A damage inhibitor that inhibits damage caused by chlorine.

Abstract

To provide a damage inhibitor capable of inhibiting damage caused by residual chlorine, and to provide use thereof.SOLUTION: A damage inhibitor for inhibiting damage caused by chlorine, comprising a polyalkyleneimine and / or a polyalkyleneimine derivative.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a damage inhibitor that inhibits damage caused by chlorine. [Background technology]

[0002] Generally, tap water used for bathing and pool water contains chlorine for disinfection (residual chlorine). This residual chlorine is known to act on the proteins that make up skin and hair, causing skin irritation, rough skin, and damage to hair (e.g., hair breakage, discoloration, loss of luster, coarseness, etc.).

[0003] As a method for repairing damage caused by such residual chlorine, a damage repair agent containing a plant extract as an active ingredient is known (for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-165834 Summary of the Invention [Problem to be solved by the invention]

[0005] However, the above-described conventional techniques have room for improvement in terms of suppressing damage to skin and hair caused by residual chlorine.

[0006] Therefore, an object of the present invention is to provide a damage suppressant capable of suppressing damage caused by residual chlorine, and use thereof. [Means for solving the problem]

[0007] In order to solve the above problems, the inventors conducted extensive research into components that can suppress damage caused by residual chlorine, and as a result, they discovered that polyalkyleneimines and derivatives thereof have the ability to remove residual chlorine, and that the use of such polyalkyleneimines and derivatives thereof as active ingredients can suppress damage caused by residual chlorine, leading to the completion of the present invention.

[0008] That is, one aspect of the present invention includes the following. [1] A damage inhibitor containing polyalkyleneimine and / or a polyalkyleneimine derivative, which inhibits damage caused by chlorine. [2] The polyalkyleneimine derivative is a polyalkyleneimine derivative obtained by addition reaction of a compound having a structure of the following formula (1C) and / or (2C) to a nitrogen atom of the polyalkyleneimine, has a substituent having a structure of the following formula (3C) and / or (4C), The damage suppressant according to [1], wherein the amount of the substituent added to the nitrogen atoms contained in the polyalkyleneimine is 0.1 mol % to 35 mol %. R 3 -R 1 (1C) R 4 -R 1 (2C) -CHCH(OH)-R 1 ···(3C) -CH2CH(OH)CH2-OR 1 (4C) (In formulas (1C) to (4C), R 1 is an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an aryl group having 8 to 20 carbon atoms, or -(CH2CH2O)nR a where R a represents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, or an aryl group having 8 to 20 carbon atoms; n represents an integer of 1 to 50. 3 represents an epoxy group, and R 4 represents a glycidyl ether group. Here, the amount of the substituent added to the nitrogen atom contained in the polyalkyleneimine is a value calculated based on the following formula using the amine value of the polyalkyleneimine. Amount added (mol %)={[reacted amount of the compound (g) / molecular weight of the compound (g / mol)] / [amount of the polyalkyleneimine (g)×solid content of the polyalkyleneimine (%)×amine value of the polyalkyleneimine (mmol / g (non-volatile content)) / 1000]}×100(%). [3] The damage suppressant according to [1] or [2], wherein the polyalkyleneimine is polyethyleneimine. [4] The damage suppressant according to [1], wherein the polyalkyleneimine derivative is a polyalkyleneimine derivative obtained by an addition reaction of an alkylene oxide to a nitrogen atom of a polyalkyleneimine. [5] The damage suppressant according to [4], wherein the polyalkyleneimine is polyethyleneimine. [6] The damage suppressant according to any one of [1] to [5], wherein the polyalkyleneimine and / or polyalkyleneimine derivative has a weight-average molecular weight of 10,000 to 400,000. [7] A hair cosmetic comprising the damage suppressant according to any one of [1] to [6]. [Effects of the Invention]

[0009] According to the present invention, there are provided a damage suppressant capable of suppressing damage caused by residual chlorine, and use thereof. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 2 is a diagram showing the results of observation of the surface state of hair using a scanning electron microscope in an example. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these, and various modifications are possible within the scope of the description. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments and examples are also included in the technical scope of the present invention. In this specification, unless otherwise specified, "A to B" representing a numerical range means "A or more (including A and greater than A) and B or less (including B and less than B)."

[0012] [Damage suppressant] A damage suppressant according to one embodiment of the present invention (hereinafter referred to as "the damage suppressant") is a damage suppressant that contains polyalkyleneimine and / or a polyalkyleneimine derivative and suppresses damage caused by chlorine.

[0013] This damage inhibitor contains polyalkyleneimine and its derivatives as active ingredients, which are components newly discovered by the present inventors that have the ability to remove residual chlorine. Therefore, it can suppress damage caused by residual chlorine, for example, damage caused by residual chlorine to skin and hair. In addition, this damage inhibitor can also be used to repair damage.

[0014] Conventionally, plant extracts such as those described in Patent Document 1 have been known as ingredients capable of repairing damage caused by residual chlorine, but these plant extracts have had problems such as the need to be formulated at high concentrations to exert their repairing effect, which increases costs. On the other hand, polyalkyleneimine and its derivatives, which are the active ingredients of the present damage suppression agent, can exert their residual chlorine removal ability at relatively low concentrations compared to plant extracts and can suppress damage caused by residual chlorine, so in addition to having excellent damage suppression effects, they also have excellent cost benefits.

[0015] Damage caused by residual chlorine that can be suppressed by the present damage suppressant includes damage caused by residual chlorine to any human body, and specific examples include damage to the skin such as skin irritation, rough skin, itchiness, dryness, etc., and damage to the hair such as peeling of the hair cuticle, loss of luster (luster), fading, dryness, hair that is prone to breakage, and difficulty in running fingers through the hair, but are not limited to these.

[0016] The form of the damage inhibitor is not particularly limited, and examples thereof include an aqueous solution or a dispersion, but an aqueous solution is preferred.

[0017] Each component contained in this damage suppressant will be described in detail below.

[0018] <Polyalkyleneimine> The damage inhibitor may contain a polyalkyleneimine as an active ingredient. In this specification, the term "polyalkyleneimine" refers to a compound (polymer) having a main chain of repeating units composed of alkylene groups and amino groups, i.e., repeating units represented by the following formulas (A-1), (A-2), and / or (A-3):

[0019] [ka]

[0020] In the above formulas (A-1), (A-2), and (A-3), Q represents an alkylene group. Examples of the alkylene group represented by Q include an ethylene group, a propylene group, and a butylene group. In the repeating units represented by the above formula (A-1), (A-2), or (A-3) contained in the polyalkyleneimine, Q may be the same or different.

[0021] More specifically, examples of the polyalkyleneimine according to one embodiment of the present invention include polyethyleneimine, polypropyleneimine, polybutyleneimine, etc. These polyalkyleneimines may have a linear, branched, or cyclic structure. Among these, polyethyleneimine is preferred, and linear, branched, or dendritic polyethyleneimine is more preferred.

[0022] In this specification, "branched polyethyleneimine" means that the polyethyleneimine has secondary polymer chains branching from the main chain, and "dendritic polyethyleneimine" means that the polyethyleneimine has a densely packed multi-branched structure typically consisting of a core from which branches extend and numerous terminal groups.

[0023] When the polyalkyleneimine according to one embodiment of the present invention has a branched structure, the degree of branching of the polyalkyleneimine is greater than 0%, 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.

[0024] The branching degree of the polyalkyleneimine is 13 Based on the chart obtained by measuring C-NMR, the intensity ratio between the carbon atoms bonded to the tertiary amines and the carbon atoms bonded to the secondary amines is calculated, thereby calculating the number of tertiary amines, a, and the number of secondary amines, b, and the calculated values ​​of a and b can be used to calculate the following formula: Branching degree (%) = [a / (a+b)] × 100.

[0025] A linear polyalkyleneimine has no tertiary amines and therefore has a branching degree of 0%, whereas a polyalkyleneimine in which all nitrogen atoms are tertiary amines, i.e., a maximally branched polyalkyleneimine, has a branching degree of 100%.

[0026] The polyalkyleneimine according to one embodiment of the present invention is preferably a homopolymer or copolymer of these alkyleneimines, which is 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, by a conventional method. These may be used alone or in combination of two or more. More preferably, it is an ethyleneimine homopolymer (polyethyleneimine; PEI). Alternatively, it may be one obtained by polymerizing ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or the like.

[0027] From the viewpoint of providing a polyalkyleneimine derivative that has excellent storage stability when dissolved or dispersed in water, the number-average molecular weight (Mn) of the polyalkyleneimine according to one embodiment of the present invention is preferably 5,000 or more, more preferably 5,500 or more, even more preferably 6,000 or more, and particularly preferably 6,500 or more. The upper limit of the number-average molecular weight (Mn) of the polyalkyleneimine is not particularly limited, but may be, for example, 10,000 or less.

[0028] The weight-average molecular weight (Mw) of the polyalkyleneimine according to one embodiment of the present invention is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 50,000 or more, even more preferably 100,000 or more, and particularly preferably 200,000 or more, from the viewpoint of providing a polyalkyleneimine derivative having excellent storage stability when dissolved or dispersed in water. From the viewpoint of usability, the weight-average molecular weight (Mw) is preferably 500,000 or less, more preferably 400,000 or less, and even more preferably 350,000 or less.

[0029] The number average molecular weight and weight average molecular weight of the polyalkyleneimine according to one embodiment of the present invention can be measured by GPC (gel permeation chromatography) under the following conditions.

[0030] (conditions) Equipment: Shimadzu Corporation Eluent: Prepared in 0.5 mol% sodium nitrate and 0.5 mol% acetic acid Detector: RI Column: SHODEX OHpak SB-807HQ (2 columns) + SB-806M / HQ (2 columns) Column temperature: 40℃ Flow rate: 0.4ml / min Injection volume: 0.1%, 100μl Standard sample: pullulan.

[0031] The amine value per non-volatile content of the polyalkyleneimine according to one embodiment of the present invention 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 22 or less.

[0032] 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) 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.

[0033] The degree of cationization of the polyalkyleneimine according to one embodiment of the present invention 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.

[0034] The degree of cationization of the polyalkyleneimine can be measured using known methods, for example, it can be determined from the measured value of the N content measured by the Kjeldahl method, Method 2 of the Nitrogen Determination Method in the General Testing Methods of the Standards for Cosmetic Ingredients.

[0035] 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) A polyalkyleneimine according to one embodiment of the present invention contains at least one of a primary amine, a secondary amine, and a tertiary amine.

[0036] The content of primary amines in the polyalkyleneimine according to one embodiment of the present invention 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, and is preferably 50 mol% or less, more preferably 45 mol% or less, further preferably 40 mol% or less and 37 mol% or less.

[0037] The content of secondary amine in the polyalkyleneimine according to one embodiment of the present invention 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.

[0038] The content of tertiary amine in the polyalkyleneimine according to one embodiment of the present invention 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.

[0039] The molar ratio (amine ratio) of primary amine, secondary amine, and tertiary amine in the polyalkyleneimine according to one embodiment of the present invention 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.

[0040] The amine class ratio of the polyalkyleneimine can be measured by known methods such as GPC, NMR analysis, and titration.

[0041] In the polyalkyleneimine according to one embodiment of the present invention, 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.

[0042] <Polyalkyleneimine derivatives> The damage inhibitor may contain polyalkyleneimine as an active ingredient. In this specification, the term "polyalkyleneimine derivative" refers to a compound obtained by substituting the hydrogen bonded to the amino group contained in the polyalkyleneimine with another substituent. The polyalkyleneimine derivative can also be said to be a compound obtained by an addition reaction of the nitrogen atom of the polyalkyleneimine with a compound from which the substituent is derived.

[0043] Regarding the polyalkylene derivative according to one embodiment of the present invention, the description in the above <Polyalkyleneimine> section is incorporated as appropriate for specific aspects of the polyalkyleneimine before substitution (before the addition reaction).

[0044] (Polyalkyleneimine Derivative A) In one embodiment of the present invention, the polyalkyleneimine derivative contained in the damage inhibitor may be a polyalkyleneimine derivative in which the hydrogen bonded to the amino group contained in the polyalkyleneimine is substituted with any organic group (hereinafter referred to as "polyalkyleneimine derivative A").

[0045] Such a substituent is not particularly limited, but is preferably an organic group having 1 to 8 carbon atoms, more specifically, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, etc. having 1 to 8 carbon atoms. Of these substituents, an alkoxy group is preferred, an alkoxy group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group is more preferred, and an alkoxy group having 1 to 4 carbon atoms such as an ethoxy group is even more preferred.

[0046] The substitution amount of amino groups in the polyalkyleneimine derivative A according to one embodiment of the present invention, in other words, the ratio of substituted amino groups to the total amount of amino groups contained in the polyalkyleneimine derivative A, is preferably 20.0 mol% to 60.0 mol%, and more preferably 30.0 mol% to 50.0 mol%.

[0047] The number average molecular weight (Mn) of the polyalkyleneimine derivative A according to one embodiment of the present invention is preferably at least 150, more preferably at least 300, and even more preferably at least 600. There is no particular upper limit to the number average molecular weight (Mn) of the polyalkyleneimine derivative A, but it may be, for example, at most 50,000.

[0048] In this specification, the number average molecular weight of the polyalkyleneimine derivative A is a value measured by the same method as that of the polyalkyleneimine derivative B described below.

[0049] The method for producing the polyalkyleneimine derivative A according to one embodiment of the present invention is not particularly limited, but examples thereof include a method in which a primary or secondary amino group in the polyalkyleneimine is substituted with an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group.

[0050] (Polyalkyleneimine Derivative B) In another embodiment of the present invention, the polyalkyleneimine derivative contained in the damage inhibitor may be a polyalkyleneimine derivative (hereinafter, sometimes referred to as "polyalkyleneimine derivative B") obtained by addition reaction of alkylene oxide to a nitrogen atom of polyalkyleneimine. Polyalkyleneimine derivative B can also be said to be a polymer (hereinafter, sometimes referred to as "polyalkyleneimine derivative B") containing repeating units derived from alkyleneimine (i.e., repeating units represented by the above formulas (A-1), (A-2), and / or (A-3)) and repeating units derived from alkylene oxide.

[0051] Examples of alkylene oxides that are raw materials for polyalkyleneimine derivatives (to be added to polyalkyleneimine) include ethylene oxide, propylene oxide, butylene oxide, etc. Among these, ethylene oxide is preferred from the viewpoints of low irritation and safety.

[0052] The repeating unit derived from alkylene oxide contained in the polyalkyleneimine derivative B according to one embodiment of the present invention refers to, for example, the repeating unit represented in parentheses in the following general formula (2). In general formula (2), two asterisks each represent an element or group bonded to the repeating unit derived from alkylene oxide, and R2 represents an alkylene group having 2 to 10 carbon atoms which may have a substituent. Examples of the alkylene group include an ethylene group, -CH2CH2-; a propylene group, -CH(-CH3)CH2-; and the like. Examples of the substituent include an alkoxy group, an acetoxy group, an ester group, and the like.

[0053] [ka]

[0054] The repeating unit derived from alkylene oxide contained in the polyalkyleneimine derivative B may be bonded to a hydrogen atom; a linking group such as an ester group, a thioester group, an amide group, a thioamide group, an acetal group, a hemiacetal group, or a hemiketal group; a repeating unit derived from alkyleneimine, a repeating unit derived from alkylene oxide, or a residue of a group capable of reacting with a hydroxyl group.

[0055] The polyalkyleneimine derivative B may contain a structural moiety in which repeating units derived from alkylene oxide are successive (hereinafter also referred to as a structural moiety derived from polyalkylene oxide).

[0056] The repeating unit derived from alkylene oxide contained in the polyalkyleneimine derivative B may have, for example, a structure represented by the following general formula (3).

[0057] [ka]

[0058] In general formula (3), R2 represents an alkylene group having 2 to 10 carbon atoms which may have a substituent, and n represents the number of repeating units derived from alkylene oxide, and is, for example, preferably 1 to 30, and more preferably 2 to 25.

[0059] In the polyalkyleneimine derivative B according to one embodiment of the present invention, it is preferred that 50 mol % or more of all R2 (alkylene groups contained in repeating units derived from alkylene oxide) contained in the derivative are ethylene groups, -CH2CH2-, more preferably 80 mol % or more are ethylene groups, and even more preferably 90 mol % or more are ethylene groups.

[0060] The polyalkyleneimine derivative B according to one embodiment of the present invention may have repeating units other than repeating units derived from alkyleneimine and repeating units derived from alkylene oxide (hereinafter also referred to as "other repeating units"). Examples of other repeating units include, but are not limited to, hydrogen atoms; residues derived from initiators such as, but not limited to, amino groups; linking groups such as ester groups, thioester groups, amide groups, thioamide groups, acetal groups, hemiacetal groups, and hemiketal groups; and residues of compounds capable of reacting with hydroxyl groups, such as, but not limited to, acid anhydrides, isocyanates, and ester compounds.

[0061] The linking group may link a structural moiety derived from a polyalkyleneimine with a repeating unit derived from an alkylene oxide or a structural moiety derived from a polyalkylene oxide.

[0062] In the polyalkyleneimine derivative B according to one embodiment of the present invention, the molar ratio of repeating units derived from alkyleneimine to repeating units derived from alkylene oxide is preferably 1:0.1 to 1:100, more preferably 1:0.3 to 1:80, and further preferably 1:0.5 to 1:50, 1:0.5 to 1:30, 1:0.5 to 1:10, 1:0.5 to 1:5, and 1:0.5 to 1:3. A ratio within the above range has the advantage of high stability.

[0063] In the polyalkyleneimine derivative B according to one embodiment of the present invention, the total content of repeating units derived from alkyleneimine and repeating units derived from alkylene oxide is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to 100% by mass of the polyalkyleneimine derivative B according to one embodiment of the present invention. A content within the above range has the advantage of high stability.

[0064] The weight-average molecular weight (Mw) of the polyalkyleneimine derivative B according to one embodiment of the present invention is, from the viewpoint of improving stability, preferably 1,000 or more, more preferably 1,500 or more, even more preferably 2,000 or more, and particularly preferably 800 or more. From the viewpoint of the feeling during use, it is preferably 100,000 or less, more preferably 80,000 or less, and even more preferably 70,000 or less.

[0065] In this specification, the number average molecular weight and weight average molecular weight of the polyalkyleneimine derivative B are values ​​measured using GPC (gel permeation chromatography) under the following conditions.

[0066] (Measurement conditions) Measurement equipment: Tosoh EcoSEC HLC-8320GPC Elution solvent: (0.2 M nitric acid + Na, 0.5 M acetic acid) / acetonitrile = 50 / 50 vol% Detector: Differential Refractometer (RI) detector Column: Tosoh TSKgelguard column α, α-M, α-2500 Column temperature: 40℃ Flow rate: 0.8mL / min Injection volume: 20 μL (eluent preparation solution with sample concentration of 1.0 wt%) In this specification, "Na" means sodium.

[0067] The method for producing the polyalkyleneimine derivative B according to one embodiment of the present invention is not particularly limited, but can be, for example, produced by an addition reaction of alkylene oxide with amino groups contained in a polymer (i.e., polyalkyleneimine) having repeating units derived from alkyleneimine such as polyethyleneimine. The amount of alkylene oxide added (the amount of alkylene oxide subjected to the addition reaction) when producing the polyalkyleneimine derivative B is not particularly limited, but can be, for example, an average of 0.1 to 100 moles, preferably 0.5 to 50 moles, and more preferably 1.0 to 30 moles per mole of active hydrogen (hydrogen group bonded to the amino group) contained in the amino group of the polyalkyleneimine.

[0068] (Polyalkyleneimine Derivative C) In yet another embodiment of the present invention, the polyalkyleneimine derivative contained in the damage inhibitor may be a polyalkyleneimine derivative obtained by addition reaction of a compound having a structure of the following formula (1C) and / or (2C) to a nitrogen atom of a polyalkyleneimine, which has a substituent having a structure of the following formula (3C) and / or (4C), and the addition amount of the substituent relative to the nitrogen atom contained in the polyalkyleneimine (sometimes simply referred to as the addition amount or the addition amount of the substituent) is 0.1 mol % to 35 mol % (hereinafter, may be referred to as "polyalkyleneimine derivative C"): R 3 -R 1 (1C) R 4 -R 1 (2C) -CHCH(OH)-R 1 ···(3C) -CH2CH(OH)CH2-OR 1 (4C) (In formulas (1C) to (4C), R 1 is an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an aryl group having 8 to 20 carbon atoms, or -(CH2CH2O)nR а where R аrepresents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, or an aryl group having 8 to 20 carbon atoms; n represents an integer of 1 to 50. 3 represents an epoxy group, and R 4 represents a glycidyl ether group. In this specification, the amount of substituents added to the nitrogen atoms contained in the polyalkyleneimine is a value calculated based on the following formula using the amine value of the polyalkyleneimine. Amount added (mol %)={[reacted amount of the compound (g) / molecular weight of the compound (g / mol)] / [amount of the polyalkyleneimine (g)×solid content of the polyalkyleneimine (%)×amine value of the polyalkyleneimine (mmol / g (non-volatile content)) / 1000]}×100(%). In the above formula, the polyalkyleneimine is the polyalkyleneimine before the addition reaction with the compound having the structure of formula (1C) and / or (2C), in other words, before the addition of a substituent, and the amine value is the amine value of the polyalkyleneimine before the addition of a substituent.

[0069] The compound having the structure represented by the above formula (1C) is an epoxy group-containing compound from which the substituent (structural unit) represented by formula (3C) in the obtained polyalkyleneimine derivative is derived, and the compound having the structure represented by the above formula (2C) is a glycidyl ether compound from which the substituent (structural unit) represented by formula (4C) in the obtained polyalkyleneimine derivative is derived. That is, when the compound having the structure represented by the above formula (1C) is subjected to an addition reaction with a polyalkyleneimine, a structure represented by formula (3C) is formed, and when the compound having the structure represented by the above formula (2) is subjected to an addition reaction, a structure represented by formula (4C) is formed.

[0070] Specific examples of the compound represented by formula (1C) include compounds of the following formulae (1a) to (1c):

[0071] [ka]

[0072] Specific examples of the compound represented by formula (2C) include compounds of the following formulae (2a) to (2c):

[0073] [ka]

[0074] The epoxy equivalent of the compound having the structure of the above formula (1C) or (2C) is not particularly limited, but is preferably 150 to 500, and more preferably 200 to 400.

[0075] In this specification, the term "epoxy equivalent" refers to the molecular weight per epoxy group contained in a compound having an epoxy group. The epoxy equivalent of a compound can be measured, for example, in accordance with JIS K7236.

[0076] The alkyl group having 8 to 20 carbon atoms in the formulae (1C) to (4C) is not particularly limited and may be a straight-chain or branched-chain alkyl group having 8 to 20 carbon atoms. Specific examples of the alkyl group having 8 to 20 carbon atoms include an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group (a lauryl group), a 2-ethylhexyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0077] The alkenyl group having 8 to 20 carbon atoms in the formulae (1C) to (4C) is not particularly limited and may be a straight-chain or branched-chain alkenyl group having 8 to 20 carbon atoms. Specific examples of the alkenyl group having 8 to 20 carbon atoms include an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, a dodecenyl group, a 2-ethylhexenyl group, a tridecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, and a nonadecenyl group.

[0078] The aryl group having 8 to 20 carbon atoms in the formulae (1C) to (4C) is not particularly limited, and examples thereof include a 2,3- or 2,4-xylyl group, a mesityl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylyl group, a benzhydryl group, a trityl group, and a pyrenyl group.

[0079] Among these, R 1 As R, an alkyl group having 8 or more carbon atoms is preferred, an alkyl group having 9 or more carbon atoms is more preferred, an alkyl group having 10 or more carbon atoms is even more preferred, and an alkyl group having 11 or more carbon atoms is even more preferred. a is preferably an alkyl group having 8 to 20 carbon atoms, more preferably an alkyl group having 12 to 20 carbon atoms. 1 and R a If the number of carbon atoms is 15 or more, it has the advantage of being highly stable.

[0080] In the polyalkyleneimine derivative C according to one embodiment of the present invention, the amount of the substituents having the structure of formula (3C) and / or (4C) added relative to the nitrogen atoms contained in the raw material polyalkyleneimine is 0.1 mol % to 35 mol %, preferably 0.5 mol % to 30 mol %, more preferably 1.0 mol % to 25 mol %, and particularly preferably 1.5 mol % to 10 mol %. Controlling the amount of the substituents added within the above range has the advantage of high stability.

[0081] The polyalkyleneimine derivative C according to one embodiment of the present invention can be produced by a method including an addition step of subjecting the amino group of the polyalkyleneimine to an addition reaction with a compound having the structure of the above formula (1C) and / or (2C).

[0082] The polyalkyleneimine derivative C may have a highly hydrophobic structure derived from the compounds of the above formula (1C) and / or (2C). Therefore, in one embodiment of the present invention, the polyalkyleneimine derivative C can also be said to be a hydrophobically modified polyalkyleneimine derivative.

[0083] (Other polyalkyleneimine derivatives) The polyalkyleneimine derivative contained in the damage inhibitor may be a polyalkyleneimine derivative other than the above-mentioned polyalkyleneimine derivatives A to C, and may be, for example, the following polyalkyleneimine derivatives: (i) compounds 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 are added to some or all of the primary amino groups and / or secondary amino groups contained in a polyalkyleneimine, per mole of active hydrogen in the amino groups; (ii) compounds in which, for example, a compound having a carbon-carbon unsaturated double bond, such as acrylic acid, acrylic acid esters, 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 a polyalkyleneimine by Michael addition; and (iii) compounds 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 a polyalkyleneimine.

[0084] <Content of Polyalkyleneimine and Polyalkyleneimine Derivatives> The amount of polyalkyleneimine and / or polyalkyleneimine derivative contained in the damage inhibitor is not particularly limited as long as the damage inhibitor can suppress damage caused by residual chlorine. For example, it may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 1% by mass or more relative to the total amount (100% by mass) of the damage inhibitor. The upper limit is also not particularly limited, and may be, for example, 100% by mass or less, 80% by mass or less, 50% by mass or less, 20% by mass or less, or 10% by mass or less. If the content of polyalkyleneimine and / or polyalkyleneimine derivative in the damage inhibitor (when multiple types of polyalkyleneimine and / or polyalkyleneimine derivatives are contained, the total amount of these) is 0.01% by mass or more, the effect of suppressing damage caused by residual chlorine is exhibited, while if it is 30% by mass or less, there is the advantage that the feeling of use is not impaired.

[0085] <Other ingredients> In addition to the polyalkyleneimine and / or polyalkyleneimine derivative, the damage inhibitor may optionally contain the following components (other components): The damage inhibitor may contain only one type of such other component, or may contain two or more types.

[0086] (solvent) The damage suppressant may contain a solvent as another component.

[0087] The solvent that can be contained in the damage suppressant includes a water-soluble solvent including water.

[0088] The water-soluble solvent that can be contained in the damage inhibitor as a solvent is not particularly limited, but examples thereof include monoalcohols and polyhydric alcohols.

[0089] Examples of monoalcohols that the damage suppressant may contain as a water-soluble solvent include ethyl alcohol, isopropyl alcohol, propyl alcohol, benzyl alcohol, phenylethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and alkyl ethers of diethylene glycol.

[0090] Examples of polyhydric alcohols that the damage inhibitor may contain as a water-soluble solvent include glycol; glycerin; sugars such as glucose, fructose, galactose, maltose, and lactose; and sugar alcohols such as inositol, sorbitol, mannitol, and xylitol.

[0091] As used herein, glycol refers to a compound consisting of carbon, oxygen, and hydrogen with two hydroxyl groups attached to two different carbon atoms.

[0092] Examples of such glycols include aliphatic glycols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, dipropylene glycol, and pinacol; and alicyclic glycols such as cyclopentane-1,2-diol, cyclohexane-1,2-diol, and cyclohexane-1,4-diol.

[0093] The amount of solvent that the damage inhibitor may contain is not particularly limited, and may be, for example, 0.001% by mass or more, 0.01% by mass or more, or 0.05% by mass or more, and may be 20% by mass or less, 10% by mass or less, or 5% by mass or less.

[0094] The content of water contained in the damage inhibitor is not particularly limited, and may be, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.05 parts by mass or more, or 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the damage inhibitor.

[0095] The content of water contained in the damage inhibitor is not particularly limited, and may be, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.05 parts by mass or more, or 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the damage inhibitor.

[0096] (Discoloration inhibitor) The damage inhibitor may contain a discoloration inhibitor as another component. Polyalkyleneimines and their derivatives tend to discolor easily in environments such as air, heat, and sunlight. When the damage inhibitor contains a discoloration inhibitor, such discoloration can be suppressed.

[0097] Examples of discoloration inhibitors that can be contained in this damage inhibitor include sulfites, phosphonic acids (salts), aminopolycarboxylic acids (salts), etc. Aminopolycarboxylic acids are a general term for compounds that have an amino group and multiple carboxy groups in the molecule.

[0098] The sulfite that the damage inhibitor may contain as a discoloration inhibitor includes one or more selected from sodium sulfite, potassium sulfite, ammonium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, sodium disulfite, potassium disulfite, and ammonium disulfite, with sodium hydrogen sulfite, potassium hydrogen sulfite, ammonium hydrogen sulfite, and sodium disulfite being preferred, and sodium hydrogen sulfite and sodium disulfite being more preferred.

[0099] Examples of the phosphonic acid (salt) that the damage inhibitor may contain as a discoloration inhibitor include monophosphonic acids such as ethylphosphonic acid (salt), phenylphosphonic acid, n-dodecylphosphonic acid, butylphosphonic acid, tert-butylphosphonic acid (salt), (aminomethyl)phosphonic acid (salt), octadecylphosphonic acid, octylphosphonic acid, and ethephon (salt); and polyphosphonic acids such as ethylenediaminetetramethylenephosphonic acid (salt), diethylenetriaminepentakis(methylphosphonic acid) (salt), nitrilotrismethylenephosphonic acid (salt), 1-hydroxyethane-1,1-diphosphonic acid (salt) (also referred to as etidronic acid (salt)), phytic acid (salt), and triphosphoric acid (salt). Polyphosphonic acid is more preferred, with 1-hydroxyethane-1,1-diphosphonic acid being even more preferred, and phytic acid being particularly preferred. Examples of the phosphonate salt according to one embodiment of the present invention include metal salts such as sodium salts, potassium salts, and calcium salts; and amine salts, with metal salts being more preferred, and sodium salts being more preferred.

[0100] Phytic acid or its salts will now be described. Phytic acid has a structure in which all six hydroxyl groups of inositol are phosphorylated. Nine isomers are known, but the most common is myo-inositol-1,2,3,4,5,6-hexaphosphate. Any of these isomers may be used as phytic acid in one embodiment of the present invention, and some of the six hydroxyl groups may not be phosphorylated. Phytic acid is found in most plants in the form of a salt (phytin) bound with minerals such as calcium and magnesium. It can be industrially obtained by extraction from rice bran, corn, etc. with water or an acidic aqueous solution. Commercially available products are available from Tsuno Foods Co., Ltd., Shikishima Starch Co., Ltd., FC Chemical Co., Ltd., etc. The phytic acid used in the present invention may be formulated in its original form or in the form of a salt. The salt of phytic acid is not particularly limited, but specific examples include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; metal salts such as aluminum, iron, and zinc; basic amino acid salts such as lysine, arginine, histidine, and ornithine; and organic amine salts such as ammonium, monoethanolamine, diethanolamine, triethanolamine, and stearylamine.

[0101] Commercially available products containing phytic acid include Phytic Acid (IP6) (manufactured by Tsuno Foods Co., Ltd.).

[0102] Commercially available products containing etidronic acid include Chelestos PH-210SD (manufactured by Chelestos Inc.) and Chelesvit D (manufactured by Chelestos Inc.).

[0103] Examples of aminopolycarboxylic acid (salts) that the damage inhibitor may contain as a discoloration inhibitor include ethylenediaminetetraacetic acid (salts), diethylenetriaminepentaacetic acid (salts), hydroxyethylenediaminetriacetic acid (salts), and ethylenediamine disuccinate (salts), cyclohexanediaminetetraacetic acid (salts), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (salts), glycol ether diaminetetraacetic acid (salts), alanine diacetic acid (salts), alkoyl ethylenediaminetriacetic acid (e.g., lauroyl ethylenediaminetriacetic acid (salts), L-glutamic acid diacetic acid (salts), aspartic acid diacetic acid (salts), aspartic acid monoacetic acid, iminodisuccinic acid (salts), diaminocyclohexanetetraacetic acid (salts), 1,2-diaminopropanetetraacetic acid (salts), 1,3-diamino-2-propanol Examples of the aminopolycarboxylate salt include one or more selected from L-glutamic acid tetraacetic acid (salt), dipicolinic acid (salt), ethanolamine diacetic acid, ethanoldiglycine (salt), ethylenediamine diglutaric acid (salt), ethylenediamine dihydroxyphenylacetic acid (salt), ethylenediamine dipropionic acid (salt), ethylenediamine disuccinate (salt), ethylenediamine monosuccinic acid (salt), ethylenediamine tetrapropionic acid (salt), and ethylene glycol aminoethyl ester tetraacetic acid (salt), with L-glutamic acid diacetic acid being more preferred and diethylenetriamine pentaacetic acid being even more preferred. Examples of the aminopolycarboxylate salt according to one embodiment of the present invention include metal salts such as sodium salts, potassium salts, and calcium salts; amine salts, etc., with metal salts being more preferred and sodium salts being even more preferred.

[0104] Examples of the ethylenediaminetetraacetic acid (salt) according to one embodiment of the present invention include ethylenediaminetetraacetic acid, tetrasodium ethylenediaminetetraacetic acid, trisodium ethylenediaminetetraacetic acid, and disodium ethylenediaminetetraacetic acid, with disodium ethylenediaminetetraacetic acid being more preferred.

[0105] Examples of L-glutamic acid diacetate (salts) include L-glutamic acid diacetate and tetrasodium L-glutamic acid diacetate.

[0106] Examples of diethylenetriaminepentaacetic acid (salts) include diethylenetriaminepentaacetic acid and pentasodium diethylenetriaminepentaacetate.

[0107] Iminodisuccinic acid (salts) include tetrasodium 3-hydroxy-2,2'-iminodisuccinate.

[0108] The content of compound A in the damage inhibitor is not particularly limited, and may be, for example, 0.0001 parts by mass or more, 0.001 parts by mass or more, or 0.005 parts by mass or more, or 20 parts by mass or less, 10 parts by mass or less, or 5 parts by mass or less, per 100 parts by mass of the damage inhibitor.

[0109] (surfactant) The damage inhibitor may contain a surfactant as another component.

[0110] Examples of surfactants that can be contained in the damage inhibitor include anionic surfactants, nonionic surfactants, and amphoteric surfactants. From the viewpoint of use in cosmetics, it is preferable that the damage inhibitor contain an anionic surfactant.

[0111] The anionic surfactants that may be contained in the damage inhibitor are preferably polyoxyethylene lauryl ether sulfate and polyoxyethylene lauryl ether acetate from the viewpoint of use in cosmetics. Examples of polyoxyethylene lauryl ether sulfate include sodium laureth sulfate (EO addition moles: 3 mol), sodium laureth sulfate (EO addition moles: 2 mol), sodium laureth sulfate (EO addition moles: 1 mol), ammonium laureth sulfate, and TEA laureth sulfate. Examples of polyoxyethylene lauryl ether acetate include sodium laureth-4 carboxylate, sodium laureth-6 carboxylate, and sodium laureth-11 carboxylate.

[0112] Examples of anionic surfactants that may be contained in the damage inhibitor other than those mentioned above include alkenyl sulfonates (α-olefin sulfonates), alkyl sulfoacetates, alkyl sulfates, alkanesulfonates, higher fatty acid salts, N-acylamine salts, higher fatty acid amide sulfonates, and polyoxyethylene fatty acid phosphate ester salts.

[0113] Examples of amphoteric surfactants that may be contained in the damage inhibitor include amino acid-type, betaine-type, and amine oxide-type amphoteric surfactants, from the viewpoint of use in cosmetics or quasi-drugs.

[0114] Examples of amino acid type amphoteric surfactants include glycine type amphoteric surfactants such as N-lauroyl-N'-carboxymethyl-N'-hydroxyethylethylenediamine sodium (sodium lauroamphoacetate), alkyldiaminoethylglycine hydrochloride, sodium lauryldiaminoethylglycine, and palm oil fatty acid acyl-N-carboxyethyl-N-hydroxyethylethylenediamine sodium; and aminopropionic acid type amphoteric surfactants such as sodium laurylaminopropionate, sodium laurylaminodipropionate, and triethanolamine laurylaminopropionate.

[0115] Specific examples of betaine-type amphoteric surfactants include aminoacetic acid betaine-type amphoteric surfactants such as lauryl dimethylaminoacetic acid betaine, coconut oil alkyl betaine, myristyl dimethylaminoacetic acid betaine, stearyl dimethyl betaine sodium, coconut oil fatty acid amidopropyl betaine, palm oil fatty acid amidopropyl betaine, lauric acid amidopropyl betaine, ricinoleic acid amidopropyl betaine, and stearyl dihydroxyethyl betaine; and sulfobetaine-type amphoteric surfactants such as lauryl hydroxysulfobetaine.

[0116] Specific examples of amine oxide type amphoteric surfactants include lauramidopropylamine oxide, cocamidopropylamine oxide, wheat germ oil fatty acid amidopropylamine oxide, soyamidopropylamine oxide, myristamidopropylamine oxide, milk fat fatty acid amidopropylamine oxide, oleamine oxide, cocoamine oxide, dihydroxyethyl cocamine oxide, dihydroxyethyl lauramine oxide, stearamine oxide, decylamine oxide, decyltetradecylamine oxide, behenamine oxide, myristamine oxide, and lauramine oxide.

[0117] As the amphoteric surfactant, it is preferable to use a desalted purified product from the viewpoint of compatibility with the cationic polymer.

[0118] The content of the surfactant in the present damage inhibitor is not particularly limited, and may be, for example, 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more, or 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less, per 100 parts by mass of the present damage inhibitor.

[0119] (Other additives) The damage inhibitor may contain various additives (other additives) other than the above-mentioned components, such as hydrocarbons, triglycerides including fats and oils, ester oils, animal and vegetable oils, higher alcohols, higher fatty acids, silicone oils, vitamins, ultraviolet absorbers, water-soluble polymers, antioxidants, sequestering agents, thickeners, preservatives, dyes, pigments, and fragrances.

[0120] [Cosmetics] In one embodiment of the present invention, a cosmetic preparation containing the present damage suppression agent (hereinafter referred to as "the present cosmetic preparation") is provided. Because the present cosmetic preparation contains the present damage suppression agent, it is possible to suppress damage caused by chlorine in addition to providing cosmetic effects. The present cosmetic preparation can also be said to be a cosmetic preparation containing polyalkyleneimine or a derivative thereof, which is the active ingredient of the present damage suppression agent.

[0121] The present cosmetic may contain any of the above polyalkyleneimines or their derivatives, but polyalkyleneimine derivative B is particularly suitable for use because it has low cationicity and is less likely to aggregate with anionic components that tend to be contained in large amounts in cosmetic preparations. In other words, it is particularly preferable for the present cosmetic to contain polyalkyleneimine derivative B.

[0122] The target area for the present cosmetic composition is not particularly limited and may be, for example, skin or hair, but is particularly suitable for use on hair. That is, the present cosmetic composition can be suitably used as a hair cosmetic composition.

[0123] The form of the present cosmetic is not particularly limited, and possible forms include W / O emulsion cosmetics, O / W emulsion cosmetics, W / O / W emulsion cosmetics, cosmetics consisting of an oil-water bicontinuous phase, oil-based cosmetics, aqueous cosmetics, etc. More specific examples of product forms of the present cosmetic include hair cosmetics such as hair mists, hair liquids, hair milks, hair tonics, hair conditioners, hair treatments, rinses, hair masks, hair shampoos, and hair growth agents; skin care cosmetics such as lotions, emulsions, creams, and packs; makeup cosmetics such as foundations, lipsticks, and eye shadows; sunscreen cosmetics (sunscreens); body cosmetics; fragrance cosmetics; skin cosmetics such as makeup removers and body soaps (body shampoos); antiperspirants, ointments, etc. [Example]

[0124] 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."

[0125] <Number-average molecular weight and weight-average molecular weight of polyalkyleneimine> The number average molecular weight and weight average molecular weight of the polyalkyleneimine were measured by GPC (gel permeation chromatography) under the following conditions.

[0126] (conditions) Measuring equipment: Shimadzu Corporation Columns used: Showa Denko SHODEX OHpak SB-807HQ (2 columns) + SB-806M / HQ (2 columns) Column temperature: 40℃ Eluent: Prepared with 0.5 mol% sodium nitrate and 0.5 mol% acetic acid Flow rate: 0.4ml / min Injection volume: 0.1%, 100μL Standard substance: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: differential refractometer (Shimadzu Corporation).

[0127] <Number-average molecular weight and weight-average molecular weight of polyalkyleneimine derivative B> The number average molecular weight and weight average molecular weight of the polyalkyleneimine derivative B were measured by GPC (gel permeation chromatography) under the following conditions.

[0128] (conditions) Measurement equipment: Tosoh EcoSEC HLC-8320GPC Elution solvent: (0.2 M nitric acid + Na, 0.5 M acetic acid) / acetonitrile = 50 / 50 vol% Detector: Differential Refractometer (RI) detector Column: Tosoh TSKgelguard column α, α-M, α-2500 Column temperature: 40℃ Flow rate: 0.8mL / min Injection volume: 20 μL (eluent preparation solution with sample concentration of 1.0 wt %).

[0129] Example 1 (Preparation of damage suppressant) Polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 9,000, weight average molecular weight 330,000, amine value 18 mmol / g, primary amine / secondary amine / tertiary amine = 25 / 50 / 25 (mol%)) was mixed with purified water to a solids concentration of 2% to prepare a damage inhibitor containing polyalkyleneimine (polyethyleneimine) in aqueous solution form. The pH of the resulting damage inhibitor was 11.

[0130] (Evaluation of the chlorine removal ability of damage inhibitors) 0.5g of the above damage inhibitor and 10g of 0.001% sodium hypochlorite aqueous solution were mixed, and purified water was added to the mixture to make a total of 100g to prepare a sample. The solid content of the sample was 0.1%. The chlorine concentration in this sample was 0.0001%, which corresponds to the residual chlorine concentration standard for tap water.

[0131] 2.5 ml of phosphate buffer solution was weighed into a stoppered test tube, followed by the addition of 0.5 g of DPD reagent. The sample was then added to make a total volume of 50 ml. After mixing, the absorbance at 510 nm was measured using a spectrophotometer within 1 minute, and the residual chlorine removal rate was calculated from the measured absorbance. The results are shown in Table 1.

[0132] Example 2 A damage inhibitor was prepared in the same manner as in Example 1, except that the pH of the damage inhibitor was adjusted to 5.5 using succinic acid, and the chlorine removal ability was evaluated. The results are shown in Table 1.

[0133] Example 3 A damage inhibitor was prepared in the same manner as in Example 1, except that polyalkyleneimine derivative B, polyethyleneimine ethoxylate (manufactured by Nippon Shokubai Co., Ltd., a polyalkyleneimine derivative obtained by adding 20 moles of ethylene oxide to 1 mole of active hydrogen of polyethyleneimine, weight-average molecular weight 13,000), was used instead of polyethyleneimine, and its chlorine removal ability was evaluated. The results are shown in Table 1. The pH of the resulting damage inhibitor was 8.5.

[0134] Example 4 A damage inhibitor was prepared in the same manner as in Example 3, except that the pH of the damage inhibitor was adjusted to 6.5 using succinic acid, and the chlorine removal ability was evaluated. The results are shown in Table 1.

[0135] Example 5 A damage inhibitor was prepared in the same manner as in Example 1, except that polyalkyleneimine derivative C, a hydrophobically modified polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., a polyalkyleneimine derivative obtained by adding 1.5 mol of stearyl glycidyl ether to 1 mol of active hydrogen of polyethyleneimine), was used instead of polyethyleneimine, and its chlorine removal ability was evaluated. The results are shown in Table 1. The pH of the resulting damage inhibitor was 8.9.

[0136] Example 6 A damage inhibitor was prepared in the same manner as in Example 5, except that the pH of the damage inhibitor was adjusted to 5.5 using succinic acid, and its chlorine removal ability was evaluated. The results are shown in Table 1.

[0137] [Table 1]

[0138] Comparative Example 1 A sample was prepared by adding purified water to 10 g of a 0.001% aqueous solution of sodium hypochlorite so that the total amount was 100 g, without adding any damage inhibitor.

[0139] 2.5 ml of phosphate buffer solution was weighed into a stoppered test tube, followed by the addition of 0.5 g of DPD reagent. The sample was then added to make a total volume of 50 ml. After mixing, the absorbance at 510 nm was measured using a spectrophotometer within 1 minute, and the residual chlorine removal rate was calculated from the measured absorbance. The results are shown in Table 1.

[0140] Comparative Example 2 Instead of the damage inhibitor, a 2% aqueous solution (pH = 9.3) of (acrylic acid / MA) copolymer Na (manufactured by Nippon Shokubai Co., Ltd., product name: CR-C50, weight average molecular weight 5,000) was prepared, and the chlorine removal ability was evaluated in the same manner as in Example 1, except that 0.5 g of this aqueous solution was used instead of the damage inhibitor. The results are shown in Table 1.

[0141] Comparative Example 3 Instead of the damage inhibitor, a 2% aqueous solution (pH = 8.3) of sodium polyacrylate (manufactured by Nippon Shokubai Co., Ltd., product name: CR-H35, weight average molecular weight 3,500) was prepared, and the chlorine removal ability was evaluated in the same manner as in Example 1, except that 0.5 g of this aqueous solution was used instead of the damage inhibitor. The results are shown in Table 1.

[0142] Comparative Example 4 Instead of the damage inhibitor, a 2% aqueous solution of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., product name: CR-A100, weight average molecular weight 10,000) (pH = 4.4) was prepared, and the chlorine removal ability was evaluated in the same manner as in Example 1, except that 0.5 g of this aqueous solution was used instead of the damage inhibitor. The results are shown in Table 1.

[0143] Comparative Example 5 Instead of the damage inhibitor, a 2% aqueous solution (pH = 9.7) of sodium polyacrylate (manufactured by Nippon Shokubai Co., Ltd., product name: CR-H1700, weight average molecular weight 170,000) was prepared, and the chlorine removal ability was evaluated in the same manner as in Example 1, except that 0.5 g of this aqueous solution was used instead of the damage inhibitor. The results are shown in Table 1.

[0144] Comparative Example 6 Instead of the damage inhibitor, a 2% aqueous solution of polyacrylic acid (manufactured by Nippon Shokubai Co., Ltd., product name: CR-A8000, weight average molecular weight 800,000) (pH = 4.6) was prepared, and the chlorine removal ability was evaluated in the same manner as in Example 1, except that 0.5 g of this aqueous solution was used instead of the damage inhibitor. The results are shown in Table 1.

[0145] [Table 1]

[0146] [Summary 1] As is clear from Table 1, it was shown that the damage inhibitor containing polyalkyleneimine or its derivative can remove 96% or more of the free residual chlorine in an aqueous solution with a residual chlorine concentration of 0.0001%.

[0147] [Reference example 1] A bundle of 100% human black hair was dyed with a commercially available oxidative hair dye, and the hair surface condition, hair gloss, hair fading, and hair dryness were evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0148] The evaluation method for each item was as follows:

[0149] (Hair surface condition) The surface of each hair bundle was observed using a scanning electron microscope (FE-SEM: JSM7600F, manufactured by JEOL Ltd.), and the state of the cuticle was evaluated.

[0150] (Hair shine) The glossiness of each hair bundle was measured using a Glossymeter GL200 (manufactured by Courage+Khazaka) to evaluate the shine of the hair. Note that the glossiness is an arbitrary unit, and the higher the value, the shinier the hair.

[0151] (Hair discoloration) Each hair bundle was visually inspected by five expert panelists, who evaluated the fading of the oxidative hair dye on a five-point scale according to the following criteria. The average of the five panelists' evaluation scores was used as the evaluation score. <Evaluation criteria> 5: Standards 4: Slightly faded compared to the standard 3: Faded more than 4 compared to the standard 2: Faded more than 3 compared to the standard 1: Faded more than 2 compared to the standard.

[0152] (Dry hair) Each hair bundle was touched by five expert panelists and evaluated on a four-point scale according to the following criteria. The average score of the five panelists was used as the evaluation score. <Evaluation criteria> 4: No dryness 3: Almost no dryness 2: I feel a little dryness 1: It feels dry.

[0153] In addition, peeling of the hair cuticle, loss of shine, fading, and dryness are all damage that occurs to hair due to residual chlorine.

[0154] Comparative Example 7 A 100% human black hair bundle was dyed with a commercially available oxidative hair dye and immersed in a 0.0001% sodium hypochlorite aqueous solution and dried seven times. The treated hair bundle was evaluated for hair surface condition, hair gloss, hair discoloration, and hair dryness using the same methods as in Reference Example 1. The results of the observation of the hair surface condition are shown in Figure 1, and the evaluation results for other items are shown in Table 2.

[0155] Example 7 (Preparation of damage suppressant) Polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., number average molecular weight 9,000, weight average molecular weight 330,000, amine value 18 mmol / g, primary amine / secondary amine / tertiary amine = 25 / 50 / 25 (mol%)) was mixed with purified water to a solids concentration of 0.1%, to prepare a damage inhibitor containing polyalkyleneimine (polyethyleneimine) in the form of an aqueous solution.

[0156] (Evaluation of hair damage suppression effect) A 100% human black hair bundle dyed with a commercially available oxidative hair dye was immersed in a 0.0001% sodium hypochlorite aqueous solution, then immersed in the damage inhibitor and dried, a process repeated seven times. The treated hair bundle was evaluated for hair surface condition, hair gloss, hair discoloration, and hair dryness using the same methods as in Reference Example 1. The results of the observation of the hair surface condition are shown in Figure 1, and the evaluation results for other items are shown in Table 2.

[0157] Example 8 A damage inhibitor was prepared in the same manner as in Example 7, except that polyethyleneimine derivative B, polyethyleneimine ethoxylate (manufactured by Nippon Shokubai Co., Ltd., a polyalkyleneimine derivative obtained by adding 20 mol of ethylene oxide to 1 mol of active hydrogen of polyethyleneimine, weight average molecular weight 13,000), was used instead of polyethyleneimine, and the hair damage inhibitory effect was evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0158] Example 9 A damage inhibitor was prepared in the same manner as in Example 7, except that polyalkyleneimine derivative C, hydrophobically modified polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., a polyalkyleneimine derivative obtained by adding 1.5 mol of stearyl glycidyl ether to 1 mol of active hydrogen of polyethyleneimine), was used instead of polyethyleneimine, and the hair damage inhibitory effect was evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0159] Comparative Example 8 A 100% human black hair bundle was dyed with a commercially available oxidative hair dye and immersed in a 0.0001% sodium hypochlorite aqueous solution and dried 14 times. The treated hair bundle was evaluated for hair surface condition, hair gloss, hair discoloration, and hair dryness using the same methods as in Reference Example 1. The observation results for the hair surface condition are shown in Figure 1, and the evaluation results for other items are shown in Table 2.

[0160] Example 10 A hair bundle made of 100% black human hair dyed with a commercially available oxidative hair dye was immersed in a 0.0001% aqueous solution of sodium hypochlorite, then immersed in the above damage inhibitor and dried, and the process was repeated 14 times. A damage inhibitor was prepared using the same procedure as in Example 7, and the hair damage inhibitor effect was evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0161] Example 11 A hair bundle made of 100% black human hair dyed with a commercially available oxidative hair dye was immersed in a 0.0001% aqueous solution of sodium hypochlorite, then immersed in the above damage inhibitor and dried. This process was repeated 14 times, but the damage inhibitor was prepared in the same manner as in Example 8, and the hair damage inhibitor effect was evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0162] Example 12 A hair bundle made of 100% black human hair dyed with a commercially available oxidative hair dye was immersed in a 0.0001% aqueous solution of sodium hypochlorite, then immersed in the above damage inhibitor and dried, and the process was repeated 14 times. A damage inhibitor was prepared using the same procedure as in Example 9, and the hair damage inhibitor effect was evaluated. The observation results of the hair surface condition are shown in Figure 1, and the evaluation results of other items are shown in Table 2.

[0163] [Table 2]

[0164] [Summary 2] As is clear from Figure 1 and Table 2, the hair bundles of Examples 7 to 9 and Examples 10 to 12, to which the damage inhibitor was applied after chlorine treatment, showed less cuticle peeling, higher hair gloss, less fading of the oxidative hair dye, and less dryness, compared to Comparative Examples 7 and 8. These findings demonstrate that the damage inhibitor can suppress damage caused by residual chlorine.

[0165] [Reference example 2] The chloride ion content on a hair bundle made of 100% black human hair (manufactured by Beaulax, product number: BS-BA) was measured. The evaluation results are shown in Table 3.

[0166] (Method for measuring chloride ions) The chloride ion measurement was carried out using the following apparatus under the following conditions. Equipment used: Shimadzu AXIS-NOVA (narrow scan performed with XPS) Measurement conditions: NarrowScan LensMode: FOV1*Survey Res: 20 Iris(Aper): slot(SPECTRUM SLIT) Anode: Mono (Al (Mono)) (144W) Step(meV): 100 DwellTime(ms): 100 ChargeNeutraliser: ON(3.6).

[0167] Comparative Example 9 The above hair bundle was immersed in a 0.0001% sodium hypochlorite aqueous solution at 25°C for 30 minutes and then dried. The chloride ions on the hair of the hair bundle were measured. The evaluation results are shown in Table 3.

[0168] Example 13 The above hair bundle was immersed in a 0.0001% sodium hypochlorite aqueous solution at 25°C for 30 minutes, then immersed in a 0.1% polyethyleneimine aqueous solution (adjusted to pH 5.5 with succinic acid) at 25°C for 5 minutes, and then dried. The chloride ions on the hair bundle were measured. The evaluation results are shown in Table 3.

[0169] Example 14 The above hair bundle was immersed in a 0.0001% sodium hypochlorite aqueous solution at 25°C for 30 minutes, then immersed in a 0.1% polyethyleneimine ethoxylate (polyalkyleneimine derivative B) aqueous solution (adjusted to pH 5.5 with succinic acid) at 25°C for 5 minutes, and then dried. The chloride ions on the hair bundle were measured. The evaluation results are shown in Table 3.

[0170] Example 15 The above hair bundle was immersed in a 0.0001% aqueous solution of sodium hypochlorite at 25°C for 30 minutes, then immersed in a 0.1% aqueous solution of hydrophobically modified polyethyleneimine (polyalkyleneimine derivative C) (adjusted to pH 5.5 with succinic acid) at 25°C for 5 minutes, and then dried. The chloride ions on the hair bundle were measured. The evaluation results are shown in Table 3.

[0171] [Table 3]

[0172] [Summary 3] As is clear from Table 3, the hair bundles of Examples 13 to 15, to which the damage inhibitor was applied after chlorine treatment, had a reduced chloride ion concentration on the hair compared to the hair bundle of Comparative Example 9, to which only chlorine treatment was performed. These results demonstrate that the damage inhibitor can remove residual chlorine from the hair, thereby suppressing damage caused by such residual chlorine.

[0173] Example 16 A rinse-off conditioner containing the damage inhibitor was prepared using the amounts and types of ingredients listed in Table 4 below, as follows: (1) ingredients 1 and 2 were dissolved uniformly at 80±5°C; (2) ingredients 3 to 6 were dissolved uniformly at 80±5°C separately; (3) the solution of (2) was added to the solution of (1), and emulsified at 80±5°C for 5 minutes at 200 rpm; (4) the emulsion of (3) was slowly cooled to 50°C; (5) ingredients 7 to 9 were mixed uniformly; (6) the mixture of (5) was slowly added to the emulsion of (4), and mixed uniformly; (7) ingredient 10 was added to the mixture of (6), and after uniform mixing, ingredient 11 was added and the pH was adjusted to 4.0 to 4.5, thereby obtaining a rinse-off conditioner containing the damage inhibitor.

[0174] The resulting rinse-off conditioner was a rinse-off conditioner that was capable of suppressing damage caused by residual chlorine.

[0175] [Table 4]

[0176] Raw material 1: Stearamidopropyl dimethylamine, manufactured by Nikko Chemicals Co., Ltd., NIKKOL Amidoamine MPS Ingredient 2: Cetearyl alcohol, Kao Corporation, Kalcol 6850 Ingredient 3: Purified water Raw material 4: Succinic acid, Nippon Shokubai Co., Ltd., CG-SA Ingredient 5: Glycerin, Miyoshi Oil & Fat Co., Ltd., concentrated glycerin for cosmetics Raw material 6: Etidronic acid aqueous solution, manufactured by Chelest Co., Ltd., Chelest 210SD Raw material 7: PEI-1500 aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 30% aqueous solution of polyethyleneimine (molecular weight 250,000) Ingredient 8: Dimethicone, Shin-Etsu Chemical Co., Ltd., KF-96H-500,000 CS Ingredient 9: Dimethicone, Shin-Etsu Chemical Co., Ltd., KF-96A-10CS Ingredient 10: Guar hydroxypropyltrimonium chloride aqueous solution, MP Gokyo Food & Chemicals Co., Ltd., 2% aqueous solution of Labolgum CG-M8M Raw material 11: Succinic acid aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SA.

[0177] Example 17 A shampoo containing the damage inhibitor was prepared using the amounts and types of ingredients listed in Table 5 below, using the following procedure: (1) ingredients 1 and 2 were dissolved uniformly at 80±5°C; (2) ingredients 3 to 6 were added sequentially to the solution of (1) at 80±5°C and dissolved uniformly; (3) ingredients 7 to 12 were added sequentially to the solution of (2) at 80±5°C and dissolved uniformly; (4) the solution of (3) was slowly cooled to 50°C; (5) ingredient 13 was added to the solution of (4) and mixed uniformly; (6) ingredient 14 was added to the mixture of (5) and the pH was adjusted to 5.5 to 6.0, thereby obtaining a shampoo containing the damage inhibitor.

[0178] The obtained shampoo was capable of suppressing damage caused by residual chlorine.

[0179] [Table 5]

[0180] Ingredients 1: Purified water Raw material 2: Lauryl betaine aqueous solution, NOF Corporation, Nissan Anon BL-SF Raw material 3: PEI-1500 aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 30% aqueous solution of polyethyleneimine (molecular weight 250,000) Raw material 4: Etidronic acid aqueous solution, manufactured by Chelest, Chelest 210SD Ingredient 5: Polyquaternium-10 aqueous solution, manufactured by Toho Chemical Co., Ltd., 2% aqueous solution of Catinal LC-200 Ingredient 6: Glycerin, Miyoshi Oil & Fat Co., Ltd., concentrated glycerin for cosmetics Ingredient 7: Sodium laureth-4 carboxylate aqueous solution, Sanyo Chemical Industries, Ltd., Viewlite LCA-25F Ingredient 8: EDTA-2Na, manufactured by Chelest, Chelest 2B-SD Ingredient 9: Sodium bisulfite, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., sodium bisulfite Raw material 10: Sodium benzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., sodium benzoate Ingredient 11: PPG-2 Cocamide, manufactured by Kawaken Fine Chemicals, Amizet 1pc Ingredient 12: Ceteareth-60 Myristyl Glycol, Lion Specialty Chemicals, Elfacos GT-282S Ingredient 13: Phenoxyethanol, Yokkaichi Synthetic Co., Ltd., Phenoxyethanol-S Raw material 14: Succinic acid aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SA.

[0181] Example 18 A body soap containing this damage inhibitor was prepared using the amounts and types of each ingredient listed in Table 6 below, using the following procedure: (1) Ingredients 1 to 3 were mixed and heated to 80±5°C in a water bath; (2) Separately, ingredients 4 to 7 were mixed and heated to 80±5°C in a water bath; (3) While stirring the mixture of (1) with a propeller (300 rpm), mixture (2) was slowly added and mixed uniformly at 200 rpm; (4) The mixture of (3) was removed from the water bath and, while stirring at 100 rpm, was slowly cooled until the temperature of the mixture reached 40°C; (5) Ingredients 8 to 10 were added sequentially to the cooled mixture of (4) and mixed uniformly to obtain a body soap containing this damage inhibitor.

[0182] The obtained body soap was a body soap that could suppress damage caused by residual chlorine.

[0183] [Table 6]

[0184] Ingredient 1: Lauric acid, manufactured by Kao Corporation, Lunac L-98 Ingredient 2: Myristic acid, manufactured by Kao Corporation, Lunac MY-98 Ingredient 3: Palmitic acid, manufactured by Kao Corporation, Lunac P-95 Raw material 4: Potassium hydroxide aqueous solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 50% aqueous solution of KOH Ingredient 5: Milli-Q water Raw material 6: Etidronic acid tetrasodium aqueous solution, manufactured by Chelest Co., Ltd., Chelest PH-214SD Raw material 7: Hydroxyiminodisuccinic acid tetrasodium aqueous solution, manufactured by Nippon Shokubai Co., Ltd., CU-350 Raw material 8: PEI-1500 aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 30% aqueous solution of polyethyleneimine (molecular weight 250,000) Ingredient 9: Sodium laureth sulfate aqueous solution, manufactured by Kao Corporation, Emeral E-27C Raw material 10: Cocamidopropyl betaine aqueous solution, manufactured by Kawaken Fine Chemicals Co., Ltd., Softazoline CPB.

[0185] Example 19 A body soap containing this damage inhibitor was prepared using the amounts and types of each ingredient listed in Table 7 below, using the following procedure: (1) Ingredients 1 to 3 were mixed and heated to 80±5°C in a water bath; (2) Separately, ingredients 4 to 7 were mixed and heated to 80±5°C in a water bath; (3) While stirring the mixture of (1) with a propeller (300 rpm), mixture (2) was slowly added and mixed uniformly at 200 rpm; (4) The mixture of (3) was removed from the water bath and, while stirring at 100 rpm, was slowly cooled until the temperature of the mixture reached 40°C; (5) Ingredients 8 to 10 were added sequentially to the cooled mixture of (4) and mixed uniformly to obtain a body soap containing this damage inhibitor.

[0186] The obtained body soap was a body soap that could suppress damage caused by residual chlorine.

[0187] [Table 7]

[0188] Ingredient 1: Lauric acid, manufactured by Kao Corporation, Lunac L-98 Ingredient 2: Myristic acid, manufactured by Kao Corporation, Lunac MY-98 Ingredient 3: Palmitic acid, manufactured by Kao Corporation, Lunac P-95 Raw material 4: Potassium hydroxide aqueous solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 50% aqueous solution of KOH Ingredient 5: Milli-Q water Raw material 6: Etidronic acid tetrasodium aqueous solution, manufactured by Chelest Co., Ltd., Chelest PH-214SD Raw material 7: Hydroxyiminodisuccinic acid tetrasodium aqueous solution, manufactured by Nippon Shokubai Co., Ltd., CU-350 Raw material 8: (PEI-14 / PEG-20) copolymer aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 80% aqueous solution of polyethyleneimine ethoxylate (20 mol of ethylene oxide added) Ingredient 9: Sodium laureth sulfate aqueous solution, manufactured by Kao Corporation, Emeral E-27C Raw material 10: Cocamidopropyl betaine aqueous solution, manufactured by Kawaken Fine Chemicals Co., Ltd., Softazoline CPB.

[0189] Example 20 A hair mist containing the damage inhibitor was prepared using the amounts and types of each ingredient listed in Table 8 below, using the following procedure: (1) Ingredients 1 to 4 were dissolved uniformly at room temperature; (2) Ingredients 5 and 6 were mixed separately, and this mixture was added to the solution of (1) and mixed uniformly at room temperature; (3) Ingredients 7 and 8 were added sequentially to the mixture of (2) and mixed uniformly to obtain a hair mist containing the damage inhibitor.

[0190] The obtained hair mist was a hair mist that was able to suppress damage caused by residual chlorine.

[0191] [Table 8]

[0192] Ingredients 1: Purified water Raw material 2: BG, Daicel Corporation, 1,3-BG (UK) Raw material 3: (PEI-14 / PEG-20) copolymer aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 80% aqueous solution of polyethyleneimine ethoxylate (20 mol of Ethylene Oxide added) Ingredient 4: Ethanol, Fujifilm Wako Pure Chemical Industries, 99.5% ethanol Raw material 5: BG, Daicel Corporation, 1,3-BG (UK) Ingredient 6: Phenoxyethanol, Yokkaichi Synthetic Co., Ltd., Phenoxyethanol-S Raw material 7: Succinic acid aqueous solution, Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SA Raw material 8: Disodium succinate aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SS.

[0193] Example 21 A hair mist containing the damage inhibitor was prepared using the amounts and types of each ingredient listed in Table 9 below, using the following procedure: (1) Ingredients 1 to 6 were uniformly dissolved at 80±5°C; (2) Ingredients 7 to 10 were added sequentially to the solution of (1) and mixed uniformly; (3) Ingredient 12 was further added to the mixture of (2) and mixed uniformly to obtain a shampoo containing the damage inhibitor.

[0194] The obtained shampoo was capable of suppressing damage caused by residual chlorine.

[0195] [Table 9]

[0196] Ingredients 1: Purified water Ingredient 2: Cocamidopropyl betaine aqueous solution, manufactured by Kawaken Fine Chemicals Co., Ltd., Softazoline CPB Ingredient 3: Glycerin, Miyoshi Oil & Fat Co., Ltd., concentrated glycerin for cosmetics Raw material 4: Sodium benzoate, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., sodium benzoate Raw material 5: Etidronic acid aqueous solution, manufactured by Chelest, Chelest 210SD Ingredient 6: Polyquaternium-10 aqueous solution, manufactured by Toho Chemical Co., Ltd., 2% aqueous solution of Catinal LC-200 Raw material 7: (PEI-14 / PEG-20) copolymer aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 80% aqueous solution of polyethyleneimine ethoxylate (20 mol of ethylene oxide added) Ingredient 8: Sodium laureth sulfate aqueous solution, manufactured by Kao Corporation, Emeral E-27C Ingredient 9: Sodium laureth-4 carboxylate aqueous solution, Sanyo Chemical Industries, Ltd., Viewlite LCA-25F Ingredient 10: Cocamidomethyl MEA, manufactured by Kao Corporation, Aminone C-11S Raw material 11: Phenoxyethanol, Yokkaichi Synthetic Co., Ltd., Phenoxyethanol-SP Raw material 12: Succinic acid aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SA.

[0197] Example 22 A rinse-off conditioner containing the damage inhibitor was prepared using the amounts and types of ingredients listed in Table 10 below, as follows: (1) ingredients 1 and 2 were dissolved uniformly at 80±5°C; (2) ingredients 3 to 6 were dissolved uniformly separately at 80±5°C; (3) the solution of (2) was added to the solution of (1), and emulsified at 80±5°C for 5 minutes at 200 rpm; (4) the emulsion of (3) was slowly cooled to 50°C; (5) ingredients 7 to 9 were mixed uniformly; (6) the mixture of (5) was slowly added to the emulsion of (4), and mixed uniformly; (7) ingredient 10 was added to the mixture of (6), and after uniform mixing, ingredient 11 was added and the pH was adjusted to 4.0 to 4.5, thereby obtaining a rinse-off conditioner containing the damage inhibitor.

[0198] The resulting rinse-off conditioner was a rinse-off conditioner that was capable of suppressing damage caused by residual chlorine.

[0199] [Table 10]

[0200] Raw material 1: Stearamidopropyl dimethylamine, manufactured by Nikko Chemicals Co., Ltd., NIKKOL Amidoamine MPS Ingredient 2: Cetearyl alcohol, Kao Corporation, Kalcol 6850 Ingredient 3: Purified water Raw material 4: Succinic acid, Nippon Shokubai Co., Ltd., CG-SA Ingredient 5: Glycerin, Miyoshi Oil & Fat Co., Ltd., concentrated glycerin for cosmetics Raw material 6: Etidronic acid aqueous solution, manufactured by Chelest Co., Ltd., Chelest 210SD Raw material 7: Stearoxy PEI aqueous solution, manufactured by Nippon Shokubai Co., Ltd., a 30% aqueous solution of hydrophobically modified polyethyleneimine derivative Ingredient 8: Dimethicone, Shin-Etsu Chemical Co., Ltd., KF-96H-500,000 CS Ingredient 9: Dimethicone, Shin-Etsu Chemical Co., Ltd., KF-96A-10CS Ingredient 10: Guar hydroxypropyltrimonium chloride aqueous solution, MP Gokyo Food & Chemicals Co., Ltd., 2% aqueous solution of Labolgum CG-M Raw material 11: Succinic acid aqueous solution, manufactured by Nippon Shokubai Co., Ltd., 5% aqueous solution of CG-SA.

[0201] The damage suppressant of this embodiment can suppress damage caused by residual chlorine, particularly damage to skin and / or hair, and therefore, can be suitably used in, for example, cosmetics.

Claims

1. A damage inhibitor containing polyalkyleneimine and / or a polyalkyleneimine derivative, which inhibits damage caused by chlorine.

2. The polyalkyleneimine derivative is a polyalkyleneimine derivative obtained by addition reaction of a nitrogen atom of a polyalkyleneimine with a compound having a structure represented by the following formula (1C) and / or (2C): has a substituent having a structure of the following formula (3C) and / or (4C), The damage suppressant according to claim 1, wherein the amount of the substituent added to the nitrogen atoms contained in the polyalkyleneimine is 0.1 mol % to 35 mol %. R ３ -R １ ・・・(1C) R ４ -R １ ・・・(2C) -CH ２ CH(OH)-R １ ・・・(3C) -CH ２ CH(OH)CH ２ -O-R １ ・・・(4C) (In formulas (1C) to (4C), R １ represents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, an aryl group having 8 to 20 carbon atoms, or —(CH ２ CH ２ O)n-R ａ where R ａ represents an alkyl group having 8 to 20 carbon atoms, an alkenyl group having 8 to 20 carbon atoms, or an aryl group having 8 to 20 carbon atoms; n represents an integer of 1 to 50. ３ represents an epoxy group, and R ４ represents a glycidyl ether group. Here, the amount of the substituent added to the nitrogen atom contained in the polyalkyleneimine is a value calculated based on the following formula using the amine value of the polyalkyleneimine. Amount added (mol %)={[reacted amount of the compound (g) / molecular weight of the compound (g / mol)] / [amount of the polyalkyleneimine (g)×solid content of the polyalkyleneimine (%)×amine value of the polyalkyleneimine (mmol / g (non-volatile content)) / 1000]}×100(%).

3. The damage suppressant according to claim 2 , wherein the polyalkyleneimine is polyethyleneimine.

4. 2. The damage suppressant according to claim 1, wherein the polyalkyleneimine derivative is a polyalkyleneimine derivative obtained by addition reaction of an alkylene oxide with a nitrogen atom of a polyalkyleneimine.

5. The damage suppressant according to claim 4 , wherein the polyalkyleneimine is polyethyleneimine.

6. 2. The damage suppressant according to claim 1, wherein the polyalkyleneimine and / or polyalkyleneimine derivative has a weight average molecular weight of 10,000 to 400,000.

7. A hair cosmetic comprising the damage inhibitor according to any one of claims 1 to 6.

Images