Hair treatment agent and hair treatment method.

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]

[0001] 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 that reduces unpleasant odors after permanent treatment or hair color treatment. [Background technology]

[0002] Conventionally, permanent wave agents and hair straighteners (hereinafter collectively referred to as permanent treatment agents) such as Pluronic (registered trademark) have been widely used as a means for changing the shape of hair. The first agent of the permanent treatment agent is used for the purpose of cleaving 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 for permanent wave treatment, which is characterized by containing at least (A) cysteamine as a reducing agent and also (B) an anionic polymer, and states that it significantly improves the feel of hair after permanent wave treatment and can maintain this effect. Furthermore, Patent Document 2 describes a perm agent containing a reducing agent in an amount of 3% by mass or more and 10% by mass or less and a pH of 7.0 or more and 9.0 or less, and describes that the agent can provide a perm treatment that has an excellent balance between deformation of hair and suppression of dryness and a rough feel. Patent Document 3 describes a hair color deodorant composition that can reduce the unpleasant odor caused by ammonia, and that contains at least one component selected from abietic acid, a salt thereof, or a derivative thereof, persimmon tannin, and fruit polyphenol as an active ingredient. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2013-95696 [Patent Document 2] Patent Publication No. 2018-162226 [Patent Document 3] Patent Publication No. 2003-231620 Summary of the Invention [Problem to be solved by the invention]

[0004] However, because Patent Documents 1 and 2 use thiol compounds, there is a problem that a specific unpleasant odor remains for several weeks after permanent wave treatment or hair straightening treatment. In addition, there has been a need to improve the unpleasant odor caused by alkaline agents such as ammonia, which are used in addition to thiol compounds to break salt bonds in the hair, swell the hair, and promote penetration of the agent into the hair, while also assisting the action of the reducing agent. [Means for solving the problem]

[0005] The present inventors have conducted studies in consideration of the above-mentioned problems and have found that a polyalkyleneimine-containing hair treatment agent is excellent at reducing unpleasant odors after permanent treatment, hair color treatment, etc., and have completed the present invention. [Effects of the Invention]

[0006] According to the present invention, a hair treatment agent and a hair treatment method are provided that can reduce unpleasant odors after permanent treatment, hair color treatment, etc. DETAILED DESCRIPTION OF THE INVENTION

[0007] The hair treatment agent of the present disclosure contains a polyalkyleneimine.

[0008] <Polyalkyleneimine> The polyalkyleneimine of the present disclosure is preferably a homopolymer or copolymer of these alkyleneimines obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, or 1,1-dimethylethyleneimine, using a conventional method. These may be used alone or in combination of two or more. More preferably, it is an ethyleneimine homopolymer (polyethyleneimine; PEI). It may also be one obtained by polymerizing ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or the like.

[0009] The weight-average molecular weight (Mw) of the polyalkyleneimine of the present disclosure is preferably 400 or more, more preferably 1,000 or more, even more preferably 10,000 or more, even more preferably 50,000 or more, and even more preferably 300,000 or more from the viewpoint of safety to the skin, and is preferably 1,000,000 or less, more preferably 800,000 or less, and even more preferably 500,000 or less from the viewpoint of usability. The weight-average molecular weight of the polyalkyleneimine of the present disclosure can be measured by GPC (gel permeation chromatography). Specifically, it can be measured by the method described in the Examples.

[0010] Specifically, it can be measured by the method described in the Examples, but it is preferable to adjust the measurement conditions appropriately 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 high molecular weight, may be about 100,000, and when it exceeds 100,000, the measurement may be performed under condition 2.

[0011] (Condition 1) Measuring equipment: Shimadzu Corporation Column used: SHODEX Asahipac GF-710HQ + GF-510HQ + GF-310HQ manufactured by Showa Denko K.K. Eluent: 0.2 mol% monoethanolamine aqueous solution adjusted to pH 5.1 by adding acetic acid Standard substance: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (Shimadzu Corporation) (Condition 2) Measuring equipment: Shimadzu Corporation Columns used: Showa Denko SHODEX OHpak SB-807HQ (2 columns) + SB-806M / HQ (2 columns) Eluent: Prepared in 0.5 mol% sodium nitrate and 0.5 mol% acetic acid Standard substance: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (Shimadzu Corporation) The amine value per nonvolatile content of the polyalkyleneimine of the present disclosure is preferably 5 or more, more preferably 10 or more, and even more preferably 15 or more, and is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0012] The non-volatile content (resin content) of the polyalkyleneimine can be measured by the Karl Fischer method or the dry weight method. Specific measurement methods are described below. Karl Fischer method Measuring equipment: Karl Fischer moisture meter Solvent: Methanol 20-30ml Amine neutralizer: 7ml acetic acid Calculation formula: Resin content (wt%)=100-V×F / S×100 V=KF titer (ml) F = KF titer (mg / ml) S = sample amount (mg) ·Dry weight method Approximately 1 g of the sample was placed on an aluminum dish, dried in a hot air circulating dryer at 150±5°C for 1 hour, and then allowed to cool in a desiccator for 10 minutes. Calculation formula: Resin content (wt%)=W / S×100 W: Residual weight after drying (g) S: Sample weight before drying (g)

[0013] The amine value per unit nonvolatile content of polyalkyleneimine is the number of moles (mmol) of amino groups contained in 1 g of nonvolatile content of polyalkyleneimine. The amine value of polyethyleneimine can be calculated by potentiometric titration in methanol solution using a 0.5 mol / L standard solution of p-toluenesulfonic acid. 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, and even more preferably 15 meq / g or more, and is preferably 30 meq / g or less, more preferably 25 meq / g or less, and even more preferably 22 meq / g or less.

[0014] The degree of cationization in the present disclosure can be measured using known methods, but can also be determined from the measured value of the N content measured, for example, by the Kjeldahl method, Method 2 of the Nitrogen Determination Method in the General Testing Methods of the Standards for Cosmetic Ingredients. The unit of the degree of cationization, meq / g, 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) × 1000 Moles of cationized glucose units in 1 g of polyalkyleneimine = (nitrogen content in polyalkyleneimine) / (atomic weight of N)

[0015] The polyalkyleneimine of the present disclosure includes at least one of a primary amine, a secondary amine, and a tertiary amine. The content of primary amines in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more and 27 mol% or more, in that order; preferably 50 mol% or less, more preferably 45 mol% or less, further preferably 40 mol% or less and 37 mol% or less. The content of secondary amines in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, and is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

[0016] The content of tertiary amine in the polyalkyleneimine of the present disclosure is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more, and is preferably 50 mol% or less, more preferably 40 mol% or less, and even more preferably 35 mol% or less. The molar ratio of primary amine, secondary amine, and tertiary amine in the polyalkyleneimine of the present disclosure is preferably 10-50:10-60:10-50, more preferably 20-45:20-55:10-40, and even more preferably 25-40:30-50:20-35, where primary amine:secondary amine:tertiary amine.

[0017] The polyalkyleneimine of the present disclosure may be a modified polyalkyleneimine (hereinafter also referred to as a modified polyalkyleneimine). The modified polyalkyleneimine is not particularly limited, and examples thereof include: (i) a compound in which, for example, 1 mole to 300 moles of an alkylene oxide and / or a glycidyl ether compound having 2 to 30 carbon atoms is added to some or all of the primary amino groups and / or secondary amino groups contained in the polyalkyleneimine, per mole of active hydrogen in the amino groups; (ii) a compound in which, for example, a compound having a carbon-carbon unsaturated double bond, such as acrylic acid, an acrylic acid ester, styrene, acrylonitrile, N-vinylpyrrolidone, or vinyl acetate, is added to some or all of the primary amino groups and / or secondary amino groups contained in the polyalkyleneimine by Michael addition; and (iii) a compound in which, for example, an isocyanate group-containing compound, an ester group-containing compound, a ketone group-containing compound, or an acid anhydride is added to some or all of the primary amino groups and / or secondary amino groups contained in the polyalkyleneimine. When the polyalkyleneimine of the present disclosure contains a polyalkyleneimine having an alkylene oxide added thereto, from the viewpoint of reducing unpleasant odors, the amount of alkylene oxide added is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the polyalkyleneimine, and no alkylene oxide may be added.

[0018] 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.

[0019] The polyalkyleneimine of the present disclosure may have a branched structure. The degree of branching of the polyalkyleneimine of the present disclosure exceeds 0%, and is preferably 1% or more, more preferably 5% or more, even more preferably 10% or more, and particularly preferably 15% or more. The upper limit of the degree of branching of the polyethyleneimine is preferably 50% or less, more preferably 40% or less, and even more preferably 35% or less. The degree of branching of a polyalkyleneimine can be calculated from the number a of tertiary amines and the number b of secondary amines by determining the intensity ratio between the carbon atoms bonded to the tertiary amines and the carbon atoms bonded to the secondary amines from a chart obtained by measuring the polyethyleneimine by C-NMR, and then the degree of branching of a polyalkyleneimine can be calculated from a and b using the following formula: Branching degree (%) = [a / (a+b)] x 100 In other words, linear polyethyleneimine has no tertiary amines and has a branching degree of 0%, and all nitrogen atoms are tertiary amines. In other words, maximally branched polyethylene has a branching degree of 100%.

[0020] <Hair treatment agent> The hair treatment agent of the present disclosure is not particularly limited as long as it contains a polyalkyleneimine. The content of polyalkyleneimine in the hair treatment agent of the present disclosure is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and even more preferably 0.05 part by mass or more, per 100 parts by mass of the hair treatment agent; and 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 of an organic acid and an organic acid salt.

[0021] Examples of organic acids of the present disclosure include 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; and tricarboxylic acids such as citric acid. From the viewpoint of reducing unpleasant odors, fumaric acid and succinic acid are more preferred. The organic acid salts of the present disclosure include salts of the above organic acids, with sodium salts and potassium salts being preferred, and sodium salts being more preferred.

[0022] 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, even more preferably 0.01 parts by mass or more, and is 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 the 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 preferably 0.002 parts by mass or more, more preferably 0.015 parts by mass or more, and even more preferably 0.06 parts by mass or more, and is preferably 15.0 parts by mass or less, and more preferably 11.5 parts by mass or less. It is preferably 8.0 parts by mass or less, and more preferably 8.0 parts by mass or less. The hair treatment agent of the present disclosure may contain at least one of an organic acid or an organic acid salt without using a polyalkyleneimine, from the viewpoint of reducing unpleasant odors after hair treatment. However, as described above, it is preferable to use the organic acid or organic acid salt in combination with a polyalkyleneimine.

[0023] The compounds other than polyalkyleneimine in the hair treatment agent of the present disclosure are not particularly limited, but examples include various organic and inorganic alkaline agents, perm effect regulators, various cationic, anionic, nonionic, and amphoteric surfactants, polyhydric alcohols, sugars, sequestering agents, thickeners, oils, pH adjusters, various polymers, moisturizers, higher alcohols, ultraviolet absorbers, urea, preservatives, animal and plant extracts, fragrances, colorants, and water.

[0024] Examples of the cationic surfactant of the present disclosure include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, dialkyldimethylammonium salts such as distearyldimethylammonium chloride, alkylpyridinium salts such as cetylpyridinium chloride, alkyldimethylbenzylammonium salts, benzalkonium chloride, and benzethonium chloride.

[0025] Examples of the anionic surfactants of the present disclosure include fatty acid soaps such as sodium palmitate, higher alkyl sulfates such as sodium lauryl sulfate, alkyl ether sulfates such as POE triethanolamine lauryl sulfate, N-acyl sarcosinates such as sodium lauroyl sarcosinate, higher fatty acid amide sulfonates such as coconut oil fatty acid methyl taurate sodium, phosphate ester salts such as POE stearyl ether phosphate, sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate, N-acyl glutamates such as monosodium N-lauroyl glutamate, and higher fatty acid ester sulfates such as hydrogenated coconut oil fatty acid glycerin sodium sulfate.

[0026] Examples of the nonionic surfactants disclosed herein include sorbitan fatty acid esters such as sorbitan monostearate and sorbitan sesquioleate, glycerin fatty acids such as glycerin monostearate, 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, and POE glycerin such as POE glycerin monoisostearate. Examples of the fatty acid ester include fatty acid esters, 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, tetraPOE·tetraPOP ethylenediamine condensates such as Tetronic, 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, and alkyl glucosides.

[0027] Examples of the amphoteric surfactant of the present disclosure include imitazoline-based amphoteric surfactants such as 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, and betaine-based surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkyl betaine, amido betaine, and sulfobetaine.

[0028] The polyhydric alcohols and sugars of the present disclosure function as humectants, and examples thereof include propylene glycol, 1,3-butylene glycol, 1,3-propanediol, dipropylene glycol, 1,2-pentanediol, isoprene glycol, glycerin, diglycerin, xylitol, sorbitol, maltitol, mannitol, and erythritol.

[0029] Examples of sequestering agents of the present disclosure include pentasodium diethylenetriaminepentaacetic acid, tetrasodium 1-hydroxyethane-1,1-diphosphonic acid, disodium edetate, and the biodegradable chelating agent 3-hydroxy-2,2'iminodisuccinic acid or a salt thereof (e.g., the tetrasodium salt).

[0030] Examples of thickeners of the present disclosure include carrageenan, xanthan gum, guar gum, gum arabic, pectin, mannan, chitin, chitosan, agar, polyvinylpyrrolidone, carboxyvinyl polymer, succinoglucan, sodium polyacrylate, alkanolamides such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, and fatty acid isopropanolamide.

[0031] Examples of oil agents according to the present disclosure include hydrocarbons such as liquid paraffin and squalane, waxes such as jojoba oil and liquid lanolin, esters such as isopropyl myristate, glyceryl tri-2-ethylhexanoate, diglyceryl diisostearate and trimethylolpropane tri-2-ethylhexanoate, fats and oils such as castor oil and macadamia nut oil, linear polysiloxanes such as dimethylpolysiloxane and methylphenylpolysiloxane, cyclic polysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, and silicone oils such as amino-modified silicone.

[0032] Examples of higher alcohols of the present disclosure include cetyl alcohol, cetostearyl alcohol, stearyl alcohol, oleyl alcohol, hydrogenated rapeseed oil alcohol, and behenyl alcohol.

[0033] The hair treatment agent of the present disclosure can be in the form of a liquid, emulsion, water-in-oil emulsion, oil-in-water emulsion, complex emulsion, microemulsion, spray, gel, foam, granule, lotion, cream, etc. It can also be a ready-to-use type that is mixed at the time of use. The hair treatment agent of the present disclosure is not particularly limited, but 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 hair. When used as a permanent treatment agent, it may be used as a first agent that cleaves the disulfide bonds of keratin contained in hair, or it may be used as a post-treatment agent that is used after using the first agent. The post-treatment agent used after use of the first agent of the present disclosure is not particularly limited as long as it is a hair treatment agent used after use of the first agent, but it may be used as an oxidizing agent (second agent) used to recombine disulfides cleaved by the first agent, or as a cleanser for rinsing away the first agent and / or the second agent.

[0034] The first agent in the permanent treatment of the present disclosure preferably contains a thiol compound from the viewpoint of cleaving the disulfide bonds of keratin. Examples of the thiol compound of the present disclosure include lactone thiols such as butyrolactone thiol, thioglycolic acid salts such as thioglycolic acid, ammonium thioglycolate, and monoethanolamine thioglycolate, cysteine ​​salts such as cysteine, guanylcysteine, and cysteine ​​hydrochloride, acetylcysteine ​​or a salt thereof, thiolactic acid, thiolactic acid salts such as ammonium thiolactic acid, monoethanolamine thiolactic acid, and isopropanolamine thiolactic acid, thiopropionic acid or a salt thereof, thiomalic acid, and esters of thioglycolic acid such as glyceryl thioglycolate such as glyceryl monothioglycolate, and salts of cysteamine such as cysteamine hydrochloride, and from the viewpoint of cleaving disulfide bonds, butyrolactone thiol, thioglycolic acid, glyceryl thioglycolate, thioglycerin, cysteine, acetylcysteine, and cysteamine are preferred, butyrolactone thiol, cysteamine, thioglycolic acid, and cysteine ​​are more preferred, and butyrolactone thiol is even more preferred.

[0035] In the first agent in the permanent treatment of the present disclosure, it is preferable to use ammonia as a pH adjuster for the first agent. By using a thiol compound or ammonia in the first agent in the permanent treatment of the present disclosure, good permanent treatment becomes possible. Although the use of a thiol compound or ammonia in the first agent in permanent treatment can result in the problem of a lingering unpleasant odor, the use of polyalkyleneimine in the permanent treatment agent of the present disclosure can reduce the unpleasant odor after permanent treatment, and by using the hair treatment agent of the present disclosure after using the first agent, further reduction in unpleasant odor can be expected.

[0036] 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 may include oily ingredients, surfactants, solvents, anti-dandruff agents, vitamins, preservatives, anti-inflammatory agents, chelating agents, colorants such as dyes and pigments, viscosity adjusters such as carboxyvinyl polymers, xanthan gum and clay minerals, pH adjusters such as citric acid, 2-amino-2-methyl-1-propanol and sodium hydroxide, hydrolyzed PPTs such as hydrolyzed keratin, hydrolyzed collagen and hydrolyzed wheat protein, amino acids and derivatives thereof such as glycine, alanine, glutamic acid and theanine, vitamins such as vitamins A, B and C and derivatives thereof, sugar alcohols such as inositol and xylitol, reducing agents, oxidizing agents, extracts extracted from plants, animals and microorganisms, pearlizing agents, fragrances, pigments, UV absorbers, antioxidants, propellants, etc.

[0037] The pH of the post-treatment agent for permanent wave treatment according to the present disclosure is preferably adjusted to a pH between 3 and 10, and more preferably between 4.5 and 8.5. Adjustment to a pH between 6.0 and 8.0 is particularly preferred. 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, while examples of inorganic acids include phosphoric acid, sulfuric acid, and nitric acid. Examples of salts of these acids include alkali metal salts such as sodium salts and potassium salts, ammonium salts, and alkanolamine salts such as triethanolamine salts.

[0038] The hair color treatment agent of the present disclosure includes not only a color treatment agent intended for coloring hair, but also a bleach treatment agent intended for bleaching. The color treatment agent of the present disclosure also includes a color treatment agent having a bleaching effect (a color treatment agent used for single color). The bleach treatment agent of the present disclosure refers to a treatment agent intended only for bleaching and does not contain a colorant. In the hair color treatment agent of the present disclosure, the compound other than the polyalkyleneimine is not particularly limited, but it is preferable that it contains ammonia from the viewpoint of swelling and softening the hair during bleaching or coloring. By using ammonia, the hair color effect (bleaching or coloring effect) is improved, and by containing the polyalkyleneimine, the unpleasant odor derived from ammonia can be reduced.

[0039] The hair color treatment agent of the present disclosure may contain other compounds in addition to the polyalkyleneimine or ammonia. Other compounds that can be used in the hair color treatment agent of the present disclosure include oxidative 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 bicarbonate, and potassium bicarbonate; oxidizing agents; hydrogen peroxide and hydrogen peroxide generators such as urea peroxide, melamine peroxide, sodium perborate, potassium perborate, sodium percarbonate, and potassium percarbonate; silicones; amino-modified silicones, highly polymerized silicones, and dimethylpolysiloxanes with a degree of polymerization of less than 1,000. , cyclic polysiloxane, phenyl polysiloxane, modified silicones excluding amino-modified silicones, etc., oils; hydrocarbon oils, vegetable oils, ester oils, triglycerides, etc., 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, herbal extracts, vitamins, fragrances, and UV absorbers.

[0040] The hair color treatment agent of the present disclosure can also be used as a post-treatment agent to be used after using an ammonia-containing color treatment agent or bleach treatment agent.

[0041] <Hair treatment method> The hair treatment method of the present disclosure preferably includes a step of contacting hair with the hair treatment agent of the present disclosure (hereinafter also referred to as a "contacting step"). The contacting method in the contacting step is not particularly limited, and examples include a method of spraying the hair treatment agent onto the hair, a method of applying the hair treatment agent to the hair using a brush, or a method of immersing the hair in the hair treatment agent. The contact time between the hair and the hair treatment agent in the contacting step is not particularly limited, but is preferably, for example, 30 seconds or more and 3 hours or less. The contacting step may be carried out at room temperature, or may be carried out after heating or cooling in part or in whole. For example, after contacting the hair with the hair treatment agent, the hair may be heated using a heater or the like. The contacting step may be carried out so that the surface temperature of the hair is -5°C or higher and 50°C or lower.

[0042] 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 the "removal step"). The removal step is not particularly limited, but is preferably carried out by 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 to improve washing efficiency. When using the water washing method, water at room temperature, cooled water, or heated water may be used. Preferably, water at a temperature of -5°C or higher and 45°C or lower is used. The hair treatment composition of the present disclosure is preferably used as a permanent treatment composition, a hair color treatment composition, etc. It may also be used as a first agent in a permanent treatment composition, or as a post-treatment composition to be used after use of a color treatment composition or a bleach treatment composition during hair color treatment. For example, in a permanent treatment agent, it may be used as a first agent that cleaves the disulfide bonds of keratin contained in hair, or it may be used as a post-treatment agent to be used after use of the first agent, but from the viewpoint of reducing unpleasant odors after permanent treatment, it is preferable to use it as a post-treatment agent to be used after use of the first agent. The first agent in the permanent treatment of the present disclosure preferably contains a thiol compound.

[0043] Examples of the thiol compound of the present disclosure include lactone thiols such as butyrolactone thiol; thioglycolic acid, thioglycolic acid salts such as ammonium thioglycolate, and monoethanolamine thioglycolate; cysteine ​​salts such as cysteine, guanylcysteine, and cysteine ​​hydrochloride; acetylcysteine ​​or a salt thereof; thiolactic acid, thiolactic acid salts such as ammonium thiolactic acid, monoethanolamine thiolactic acid, and isopropanolamine thiolactic acid; thiopropionic acid or a salt thereof; thiomalic acid; esters of thioglycolic acid such as glyceryl thioglycolate, e.g., glyceryl monothioglycolate; and cysteamine salts such as cysteamine and cysteamine hydrochloride. From the viewpoint of cleaving disulfide bonds, butyrolactone thiol, thioglycolic acid, glyceryl thioglycolate, thioglycerin, cysteine, acetylcysteine, and cysteamine are preferred, butyrolactone thiol, cysteamine, thioglycolic acid, and cysteine ​​are more preferred, and butyrolactone thiol is even more preferred. The hair color treatment agent of the present disclosure can be used as a color treatment agent or a bleach treatment agent, or as a post-treatment agent to be used after using a color treatment agent or a bleach treatment agent. [Example]

[0044] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0045] <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 gel permeation chromatography (GPC) with pullulan as a standard substance. The following conditions are adopted as the GPC measurement conditions in the present invention. (Condition 1) Measuring equipment: Shimadzu Corporation Column used: SHODEX Asahipac GF-710HQ + GF-510HQ + GF-310HQ manufactured by Showa Denko K.K. Eluent: 0.2 mol% monoethanolamine aqueous solution adjusted to pH 5.1 by adding acetic acid Standard substance: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (Shimadzu Corporation) (Condition 2) Measuring equipment: Shimadzu Corporation Columns used: Showa Denko SHODEX OHpak SB-807HQ (2 columns) + SB-806M / HQ (2 columns) Eluent: Prepared in 0.5 mol% sodium nitrate and 0.5 mol% acetic acid Standard substance: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: Differential refractometer (Shimadzu Corporation)

[0046] <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 in methanol solution using a 0.5 mol / L standard solution of p-toluenesulfonic acid. <Mole % of primary amine, secondary amine, and tertiary amine> Using 13C-NMR, the ratio of each amine was calculated by taking advantage of the fact that the carbon atoms adjacent to the primary, secondary, and tertiary amines show different chemical shifts.

[0047] <Cationization degree> The value was calculated from the nitrogen content measured by the Kjeldahl method, Method 2 of the Nitrogen Determination Method in the General Testing Methods for Cosmetic Ingredients Standards. Cationization degree (meq / g) = (number of moles of cationized glucose units in 1 g of polyalkyleneimine) × 1000 Moles of cationized glucose units in 1 g of polyalkyleneimine = (nitrogen content in polyalkyleneimine) / (atomic weight of N)

[0048] <Non-volatile content (resin content)> The nonvolatile content (resin content) was measured by the dry weight method. (dry weight method) Approximately 1 g of the sample was placed on an aluminum dish, dried in a hot air circulating dryer at 150±5°C for 1 hour, and then allowed to cool in a desiccator for 10 minutes. Calculation formula: Resin content (wt%)=W / S×100 W: Residual weight after drying (g) S: Sample weight before drying (g)

[0049] <Butyrolactone thiol deodorizing test 1: Hair bundle> Solution 1 was prepared by mixing 10 g of "Glatz R33 Essence" (manufactured by Pymore Co., Ltd., containing 10% butyrolactone thiol, pH = 4.0), a commercially available product containing butyrolactone thiol as a reducing agent, with 100 g of purified water. A hair swatch (manufactured by Beaulux Co., Ltd., yak hair, product number: BM-YK-A, 10 cm x 1 g) was impregnated with Solution 1 and left to stand at 40°C for 10 minutes. The hair swatch was removed, towel-dried, and then air-dried. The dried hair swatch was then impregnated with polyethyleneimine Solution 2, which had been diluted with purified water to a solids concentration of 1%, and left to stand at room temperature for 5 minutes before being removed and air-dried. The hair swatch was then smelled and rated on a 5-point scale by five expert panelists. The average evaluation score was rounded to the nearest whole number. <Odor determination:> 5: Keeps the original smell 4: The smell is slightly weaker than the original. 3: The smell is weaker than the original smell 2: The smell is much weaker than the original smell. 1: The original smell is almost gone

[0050] [Examples 1 to 6] The polyethyleneimines used in Examples 1 to 6 are as shown in Table 1. A deodorizing test of butyrolactone thiol was carried out using a hair bundle and each polyethyleneimine described above. The results are shown in Table 1. [Comparative Example 1] The polyethyleneimine solutions of Examples 1 to 6 were evaluated in the same manner as in Examples 1 to 6, except that purified water was used instead. The results are shown in Table 1.

[0051] [Table 1]

[0052] <Butyrolactone thiol deodorizing test 2> [Example 7] 0.2 g of "Glatz R33 Essence" (manufactured by Pymore Co., Ltd., containing 10% butyrolactone thiol, pH 4.0), a commercially available product containing butyrolactone thiol as a reducing agent, and 39.8 g of polyethyleneimine aqueous solution diluted with purified water to a solids concentration of 1%, were placed in a 50 ml screw cap bottle, stirred, and allowed to stand for 5 minutes. The cap of the screw cap bottle was then opened, and the odor of the screw cap bottle was smelled by five expert panelists and rated on a 5-point scale. The rating was the average of the five ratings and rounded to the nearest whole number. The results are shown in Table 2. The odor was judged according to the same criteria as those mentioned above. [Examples 8 to 12] Evaluation was carried out in the same manner as in Example 7, except that the molecular weight of the polyethyleneimine aqueous solution having a high solids concentration was changed. Comparative Example 2 Evaluation was carried out in the same manner as in Example 7, except that the aqueous polyethyleneimine solution was replaced with purified water. [Reference example 1] Evaluation was carried out in the same manner as in Example 7, except that polyethyleneimine was changed to succinic acid. [Reference example 2] Evaluation was carried out in the same manner as in Example 7, except that the polyethyleneimine was changed to sodium fumarate.

[0053] [Examples 13 to 18] 0.2g of "Glatz R33 Essence" (manufactured by Pymore Co., Ltd., containing 10% butyrolactone thiol, pH 4.0), a commercially available product containing butyrolactone thiol as a reducing agent, 20.0g of polyethyleneimine aqueous solution diluted with purified water to a solids concentration of 2%, 0.4g of succinic acid, and 19.4g of purified water were each placed in a 50ml screw cap bottle, stirred, and allowed to stand for 5 minutes. The screw cap was then opened, and the odor of the screw cap bottle was smelled by five expert panelists and rated on a 5-point scale. The rating score was the average of the five ratings and rounded to the nearest whole number. The results of Examples 7 to 18, Comparative Example 2, and Reference Examples 1 and 2 are shown in Tables 2 and 3. <Odor evaluation: The same criteria as above were used for the evaluation.>

[0054] [Table 2]

[0055] [Table 3]

[0056] <Cysteamine deodorizing test> [Examples 19 to 22] 5g of cysteamine, 5g of polyethyleneimine, and 90g of purified water were each placed in a 200ml screw cap bottle, stirred, and allowed to stand for 5 minutes. The lid of the screw cap bottle was then opened, and the odor of the screw cap bottle was smelled by five expert panelists, who rated it on a 5-point scale. The scores were calculated by averaging the scores of the five panelists and rounding them up or down. The results are shown in Table 3. <Odor determination:> 5: Keeps the original smell 4: The smell is slightly weaker than the original. 3: The smell is weaker than the original smell 2: The smell is much weaker than the original smell. 1: The original smell is almost gone [Examples 23 and 24] The evaluation was carried out in the same manner as in Examples 19 to 22, except that the amount of polyethyleneimine solution added 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 solution was changed to purified water. [Reference examples 3 and 4] The evaluation was carried out 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] The amount of the polyethyleneimine solution in Examples 21 to 26 was changed so that the solid content concentration was the same, and evaluation was carried out in the same manner except that 1 g of succinic acid was added. The results of Examples 19 to 26, Comparative Example 3, and Reference Examples 3 and 4 are shown in Tables 4 and 5.

[0057] [Table 4]

[0058] [Table 5]

[0059] <Thioglycolic acid deodorization test> [Examples 27 to 35, Comparative Example 4, Reference Examples 5 to 6] Examples 19 to 26, Comparative Example 3, and Reference Examples 3 and 4 were evaluated in the same manner as above, except that cysteamine was replaced with thioglycolic acid. The results of Examples 27 to 35, Comparative Example 4, and Reference Examples 3 and 4 are shown in Tables 6 and 7.

[0060] [Table 6]

[0061] [Table 7]

[0062] <Cysteine ​​deodorization test> [Examples 36 to 44, Comparative Example 5, Reference Examples 7 to 8] Examples 19 to 26, Comparative Example 3, and Reference Examples 3 and 4 were evaluated in the same manner as above, except that cysteamine was replaced with cysteine. The results of Examples 36 to 44, Comparative Example 5, and Reference Examples 7 and 8 are shown in Tables 8 and 9.

[0063] [Table 8]

[0064] [Table 9]

[0065] <Ammonia deodorization test> [Examples 45 to 53, Comparative Example 6, Reference Examples 9 to 10] Examples 19 to 26, Comparative Example 3, and Reference Examples 3 and 4 were evaluated in the same manner as above, except that cysteamine was replaced with ammonia. The results of Examples 45 to 53, Comparative Example 6, and Reference Examples 9 and 10 are shown in Tables 10 and 11.

[0066] [Table 10]

[0067] [Table 11]

[0068] *1 Product name: Epomin SP-003 (manufactured by Nippon Shokubai Co., Ltd.) Mw 450, amine ratio of primary amine: secondary amine: tertiary amine = 45:35:20, resin content 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 of 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 of 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 of 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 of 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 of 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: Monofumarate (registered trademark) (monosodium fumarate) (manufactured by Nippon Shokubai Co., Ltd.) *9 Product name: 2-Aminoethanethiol (Tokyo Chemical Industry Co., Ltd.) *10 Product name: Thioglycolic Acid (Tokyo Chemical Industry Co., Ltd.) *11 Product name: L-Cysteine ​​(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 shown in Table 12.

[0069] [Table 12]

[0070] The weight average molecular weights of polyethyleneimines described in *1 to *4 were measured under condition 1. The weight average molecular weight of polyethyleneimine described in *5 and *6 was 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. The hair cosmetics of these Formulation Examples also had the effect of reducing unpleasant odors after permanent treatment or hair color treatment, and were satisfactory.

[0071] <Prescription example 1: Shampoo> POE(2) sodium lauryl ether sulfate (27% by mass aqueous solution) 18.0% by mass Coconut oil fatty acid amidopropyl betaine (30% by weight aqueous solution) 33.0% by weight 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% by mass aqueous solution) 0.3% by mass 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 Fragrance 0.2% by mass Purified water remainder Total 100.0% by mass

[0072] <Manufacturing prescription 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% by mass aqueous solution) 1.6% by mass Phenoxyethanol 0.2% by mass Fragrance 0.2% by mass Purified water remainder Total 100.0% by mass

[0073] <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% by mass aqueous solution) 0.6% by mass Cyclopentasiloxane 5.0% by mass Dimethicone 2.0% by mass Phenoxyethanol 0.2% by mass Purified water remainder Total 100.0% by mass

[0074] <Manufacturing prescription example 4: Hair mist> Glycerin 3.0% by mass Ethanol 30.0% by mass Polyethyleneimine (Mw 350,000) (30% by mass aqueous solution) 0.16% by mass 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 Fragrance 0.1% by mass Purified water remainder Total 100.0% by mass

Claims

1. A polyalkyleneimine-containing hair treatment agent, the weight average molecular weight of the polyalkyleneimine is 10,000 or more and 1,000,000 or less; the hair treatment agent is a permanent treatment agent or a hair color treatment agent, the permanent treatment agent is a post-treatment agent used after use of a first agent, or a permanent treatment agent containing ammonia, The hair treatment agent is a post-treatment agent used after the use of an ammonia-containing coloring treatment agent or a bleaching treatment agent.

2. The hair treatment composition according to claim 1, further comprising an organic acid.

3. 3. The hair treatment agent according to claim 1, wherein the polyalkyleneimine has an amine value of from 10 mmol / g to 30 mmol / g.

4. The hair treatment agent according to any one of claims 1 to 3, wherein the first agent contains a thiol compound and / or ammonia.

5. A hair treatment method using a polyethyleneimine-containing hair treatment agent, the weight average molecular weight of the polyalkyleneimine is 10,000 or more and 1,000,000 or less; the hair treatment agent is a permanent treatment agent or a hair color treatment agent, the permanent treatment agent is a post-treatment agent used after use of a first agent, or a permanent treatment agent containing ammonia, The hair treatment method, wherein the hair color treatment agent is an ammonia-containing color treatment agent or a post-treatment agent used after using a bleach treatment agent.

6. The hair treatment method according to claim 5, further comprising an organic acid.

7. 7. The hair treatment method according to claim 5, wherein the polyalkyleneimine has an amine value of 10 mmol / g or more and 30 mmol / g or less.

8. The hair treatment method according to any one of claims 5 to 7, wherein the first agent contains a thiol compound and / or ammonia.

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