid salt) per 100 parts by mass of the hair treatment agent of the present disclosure is 0. 0.002 parts by mass or more is preferable, 0.015 parts by mass or more is more preferable, 0.06 parts by mass or more is more preferable, 15.0 parts by mass or less is preferable, 11.5 parts by mass or less is more preferable, and 8.0 Part by mass or less is more preferable.
The hair treatment agent of the present disclosure may contain at least one organic acid or organic acid salt without using polyalkyleneimine from the viewpoint of reducing an unpleasant odor after hair treatment. A mode in which it is used in combination with is preferred.

The compound other than the polyalkyleneimine in the hair treatment agent of the present disclosure is not particularly limited, but examples include various organic and inorganic alkaline agents, permanent effect modifiers, cationic, anionic, nonionic, amphoteric and other surfactants. agents, polyhydric alcohols, sugars, sequestering agents, thickeners, oils, pH adjusters, various polymers, moisturizers, higher alcohols, UV absorbers, urea, preservatives, extracts from animals and plants, fragrances, pigments, Water etc. are mentioned.

Cationic surfactants of the present disclosure include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, dialkyldimethylammonium salts such as distearyldimethylammonium chloride, alkylpyridium salts such as cetylpyridium chloride, and alkyldimethylbenzylammonium salts. , benzalkonium chloride, benzethonium chloride and the like.

The anionic surfactants of the present disclosure include, for example, fatty acid soaps such as sodium palmitate, higher alkyl sulfates such as sodium lauryl sulfate, alkyl ether sulfates such as POE triethanolamine lauryl sulfate, sodium lauroyl sarcosinate, and the like. N-acyl sarcosinate, higher fatty acid amide sulfonates such as sodium coconut oil fatty acid methyl taurate, phosphate ester salts such as POE stearyl ether phosphate, sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, N-lauroyl N-acyl glutamates such as monosodium glutamate, higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid sodium glycerin sulfate, and the like.

The nonionic surfactants of the present disclosure include sorbitan fatty acid esters such as sorbitan monostearate and sorbitan sesquioleate, glycerol fatty acids such as glyceryl monostearate, and propylene glycol fatty acid esters such as propylene glycol monostearate. , hydrogenated castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters such as POE sorbitan monooleate, POE sorbit fatty acid esters such as POE sorbit monostearate, POE glycerin fatty acid esters such as POE glycerin monoisostearate, POE fatty acid esters such as POE monooleate; POE alkyl ethers such as POE 2-octyldodecyl ether; Pluronic types such as Pluronic (registered trademark); POE/POP alkyl ethers such as POE/POP cetyl ether; Tetra-POE/tetra-POP ethylenediamine condensates, POE castor oil derivatives such as POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil derivatives such as POE hydrogenated castor oil monoisostearate, sucrose fatty acid esters, alkyl glucosides, etc. mentioned.

Amphoteric surfactants of the present disclosure include imitazoline amphoteric surfactants such as 2-cocoyl-2-imitazolinium hydroxide-1-carboxyethyloxy disodium salt, 2-heptadecyl-N-carboxymethyl-N -Betaine surfactants such as hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amidobetaine, sulfobetaine and the like.

Polyhydric alcohols and sugars of the present disclosure function as humectants and include, for example, propylene glycol, 1,3-butylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-pentanediol, isoprene glycol, glycerin, diglycerin, xylitol, sorbitol, maltitol, mannitol, erythritol and the like.

Sequestering agents of the present disclosure include, for example, diethylenetriaminepentaacetic acid pentasodium salt, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium salt, biodegradable chelating agent 3hydroxy-2, 2′ iminodisuccinic acid or salts thereof (eg, tetrasodium salt), and the like.

Thickeners of the present disclosure include, for example, carrageenan, xanthan gum, guar gum, gum arabic, pectin, mannan, chitin, chitosan, agar, polyvinylpyrrolidone, carboxyvinyl polymer, succinoglucan, sodium polyacrylate, diethanolamide coconut oil. and alkanolamides such as lauric acid monoethanolamide, fatty acid isopropanolamide, and the like.

Oil agents of the present disclosure include, for example, hydrocarbons such as liquid paraffin and squalane, waxes such as jojoba oil and liquid lanolin, isopropyl myristate, glyceryl tri-2-ethylhexanoate, diglyceryl diisostearate, and tri-2-ethylhexane. Esters such as acid trimethylolpropane, oils such as castor oil and macadamia nut oil, chain polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, Examples thereof include silicone oils such as amino-modified silicone.

Higher alcohols of the present disclosure include, for example, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, hydrogenated rapeseed oil alcohol, behenyl alcohol, and the like.

The hair treatment agent of the present disclosure may be in the form of liquid, emulsion, water-in-oil emulsion, oil-in-water emulsion, multiple emulsion, microemulsion, spray, gel, foam, granules, lotion, cream, or the like. is possible. It can also be of the type prepared just before use, which is mixed at the time of use.
Although the hair treatment agent of the present disclosure is not particularly limited, it is preferably used as a permanent treatment agent, a hair color treatment agent, or the like.
The permanent treatment agent of the present disclosure can be used as a permanent wave treatment agent or a treatment agent for straightening curly hair. When used as a permanent treatment agent, it may be used as a first agent for cutting disulfide bonds of keratin contained in hair, or may be used as a post-treatment agent after using the first agent.
The post-treatment agent used after the use of the first agent of the present disclosure is not particularly limited as long as it is a hair treatment agent used after the use of the first agent. It may be used as an agent (second agent), or may be used as a cleaning agent for washing away the first agent and/or the second agent.

The first agent in the permanent treatment of the present disclosure preferably contains a thiol compound from the viewpoint of breaking the disulfide bond of keratin.
The thiol compounds of the present disclosure include, for example, lactone thiols such as butyrolactone thiol, thioglycolates such as thioglycolic acid, ammonium thioglycolate, and monoethanolamine thioglycolate, cysteine such as cysteine, guanylcysteine, and cysteine hydrochloride. salt, acetylcysteine or its salt, thiolactate such as thiolactic acid, thiolactate ammonium salt, thiolactic acid monoethanolamine salt, thiolactic acid isopropanolamine salt, thiopropionic acid or its salt, thiomalic acid, glyceryl monothioglycolate, etc. Thioglycolic acid esters such as glyceryl thioglycolate, cysteamine, cysteamine salts such as cysteamine hydrochloride, etc., and from the viewpoint of cleaving disulfide bonds, butyrolactone thiol, thioglycolic acid, glyceryl thioglycolate, thioglycerin, Cysteine, acetylcysteine and cysteamine are preferred, butyrolactonethiol, cysteamine, thioglycolic acid and cysteine are more preferred, and butyrolactonethiol is even more preferred.

As the first agent in the permanent treatment of the present disclosure, it is preferable to use ammonia as a pH adjuster of the first agent.
Good permanent treatment can be achieved by using a thiol compound or ammonia as the first agent in the permanent treatment of the present disclosure.
Although the use of a thiol compound or ammonia as the first agent in the permanent treatment causes a problem that a unique unpleasant odor remains, the permanent treatment can be performed by using a polyalkyleneimine in the permanent treatment agent of the present disclosure. After using the first agent, the unpleasant odor can be reduced, and by using the hair treatment agent of the present disclosure after using the first agent, a further effect of reducing the unpleasant odor can be expected.

The pH of the first agent in the permanent treatment of the present disclosure is preferably 4 to 9.5.
When used as a post-treatment agent in the permanent treatment of the present disclosure, other compounds such as oily components, surfactants, solvents, anti-dandruff agents, vitamins, antiseptics, anti-inflammatory agents, chelating agents, dyes, pigments, etc. Colorant, carboxyvinyl polymer, xanthan gum, viscosity modifiers such as clay minerals, citric acid, 2-amino-2-methyl-1-propanol, pH modifiers such as sodium hydroxide, hydrolyzed keratin, hydrolyzed collagen, water Hydrolyzed PPTs such as hydrolyzed wheat protein, amino acids such as glycine, alanine, glutamic acid and theanine and their derivatives, vitamins such as vitamins A, B and C and their derivatives, sugar alcohols such as inositol and xylitol, reducing agents, Examples include oxidizing agents, extracts extracted from plants, animals, and microorganisms, pearling agents, fragrances, pigments, ultraviolet absorbers, antioxidants, propellants, and the like.

The pH of the post-treatment agent in the permanent treatment of the present disclosure is preferably adjusted between pH 3 and 10, more preferably between pH 4.5 and 8.5. In particular, it is more preferable to adjust the pH between 6.0 and 8.0. Examples of organic acids used as pH buffers include citric acid, glycolic acid, succinic acid, tartaric acid, lactic acid, fumaric acid, malic acid, and levulinic acid. Examples of inorganic acids include phosphoric acid and sulfuric acid. , nitric acid and the like. Examples of salts of these acids include alkali metal salts such as sodium salts and potassium salts, and alkanolamine salts such as ammonium salts and triethanolamine salts.

The hair color treatment agent of the present disclosure includes not only a coloring treatment agent for coloring hair, but also a bleaching treatment agent for decoloration. The coloring agents of the present disclosure also include coloring agents having a decolorizing effect (coloring agents used for single colors). The bleaching agent of the present disclosure means a processing agent that does not contain a coloring agent and is intended only for decolorization.
As the hair color treatment agent of the present disclosure, compounds other than polyalkyleneimine are not particularly limited, but those containing ammonia are preferable from the viewpoint of swelling and softening of hair during bleaching or coloring. By using ammonia, the hair coloring effect (bleaching or coloring effect) is improved, and by containing polyalkyleneimine, unpleasant odors derived from ammonia can be reduced.

The hair color treatment agent of the present disclosure may contain other compounds besides polyalkyleneimine or ammonia.
Other compounds used in the hair color treatment agent of the present disclosure include oxidation dye intermediates, direct dyes, alkaline agents; alkanolamines such as monoethanolamine, isopropanolamine, 2-amino-2-methylpropanol, and 2-aminobutanol; alkanediamines such as 1,3-propanediamine; inorganic bases such as sodium hydroxide and potassium hydroxide; carbonates such as guanidine carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; Hydrogen and hydrogen peroxide generators such as urea peroxide, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, potassium percarbonate, silicones; amino-modified silicone, highly polymerized silicone, degree of polymerization Dimethylpolysiloxane less than 1000, cyclic polysiloxane, phenylpolysiloxane, modified silicone excluding amino-modified silicone, etc., oils; hydrocarbon oils, vegetable oils, ester oils, triglycerides, higher alcohols; cetyl alcohol, stearyl alcohol, behenyl alcohol, etc. Surfactants, organic solvents; lower alkanols such as ethanol and 2-propanol, aromatic alcohols such as benzyl alcohol and benzyloxyethanol, polyols such as propylene glycol, 1,3-butanediol, diethylene glycol and glycerin, natural Or synthetic polymers, ethers, protein derivatives, hydrolyzed proteins, amino acids, preservatives, chelating agents, stabilizers, antioxidants, plant extracts, crude drug extracts, vitamins, fragrances, UV absorbers etc.

The hair color treatment agents of the present disclosure can also be used as post-treatment agents after using ammonia-containing coloring or bleaching agents.

<Hair treatment method>
The hair treatment method of the present disclosure preferably includes a step of contacting the hair with the hair treatment agent of the present disclosure (hereinafter also referred to as a “contact step”). The contact method in the contacting step is not particularly limited, but a method of spraying the hair treatment agent onto the hair, for example, a method of applying the hair treatment agent to the hair using a brush or the like, or a method of immersing the hair in the hair treatment agent. A method of (dipping) is exemplified.
The contact time between the hair and the hair treatment agent in the contact step is not particularly limited, but is preferably 30 seconds or more and 3 hours or less.
The contacting step may be carried out at room temperature, or may be carried out partially or wholly with heating or cooling. For example, after bringing the hair treatment agent into contact with the hair, the hair may be heated with a heater or the like. The contacting step may be carried out, for example, so that the surface temperature of the hair is -5°C or higher and 50°C or lower.

The hair treatment method of the present disclosure may include a step of removing the hair treatment agent of the present disclosure from the hair (hereinafter also referred to as "removal step").
The removal step is not particularly limited, but is preferably carried out by a method of washing the hair treatment agent of the present disclosure with water or the like. When washing with water, a shower head or the like may be used because washing efficiency is improved. When the method of washing with water is used, any of room temperature water, cooled water, and heated water may be used. Preferably, water at -5°C or higher and 45°C or lower is used.
The hair treatment agent of the present disclosure is preferably used as a permanent treatment agent, a hair color treatment agent, or the like. It may also be used as the first agent of a permanent treatment agent, or as a post-treatment agent used after using a coloring treatment agent or a bleaching treatment agent in hair coloring treatment.
For example, in a permanent treatment agent, it may be used as the first agent for cutting disulfide bonds of keratin contained in the hair, or may be used as a post-treatment agent after using the first agent. From the viewpoint of reduction of , it is preferably used as a post-treatment agent after use of the first agent.
The first agent in the permanent treatment of the present disclosure preferably contains a thiol compound.

The thiol compounds of the present disclosure include, for example, lactone thiols such as butyrolactone thiol, thioglycolates such as thioglycolic acid, ammonium thioglycolate, and monoethanolamine thioglycolate, cysteine such as cysteine, guanylcysteine, and cysteine hydrochloride. salt, acetylcysteine or its salt, thiolactic acid, thiolactate ammonium salt, thiolactic acid monoethanolamine salt, thiolactic acid isopropanolamine salt, thiopropionic acid or its salt, thiomalic acid, glyceryl monothioglycolate, etc. Thioglycolic acid esters such as glyceryl thioglycolate, cysteamine, cysteamine salts such as cysteamine hydrochloride, etc., and from the viewpoint of cleaving disulfide bonds, butyrolactone thiol, thioglycolic acid, glyceryl thioglycolate, thioglycerin, Cysteine, acetylcysteine and cysteamine are preferred, butyrolactonethiol, cysteamine, thioglycolic acid and cysteine are more preferred, and butyrolactonethiol is even more preferred.
The hair color treatment agent of the present disclosure can be used as a coloring treatment agent or a bleaching treatment agent, and can also be used as a post-treatment agent used after using a coloring treatment agent or a bleaching treatment agent.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited only to these examples. Unless otherwise specified, "part" means "mass part" and "%" means "mass %".

<Weight average molecular weight>
The weight average molecular weight (Mw) of the ethyleneimine polymer according to the present invention can be measured by a known method using pullulan as a standard substance by gel permeation chromatography (GPC). In the present invention, the following conditions are adopted as measurement conditions for GPC.
(Condition 1)
Measuring device: manufactured by Shimadzu Corporation Column used: SHODEX Asahipac GF-710HQ + GF-510HQ + GF-310HQ manufactured by Showa Denko K.K.
Eluent: 0.2 mol % - pH adjusted to 5.1 by adding acetic acid to monoethanolamine aqueous solution Standard material: Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.)
Detector; differential refractometer (manufactured by Shimadzu Corporation)
(Condition 2)
Measuring device; manufactured by Shimadzu Corporation Column used; SHODEX OHpak SB-807HQ (2 pieces) + SB-806M/HQ (2 pieces) manufactured by Showa Denko K.K.
Eluent; 0.5 mol%-sodium nitrate, 0.5 mol%-acetic acid Standard substance; Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.)
Detector; differential refractometer (manufactured by Shimadzu Corporation)

<Amine value>
The amine value is the number of moles (mmol) of amino groups contained in 1 g of resin. The amine value of polyethyleneimine was calculated by potentiometric titration using a 0.5 mol/L p-toluenesulfonic acid standard solution in a methanol solution.
<Mole % of primary amine, secondary amine, and tertiary amine>
13C-NMR was used. Utilizing the fact that each carbon adjacent to a primary amine, secondary amine, and tertiary amine shows different chemical shifts, the ratio of each amine was calculated.

<Cationization degree>
It was determined from the measured value of the N content measured by the Kjeldahl method, Nitrogen Determination Method No. 2, General Test Methods of Standards for Cosmetic Ingredients.
Cationization degree (meq/g)
= (number of moles of cationized glucose units in 1 g of polyalkyleneimine) x 1000
Mole number of cationized glucose units in 1 g of polyalkyleneimine = (nitrogen content in polyalkyleneimine) / (atomic weight of N)

<Non-volatile content (resin content)>
The non-volatile content (resin content) was measured by the dry weight method.
(Dry weight method)
About 1 g of the sample was collected in an aluminum dish, dried in a hot air circulation dryer at 150±5° C. for 1 hour, and then allowed to cool in a desiccator for 10 minutes.
Formula: Resin content (wt%) = W/S x 100
W: residual weight after drying (g)
S: sample weight before drying (g)

<Deodorizing test 1 of butyrolactone thiol: hair bundle>
Liquid 1 was prepared by mixing 10 g of "Glatz R33 Essence (manufactured by Paimore Co., Ltd., containing 10% butyrolactone thiol, pH = 4.0)", which is a commercial product containing butyrolactone thiol as a reducing agent, and 100 g of purified water. . A bundle of hair (manufactured by Beaulux Co., Ltd., yak hair, product number: BM-YK-A, 10 cm×1 g) was impregnated with Liquid 1 and allowed to stand at 40° C. for 10 minutes. The hair tresses were taken out, dried with a towel, and then naturally dried. A dried hair tress was impregnated with polyethyleneimine solution 2 diluted with purified water so that the solid content concentration was 1%, allowed to stand at room temperature for 5 minutes, then taken out and air-dried. The tresses were sniffed by 5 professional panelists and evaluated on a 5-point scale. The evaluation value was rounded off by averaging the evaluation values of five persons.
<Determination of odor:>
5: The original odor remains 4: The odor is slightly weaker than the original 3: The odor is weaker than the original 2: The odor is much weaker than the original 1: The original odor is almost gone

[Examples 1 to 6]
The polyethylenimine used in Examples 1 to 6 is shown in Table 1. Table 1 shows the results of a butyrolactonethiol deodorizing test using polyethyleneimine described in each section and a hair bundle.
[Comparative Example 1]
Evaluation was performed in the same manner as in Examples 1 to 6, except that the polyethyleneimine liquid in Examples 1 to 6 was changed to purified water. The results are listed in Table 1.

<Deodorizing test 2 of butyrolactone thiol>
[Example 7]
0.2 g of "Glatz R33 Essence (manufactured by Paimore Co., Ltd., containing 10% butyrolactone thiol, pH = 4.0)", which is a marketed product containing butyrolactone thiol as a reducing agent, so that the solid content concentration is 1% 39.8 g of an aqueous polyethyleneimine solution diluted with purified water was placed in each 50 ml screw vial, stirred and allowed to stand for 5 minutes. After that, the lid of the screw tube was opened, and the odor of the screw tube bottle was smelled by five expert panelists and evaluated on a five-point scale. The evaluation value was rounded off by averaging the evaluation values of five persons. The results are listed in Table 2.
The odor was determined according to the same criteria as the evaluation described above.
[Examples 8 to 12]
Evaluation was performed in the same manner as in Example 7, except that the molecular weight of the polyethyleneimine aqueous solution having a solid content concentration was changed.
[Comparative Example 2]
Evaluation was performed in the same manner as in Example 7, except that the polyethyleneimine aqueous solution in Example 7 was changed to purified water.
[Reference example 1]
Evaluation was performed in the same manner as in Example 7, except that the polyethyleneimine in Example 7 was changed to succinic acid.
[Reference example 2]
Evaluation was performed in the same manner as in Example 7, except that sodium fumarate was used instead of polyethyleneimine.

[Examples 13 to 18]
0.2 g of "Glatz R33 Essence (manufactured by Paimore Co., Ltd., containing 10% butyrolactone thiol, pH = 4.0)", which is a marketed product containing butyrolactone thiol as a reducing agent, so that the solid content concentration is 2% 20.0 g of polyethyleneimine aqueous solution diluted with purified water, 0.4 g of succinic acid, and 19.4 g of purified water were each placed in a 50 ml screw tube bottle, stirred and allowed to stand for 5 minutes. After that, the lid of the screw tube was opened, and the odor of the screw tube bottle was smelled by five expert panelists and evaluated on a five-point scale. The evaluation value was rounded off by averaging the evaluation values of five persons.
Tables 2 and 3 show the results of Examples 7-18, Comparative Example 2, and Reference Examples 1-2.
<Determination of odor: It was performed according to the same criteria as the evaluation described above. ＞

<Deodorization test of cysteamine>
[Examples 19 to 22]
5 g of cysteamine, 5 g of polyethylenimine, and 90 g of purified water were each put into a 200 ml screw tube bottle, stirred, and allowed to stand for 5 minutes. After that, the cap of the screw-cap bottle was opened, and the odor of the screw-cap bottle was smelled by five expert panelists and evaluated on a five-point scale. The evaluation value was rounded off by averaging the evaluation values of five persons. The results are listed in Table 3.
<Determination of odor:>
5: The original odor remains 4: The odor is slightly weaker than the original 3: The odor is weaker than the original 2: The odor is much weaker than the original 1: The original odor is almost gone [Examples 23, 24]
Evaluation was performed in the same manner as in Examples 19 to 22, except that the blending amount of the polyethyleneimine liquid was changed so that the solid content concentration was the same.
[Comparative Example 3]
Evaluation was carried out in the same manner as in Example 1924, except that the polyethyleneimine liquid in Example 1924 was changed to purified water.
[Reference Examples 3 and 4]
Evaluation was performed in the same manner as in Examples 19 to 24 except that the polyethyleneimine was changed to 1 g of succinic acid or sodium fumarate.
[Examples 25 and 26]
Evaluation was carried out in the same manner as in Examples 21 to 26, except that the blending amount of the polyethyleneimine liquid was changed so that the solid content concentration was the same, and 1 g of succinic acid was added.
Tables 4 and 5 show the results of Examples 19-26, Comparative Example 3, and Reference Examples 3-4.

<Deodorization test of thioglycolic acid>
[Examples 27-35, Comparative Example 4, Reference Examples 5-6]
Examples 19-26, Comparative Example 3 and Reference Examples 3-4 were evaluated in the same manner except that cysteamine was changed to thioglycolic acid.
Tables 6 and 7 show the results of Examples 27-35, Comparative Example 4, and Reference Examples 3-4.

<Cysteine deodorant test>
[Examples 36-44, Comparative Example 5, Reference Examples 7-8]
Evaluation was performed in the same manner as in Examples 19-26, Comparative Example 3, and Reference Examples 3-4, except that cysteine was used instead of cysteamine.
Tables 8 and 9 show the results of Examples 36-44, Comparative Example 5, and Reference Examples 7-8.

<Ammonia deodorant test>
[Examples 45-53, Comparative Example 6, Reference Examples 9-10]
Evaluation was performed in the same manner as in Examples 19-26, Comparative Example 3, and Reference Examples 3-4, except that cysteamine was changed to ammonia.
The results of Examples 45-53, Comparative Example 6, and Reference Examples 9-10 are shown in Tables 10 and 11.

*1 Product name: Epomin SP-003 (manufactured by Nippon Shokubai Co., Ltd.) Mw 450, amine ratio is primary amine: secondary amine: tertiary amine = 45:35:20, resin content is 98 wt% or more, amine value ( mmol/g solid) 21
*2 Product name: Epomin SP-006 (manufactured by Nippon Shokubai Co., Ltd.) Mw 1,300, amine ratio primary amine: secondary amine: tertiary amine = 35:35:30, resin content 98 wt% or more, amine Value (mmol/g solid) 20
*3 Product name: Epomin SP-018 (manufactured by Nippon Shokubai Co., Ltd.) Mw 4,200, amine ratio is primary amine: secondary amine: tertiary amine = 35:35:30, resin content 98 wt% or more, amine Value (mmol/g solid) 19
*4 Product name: Epomin SP-200 (manufactured by Nippon Shokubai Co., Ltd.) Mw 17,500, amine ratio primary amine: secondary amine: tertiary amine = 35:35:30, resin content 98 wt% or more, amine Value (mmol/g solid) 18
*5 Product name: Epomin P-1000 (manufactured by Nippon Shokubai Co., Ltd.) Mw 350,000, amine ratio primary amine: secondary amine: tertiary amine = 25:50:25, resin content 30 wt%, amine value (mmol/g·solid) 18
*6 Product name: Epomin P-3000 (manufactured by Nippon Shokubai Co., Ltd.) Mw 450,000, amine ratio primary amine: secondary amine: tertiary amine = 30:40:30, resin content 35 wt%, amine value (mmol/g·solid) 18
*7 Product name: Succinic acid (manufactured by Nippon Shokubai Co., Ltd.)
*8 Product name: Monofumar (registered trademark) (monosodium fumarate) (manufactured by Nippon Shokubai Co., Ltd.)
* 9 Product name: 2-Aminoethanethiol (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 10 Product name: Thioglycolic Acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
* 11 Product name: L-Cysteine (manufactured by Tokyo Chemical Industry Co., Ltd.)
*12 Product name: Ammonia water (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
Details of the polyethyleneimine used in this example are described in Table 12.

The weight average molecular weights of polyethyleneimine described in *1 to *4 were measured under Condition 1.

The weight average molecular weights of polyethyleneimine described in *5 and *6 were measured under condition 2.
Other examples of hair cosmetics as hair treatment agents of the present invention are described below as Formulation Examples 1 to 4. It should be noted that the hair cosmetics of these formulation examples also had the effect of reducing the unpleasant odor after permanent treatment or hair coloring treatment, which was favorable.

<Prescription Example 1: Shampoo>
POE (2) sodium lauryl ether sulfate (27% by mass aqueous solution) 18.0% by mass
Coconut fatty acid amidopropyl betaine (30% by mass aqueous solution) 33.0% by mass
Decyl glucoside (40% by mass aqueous solution) 5.0% by mass
Coconut oil fatty acid diethanolamide 1.0% by mass
Cationized cellulose 0.3% by mass
Cationic guar gum 0.2% by mass
Polyethyleneimine (Mw 350,000) (30 wt% aqueous solution) 0.3 wt%
Disodium ethylenediaminetetraacetate 0.03% by mass
Sodium benzoate 0.3% by mass
Glycerin 2.0% by mass
Phenoxyethanol 0.3% by mass
Succinic acid 0.1% by mass
Perfume 0.2% by mass
Purified water Remaining total 100.0% by mass

<Manufacturing Formulation Example 2: Hair Conditioner>
Cetearyl alcohol 5.0% by mass
Glycerin 3.0% by mass
Behentrimonium chloride, isopropanol mixture 2.0% by mass
Cetrimonium chloride aqueous solution 1.0% by mass
Dimethicone 2.0% by mass
Polyethyleneimine (Mw 350,000) (30 wt% aqueous solution) 1.6 wt%
Phenoxyethanol 0.2% by mass
Perfume 0.2% by mass
Purified water Remaining total 100.0% by mass

<Manufacturing prescription example 3: Leave-on hair treatment>
Cetearyl alcohol 4.0% by mass
Glyceryl stearate 0.8% by mass
Isopropyl myristate 1.0% by mass
Glycerin 3.0% by mass
Behentrimonium chloride, isopropanol 2.5% by mass
Polyethyleneimine (Mw 350,000) (30 wt% aqueous solution) 0.6 wt%
Cyclopentasiloxane 5.0% by mass
Dimethicone 2.0% by mass
Phenoxyethanol 0.2% by mass
Purified water Remaining total 100.0% by mass

<Manufacturing Formulation Example 4: Hair Mist>
Glycerin 3.0% by mass
Ethanol 30.0% by mass
Polyethyleneimine (Mw 350,000) (30 wt% aqueous solution) 0.16 wt%
Betaine 0.2% by mass
Phenoxyethanol 0.2% by mass
Succinic acid 0.1% by mass
Polyoxyethylene hydrogenated castor oil isostearate (50E.O.) 0.2% by mass
Perfume 0.1% by mass
Purified water Remaining total 100.0% by mass

Claims (10)

A polyalkyleneimine-containing hair treatment agent. The hair treatment agent according to claim 1, further comprising an organic acid. 3. The hair preparation according to claim 1, wherein the polyalkyleneimine has a weight average molecular weight of 400 or more and 1,000,000 or less. The hair treatment agent according to any one of claims 1 to 3, wherein the polyalkyleneimine has an amine value of 10 mmol/g or more and 30 mmol/g or less. The hair treatment agent according to any one of claims 1 to 4, which is a hair color treatment agent. 6. The hair treatment agent according to claim 5, which is an ammonia-containing hair color treatment agent. The hair treatment agent according to any one of claims 1 to 4, which is a post-treatment agent used for permanent treatment and/or hair coloring treatment. A hair treatment method using a polyethyleneimine-containing hair treatment agent. 9. The method for treating hair according to claim 8, which is used after using the first agent for permanent treatment and/or hair coloring treatment. The hair treatment method according to claim 9, wherein the first agent for permanent treatment and/or hair coloring treatment contains a thiol compound or ammonia.