Hair treatment composition and hair treatment method

Abstract

There has been a demand for a hair treatment composition that has long-lasting effects and ensures safety, for the purposes of straightening hair, improving hair quality during dyeing and bleaching, improving hair quality during wave perm and straight perm, shampooing, and hair treatment. [Solution] The present invention provides a hair treatment composition containing as an active ingredient a complex of a dicarboxylic acid and a thiol, wherein the dicarboxylic acid is one or more selected from adipic acid, muconic acid, and cosmetically acceptable salts thereof, and further provides a hair treatment method using the hair treatment composition.

Description

Technical Field

[0001] The present invention relates to a hair treatment composition containing, as an active ingredient, a complex comprising a bifunctional compound, more preferably a bifunctional compound having 6 or more carbon atoms (C6), and thiols, and further relates to a hair treatment method using the hair treatment composition.

Background Art

[0002] For the purpose of improving the condition of hair, many hair treatment compositions containing organic acids such as bifunctional compounds have been developed. For example, a perm agent containing thioglycolic acid, adipic acid, etc. (see Patent Document 1), a hair shape control agent first agent composition containing a hair reducing substance having a thiol group and a bifunctional compound suitable for adipic acid (see Patent Document 2), a first composition containing a bifunctional compound such as adipic acid and muconic acid, and a hair treatment method of applying a second composition having a different pH to the hair, in which the composition not containing a reducing agent is disclosed in the embodiment (see Patent Document 3).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0004] There has been a need for a hair treatment composition that provides long-lasting effects and ensures safety for purposes such as improving hair quality during hair straightening, dyeing, and bleaching, improving hair quality during wave perms and straight perms, and for use in shampoos and hair treatments. Patent documents 1 and 2 disclose a first perming agent containing dicarboxylic acid, but their purpose is to suppress damage caused by excessive hair contraction during the reduction reaction of hair by the first perming agent, and the problems that the present invention aims to solve are different from those of these inventions. Furthermore, Patent document 3 discloses a composition that does not contain a reducing agent in its embodiments, in which the dicarboxylic acid acts on the hair alone. [Means for solving the problem]

[0005] The present invention was reached when the inventors discovered that a complex consisting of a specific dicarboxylic acid and thiols can provide a remarkable improvement effect on hair. Specifically, the present invention is a hair treatment composition in which a complex consisting of a dicarboxylic acid and thiols is used as an active ingredient, wherein the dicarboxylic acid is one or more selected from the group consisting of dicarboxylic acids having 6 to 10 carbon atoms and their salts that are acceptable for cosmetic use, and the thiols are one or more selected from the group consisting of aminothiols and their salts that are acceptable for cosmetic use. The complex may be formed by reacting thiols / dicarboxylic acid in a molar ratio of 0.01 to 100. Alternatively, it may be a complex obtained by reacting thiols / dicarboxylic acid in a molar ratio of 1 or more.

[0006] In another aspect of the present invention, the present invention provides a hair treatment composition containing a dicarboxylic acid and thiols, wherein the dicarboxylic acid is one or more selected from the group consisting of dicarboxylic acids having 6 to 10 carbon atoms and cosmetically acceptable salts thereof, and the thiols are one or more selected from the group consisting of aminothiols and cosmetically acceptable salts thereof.

[0007] Furthermore, the present invention is a hair treatment composition that substantially does not contain any active ingredients other than dicarboxylic acids, thiols, or complexes consisting of dicarboxylic acids and thiols. Another aspect of the present invention is one or more selected from the group consisting of hair straightening agents, hair quality improving agents for dyeing or bleaching, hair quality improving agents for wave perms or straight perms, shampoos, hair treatments, and hair styling agents (hair styling products), but yet another aspect of the present invention is not a first or second agent for wave perms or straight perms.

[0008] The thiols in this invention are aminothiols, and specifically, may be one or more selected from the group consisting of cysteamine, cysteine, amidinocysteine, aminothiophenol, mercaptopyridine, homocysteine, aminoundecanethiol, and cosmetically acceptable salts thereof. Furthermore, the dicarboxylic acids in this invention may be one or more selected from the group consisting of adipic acid, pimelic acid, suberic acid, azelaic acid, hexenodioic acid, heptenodioic acid, octenodioic acid, muconic acid, and cosmetically acceptable salts thereof.

[0009] The hair treatment composition of the present invention is obtained by a manufacturing method that includes at least a mixing step of mixing a dicarboxylic acid and thiols at a high temperature. The complex formed by the dicarboxylic acid and thiols is obtained by the mixing step. The mixing step may be a mixing step in which the dicarboxylic acid and thiols are mixed at 60 to 100°C. Alternatively, the mixing step may be a mixing step in which the active ingredients other than the dicarboxylic acid, thiols, their solvents, and pH adjusters are substantially absent.

[0010] Furthermore, the present invention is a hair treatment method comprising at least an application step of applying the hair treatment composition described above, or a hair treatment composition manufactured by the manufacturing method described above, to the hair, and a heating step of heating the hair after the application step. The heating step may be a step of heating the hair so that the surface temperature of the hair is 40-60°C, 80°C, 100°C, 120°C, 140°C, 160°C, or 180°C.

[0011] Another hair treatment method of the present invention, excluding the method of applying the hair treatment composition to the hair as a first or second agent for wave perm or straight perm, aims at one or more of the following: hair straightening, hair quality improvement during dyeing and bleaching, hair quality improvement during wave perm and straight perm, and shampoo and hair treatment. The hair treatment method of the present invention may be a non-therapeutic method. [Effects of the Invention]

[0012] Because the present invention consists of dicarboxylic acids and thiols, which have been conventionally used as cosmetic materials, it can provide a hair treatment composition that ensures safety for the user. Hair treatment methods using the hair treatment composition of the present invention can be used for straightening, improving hair quality during dyeing and bleaching, improving hair quality during wave perms and straight perms, and for shampooing and hair treatment, and the effects last even after multiple shampoo washes.

[0013] When the hair treatment composition of the present invention is used during hair straightening, the hair becomes free from twisting and has a soft finish. Furthermore, the effect of hair straightening and the hair's strong and flexible state are maintained even after the hair straightening treatment. When the hair treatment composition of the present invention is used during dyeing and bleaching, the hair can be finished with high elasticity and softness. In addition, damage to the hair during bleaching is reduced, and hair twisting is reduced. When the hair treatment composition of the present invention is used during wave perms and straight perms, the hair can be finished with softness, and the effect of the perm and the hair's strong and flexible state are maintained. When the hair treatment composition of the present invention is used in shampoos and hair treatments, unintended frizz can be reduced, the elasticity of the hair can be increased, and the hair can be finished with softness. These effects can persist even after washing the hair multiple times with shampoo.

[0014] In particular, the hair treatment method of the present invention is advantageous because, although the effect is obtained by applying the hair treatment composition to the hair and then heating the hair, the effect can be obtained even if the heating step is a step in which the surface temperature of the hair is raised to 40-60°C. This temperature range has a low risk of damaging the hair and is within the temperature range of everyday grooming activities at home. Therefore, the composition and method of the present invention can achieve hair treatment effects without the use of specialized equipment. [Brief explanation of the drawing]

[0015] [Figure 1] This photograph shows the effect of the hair treatment composition of the present invention, used as an intermediate treatment agent for permanent wave agents, on improving curl formation and its persistence in hair treated with the composition. [Figure 2] This photograph shows the straightening effect of the hair treatment composition of the present invention on the curly hair of an Ethiopian woman. [Figure 3] This photograph shows the effect of the hair treatment composition of the present invention on improving curl formation and the persistence of the curl in bleached hair. [Figure 4] This is a photograph showing the curl formation of bleached hair treated with a shampoo containing the hair treatment composition of the present invention. [Modes for carrying out the invention]

[0016] The present invention will be described in detail based on its embodiments, but the present invention is not limited to these embodiments.

[0017] The present invention relates to a hair treatment composition comprising a complex composed of a bifunctional compound, preferably a bifunctional compound having 6 or more carbon atoms (C6), and thiols as an active ingredient. The bifunctional compound is a general term for compounds containing two functional groups, and specifically includes dicarboxylic acids which are dicarbonyl compounds. The hair treatment composition of the present invention acts on the hair with a complex composed of the dicarboxylic acid and thiols contained in the composition as an active ingredient. In the present invention, the complex refers to a state in which a plurality of molecules are associated or bonded by intermolecular forces or covalent bonds, and includes compounds or aggregates composed of a plurality of molecules. In the hair treatment composition of the present invention, a complex formed by the reaction of thiols and dicarboxylic acid acts as an active ingredient.

[0018] Further, one embodiment of the present invention is a hair treatment composition containing a dicarboxylic acid and thiols. Although the complex formed by the dicarboxylic acid and thiols acts on the hair as an active ingredient, the dicarboxylic acid and / or thiols may act on the hair alone. Specifically, the present invention is a hair treatment composition containing a dicarboxylic acid and thiols, wherein the dicarboxylic acid may be one or more selected from the group consisting of muconic acid, adipic acid, octenedioic acid, and salts thereof acceptable as cosmetics. The thiols are one or more selected from the group consisting of aminothiols and salts thereof acceptable as cosmetics, and may be cysteamine or a salt thereof acceptable as cosmetics.

[0019] The complex which is the active ingredient of the present invention is a complex that can be formed by the reaction of a dicarboxylic acid and thiols in a solvent such as water or ethanol, preferably in an aqueous solution. Specifically, it includes complexes induced by a thiol-ene reaction in which the thiol group of the thiols acts on the alkene of the dicarboxylic acid or the double bond in the alkene formed by the reduction of the dicarboxylic acid, and complexes induced by intermolecular hydrogen bonds formed between the dicarboxylic acid and the thiols. The complex can be obtained by a mixing step of mixing the dicarboxylic acid and thiols at a high temperature.

[0020] A dicarboxylic acid refers to a compound having two carboxy groups. Among dicarboxylic acids, α, ω-dicarboxylic acids are preferably used in the hair treatment composition of the present invention. Those in which carboxy groups are added to both ends of a linear or branched alkane or alkene having 6 to 10 carbon atoms are more preferably used, and further preferably, those in which carboxy groups are added to both ends of a linear or branched alkane or alkene having 6 to 8 carbon atoms are used.

[0021] As the dicarboxylic acid used in the hair treatment composition of the present invention, linear saturated dicarboxylic acids and / or unsaturated dicarboxylic acids are preferably used. Examples of the saturated dicarboxylic acid include adipic acid, pimelic acid, suberic acid, azelaic acid, and decanoic acid. Examples of the unsaturated dicarboxylic acid include hexenedioic acid, heptenedioic acid, octenedioic acid, nonenedioic acid, decadienoic acid, hexadienoic acid, heptadienoic acid, octadienoic acid, nonadienoic acid, and decadienoic acid.

[0022] The dicarboxylic acid used in the hair treatment composition of the present invention may be one or more selected from adipic acid, pimelic acid, suberic acid, azelaic acid, hexenedioic acid, heptenedioic acid, octenedioic acid, muconic acid, and salts thereof that are acceptable as cosmetics. More preferably, it may be one or more selected from the group consisting of adipic acid, octenedioic acid, muconic acid, and salts thereof that are acceptable as cosmetics. A high hair treatment effect has been confirmed in a hair treatment composition containing a complex composed of these dicarboxylic acids and thiols.

[0023] As long as the dicarboxylic acid having cis-trans isomers exhibits the effects of the present invention, any isomer can be used. For example, muconic acid has three cis-trans isomers: trans, trans-type, cis, trans-type, and cis, cis-type. When muconic acid is used as the dicarboxylic acid, any isomer can be used in the present invention. However, trans, trans-type muconic acid has the advantage that it can form a complex with thiols in a shorter time compared to other isomers.

[0024] Thiols are compounds having at least one thiol group. The thiols used in the hair treatment composition in this invention together with dicarboxylic acids are not limited as long as they achieve the effects of the present invention, but specifically, they are aminothiols. Aminothiols are also called mercaptoamines and are thiols having one or more amino groups.

[0025] The aminothiols used in the hair treatment composition of the present invention may be one or more selected from the group consisting of cysteamine, cysteine, amidinocysteine, aminothiophenol, mercaptopyridine, homocysteine, aminoundecanethiol, and cosmetically acceptable salts thereof. Among the thiols, compounds having primary amines such as cysteamine and cysteine ​​are preferably used, and cysteamine is more preferably used.

[0026] The pH of the hair treatment composition of the present invention is preferably weakly acidic to weakly alkaline, and more preferably in the neutral range. Specifically, the pH is 5 to 8, more preferably 5.5 to 7.5, and even more preferably 6 to 7. After the mixing step described later, the pH of the composition can be adjusted to a desired pH.

[0027] Furthermore, the hair composition of the present invention can also be incorporated into hair dyes, bleaches, and perming agents. In such cases, the pH of the hair treatment composition of the present invention is preferably neutral to alkaline, and more preferably neutral to weakly alkaline. Specifically, the pH is 7 to 12, and more preferably 8 to 11.

[0028] The hair treatment composition of the present invention contains a complex formed by dicarboxylic acid and thiols as an active ingredient, but may or may not contain other active ingredients besides dicarboxylic acid and thiols or their complex. This is because even if a composition does not contain other active ingredients besides dicarboxylic acid and thiols or their complex, it can still be effective on hair as long as it contains at least the complex. Here, active ingredients other than dicarboxylic acid and thiols or their complex refer to ingredients that have some effect on hair when applied to the hair, and specifically include disulfide compounds, reducing agents other than thiols such as sodium sulfite, oxidizing agents such as sodium bromate and hydrogen peroxide, humectants such as hyaluronic acid, chondroitin sulfate, collagen, glycerin, xylitol, glucose, sucrose, amino acids, their derivatives, and their salts, thickeners such as xanthan gum, guar gum, and pectin, and surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants. Here, the active ingredients other than dicarboxylic acids, thiols, and their complexes do not include antioxidants, preservatives, fragrances, colorants, pH adjusters, or other ingredients that are not intended to directly affect the hair.

[0029] Another embodiment of the present invention provides a hair treatment composition obtained by a method comprising at least a mixing step of mixing dicarboxylic acids and thiols at a high temperature. This is because mixing at a high temperature promotes the formation of a complex of the active ingredients, dicarboxylic acids and thiols.

[0030] In the mixing step, while the presence of a solvent that does not inhibit the formation of a complex between the dicarboxylic acid and thiols (such as water or ethanol) and a pH adjuster is permissible, it is preferable to mix the dicarboxylic acid and thiols in an environment where substantially no other active ingredients are present. This is because mixing in the presence of other components may inhibit the formation of a complex between the dicarboxylic acid and thiols.

[0031] The mixing step specifically involves mixing the dicarboxylic acid and thiols, both dissolved in a solvent (water, ethanol, etc.), under high-temperature conditions. It is desirable that, aside from acids or alkalis used for pH adjustment, the solvent (water, ethanol, etc.) is substantially free of components that inhibit the formation of complexes between the dicarboxylic acid and thiols. "Substantially free" means that the components are intentionally omitted during the manufacturing process of the hair treatment composition; the presence of substances initially dissolved in the solvent (water, ethanol, etc.) or substances that dissolve into the solvent from the external atmosphere during the manufacturing process is acceptable.

[0032] In one embodiment of the present invention, the mixing step is a manufacturing method in which dicarboxylic acids, thiols, their solvents (water, ethanol, etc.), and pH adjusters are mixed in an environment where no active ingredients other than those listed above are substantially present. Active ingredients that are not permitted to be present here are those that can inhibit the formation of complexes between dicarboxylic acids and thiols, while the presence of ingredients that do not inhibit the formation of complexes between dicarboxylic acids and thiols is permitted.

[0033] In the mixing step, the temperature at which the dicarboxylic acid and thiols are mixed is 40 to 120°C, preferably 60 to 100°C. More preferably 80 to 100°C, and if the solvent is water, it is sufficient to heat it to a boil under normal pressure. The time spent under high temperature is not limited, but specifically it is 1 minute to 24 hours, preferably 1 hour to 6 hours. The mixing step may also be carried out under high pressure, in which case the complex can be obtained at a lower temperature or in a shorter time compared to the mixing step under normal pressure.

[0034] In the mixing step, pH adjustment of the mixed solvent of dicarboxylic acid and thiols is not essential, but if the dissolution of the dicarboxylic acid and / or thiols in the solvent is insufficient, adjusting the pH will promote dissolution. Since dicarboxylic acid is acidic, it is sufficient to mix it in the presence of an alkaline pH adjusting agent. The pH of the solvent at the time of mixing is not limited, but it is preferably in the acidic to weakly alkaline range, and more preferably in the acidic range. Specifically, the pH may be 4 to 9, 4 to 7, or 4 to 6.

[0035] The amount of substances (molar ratio) of dicarboxylic acid and thiols in the hair treatment composition of the present invention is not limited, and the ratio of thiols to dicarboxylic acid may be 0.01 to 100 (i.e., the molar ratio of the amount of thiols to the amount of dicarboxylic acid is 0.01 to 100), but it is preferable that the ratio of thiols to dicarboxylic acid is 1 or more (i.e., the molar ratio of the amount of thiols to the amount of dicarboxylic acid is 1 or more). Specifically, the ratio of thiols to dicarboxylic acid may be 1 to 100, 1 to 10, 1 to 5, or 1 to 3. This is because if the amount of thiols is less than the amount of dicarboxylic acid, the formation of the complex may be insufficient and the hair quality improvement effect may not be fully exhibited.

[0036] The present invention provides a hair treatment method comprising at least an application step of applying a hair treatment composition to the hair, and a heating step of heating the hair after the application step. Another embodiment of the hair treatment method of the present invention is a hair treatment method comprising, following the application step, a washing step of washing off the hair treatment composition from the hair, and a heating step of heating the hair from which the hair treatment composition has been washed off.

[0037] The heating temperature in the heating step is not limited as long as it is a temperature at which the effects of the hair treatment composition of the present invention can be obtained, but preferably it is a step in which the hair is heated so that the surface temperature of the hair is 40-60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, and more preferably it is a step in which the hair is heated so that the surface temperature of the hair is 40-60°C.

[0038] The hair treatment method of the present invention is advantageous in that it is effective even when the surface temperature of the hair is 40 to 60°C. This temperature range has a low risk of damaging the hair and is within the temperature range used for heating during everyday grooming at home. Therefore, the hair treatment effect of the present invention can be obtained without using specialized equipment.

[0039] In another embodiment, the hair treatment method provided by the present invention aims to achieve one or more of the following: hair straightening, hair quality improvement during dyeing and bleaching, hair quality improvement during wave perms and straight perms, and shampoos and hair treatments.

[0040] One embodiment of the hair treatment composition of the present invention is a hair quality improving agent containing the hair treatment composition and used for the purpose of improving hair quality during perming. Another embodiment is a hair quality improving agent used not as a first or second agent for wave perms or straight perms, but as an intermediate agent between them. Specifically, the first agent is applied to the hair, and after sufficient reduction has been achieved in the hair, the hair treatment composition of the present invention is applied. When applying, the hair treatment composition of the present invention may be applied alone, or it may be applied after mixing the hair treatment composition of the present invention with the first agent. The hair is left to stand after application, the first agent and the hair treatment composition of the present invention are washed off, the hair is heated and dried, and if necessary, further heated using a hair iron or the like, and the second agent is applied. As a result, the hair becomes soft, and even after repeated shampooing after perming, the hair remains strong and flexible.

[0041] In another embodiment, the present invention provides a hair straightening agent containing a hair treatment composition. The hair straightening agent is applied to the hair alone or mixed with the first hair straightening agent during the hair straightening process, left to stand, rinsed off, the hair is heated and dried, and if necessary, further heated using a hair iron or the like, and then the second agent is applied. As a result, the hair is free from twisting and has a soft finish, and even after repeated shampooing after the hair straightening treatment, the hair remains strong and flexible.

[0042] In another embodiment, the present invention provides a hair quality improving agent for dyeing or bleaching that contains a hair treatment composition. The hair quality improving agent is mixed with a first and second agent containing an oxidative dye, or mixed with a mixture of the first and second agents, applied to the hair, left to stand, rinsed, the hair is heated and dried, and further heated with a hair iron or the like as needed. As a result, the unpleasant odor immediately after dyeing and bleaching is suppressed, and the hair can be made more elastic and softer. In addition, damage to the hair during bleaching is reduced, and hair twisting is reduced. That is, the present invention may be a hair dye or bleach containing a hair treatment composition.

[0043] In yet another embodiment, the present invention provides a shampoo or hair treatment containing a hair treatment composition. The shampoo or hair treatment is applied to the hair alone or mixed with an existing shampoo or hair treatment, left on, rinsed, the hair is heated and dried, and if necessary, further heated using a hair iron or the like. As a result, the hair can be made to have high elasticity and softness. Even after shampooing the hair, the elasticity and softness of the hair are maintained.

[0044] Another embodiment of the hair treatment composition of the present invention provides a hair styling agent (hair styling product) containing the hair treatment composition. The hair styling agent of the present invention can maintain high elasticity and softness of styled hair and can provide a high hair styling effect.

[0045] In another embodiment of the hair treatment composition of the present invention, the present invention provides a hair tonic and / or hair growth agent containing the hair treatment composition. The hair tonic and / or hair growth agent of the present invention can provide a high hair tonic and / or hair growth effect by maintaining high elasticity and softness of the hair. [Examples]

[0046] The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

[0047] 1. Manufacture of the hair treatment composition of the present invention

[0048] As Experimental Example 1, a hair treatment composition containing a complex of muconic acid and cysteamine was prepared. Of the three isomers of muconic acid, trans,trans muconic acid was used. 1.42 g of muconic acid was added to 10 g of purified water, 3 g of ammonia water was added to adjust the pH, and the mixture was heated to 80°C. After confirming that the muconic acid had dissolved, 0.77 g of cysteamine was added and heated while mixing until it boiled (to 100°C), and the boiling state (100°C) was maintained for 3 minutes to obtain a complex of muconic acid and cysteamine. Heating was stopped and the mixture was allowed to stand at room temperature. After confirming that there were no undissolved particles, the pH was adjusted to around 7.0 with ammonia water, purified water was added, and the final concentration of muconic acid and cysteamine was adjusted to 10% by mass.

[0049] As Experimental Example 2, a hair treatment composition containing a complex of adipic acid and cysteamine was prepared. 1.46 g of adipic acid was added to 10 g of purified water, and 3 g of aqueous ammonia was added to adjust the pH, after which it was heated to 80°C. After confirming that the adipic acid had dissolved, 0.77 g of cysteamine was added and heated while mixing until it boiled (to 100°C), and the boiling state (100°C) was maintained for 3 minutes to obtain a complex of adipic acid and cysteamine. Heating was stopped and it was left to stand at room temperature, and after confirming that there were no undissolved particles, the pH was adjusted to around 7.0 with aqueous ammonia, and purified water was added to adjust the final concentration of adipic acid and cysteamine to 10% by mass.

[0050] As Experimental Example 3, a hair treatment composition was prepared using muconic acid and thioglycerin. The preparation was carried out under the same conditions as in Experimental Example 1, except that 1.08 g of thioglycerin was added instead of cysteamine.

[0051] As Experimental Example 4, a hair treatment composition was prepared using adipic acid and thioglycerin. The composition was prepared under the same conditions as in Experimental Example 2, except that 1.08 g of thioglycerin was added instead of cysteamine.

[0052] As Experimental Example 5, a hair treatment composition was prepared using muconic acid and glyceryl thioglycolate. The composition was prepared under the same conditions as in Experimental Example 1, except that 1.66 g of glyceryl thioglycolate was added instead of cysteamine.

[0053] As Experimental Example 6, a hair treatment composition was prepared using adipic acid and glyceryl thioglycolate. The preparation was carried out under the same conditions as in Experimental Example 2, except that 1.66 g of glyceryl thioglycolate was added instead of cysteamine.

[0054] As Experimental Example 7, a hair treatment composition was prepared using adipic acid and ammonium thioglycolate. The preparation was carried out under the same conditions as in Experimental Example 2, except that 2.18 g of a 50% by weight aqueous solution of ammonium thioglycolate was added instead of cysteamine.

[0055] Furthermore, as Comparative Example 1, a hair treatment composition was prepared using fumaric acid and cysteamine. It was prepared under the same conditions as in Experimental Example 2, except that 1.16 g of fumaric acid was added instead of adipic acid.

[0056] Furthermore, as Comparative Example 2, a hair treatment composition was prepared using succinic acid and cysteamine. It was prepared under the same conditions as in Experimental Example 2, except that 1.18 g of succinic acid was added instead of adipic acid.

[0057] 2. Evaluation of the hair treatment composition of the present invention (1): Evaluation of wave-forming ability and its persistence during heating treatment

[0058] The hair treatment compositions of the present invention were evaluated. 30-40 strands of healthy human hair (average length 25 cm) were bundled together and secured to a plastic measuring comb by zigzag winding. Following the Kilby method (Reference: Donald H. Kirby, Drug and Cosmetic Industry, 80 (3), 314-315, 397-400 (1957)), the hair was immersed in a 10% by mass aqueous solution of ammonium thioglycolate (pH 9.2) for 10 minutes, and then rinsed with running water at 40°C for 30 seconds. After that, the hair was immersed in each of the hair treatment compositions of Experimental Example 1, Experimental Example 2, or Comparative Example 1 for 2 minutes, removed, and the moisture on the hair was wiped off with a towel.

[0059] Hair samples fixed to a measuring comb were subjected to heating treatment at 40°C, 60°C, or 80°C. Using a hairdryer, hot air was applied to the hair samples fixed to the measuring comb for 3 minutes until the surface temperature reached 40°C, 60°C, or 80°C, and then left at room temperature of 15-20°C for 7 minutes. The hair samples were immersed in a second solution consisting of a 6% by mass sodium bromate aqueous solution for 10 minutes, removed from the measuring comb, and left to dry at 15-20°C.

[0060] The wave-forming ability of hair under various conditions was measured. Wave-forming ability is expressed as the distance between the peak of one wave formed on hair treated at each temperature and the peaks of adjacent waves. A shorter distance indicates stronger wave-forming ability on the hair.

[0061] At the same time, the texture of the hair immediately after treatment was evaluated and scored. A score was assigned to indicate that the texture had worsened compared to before treatment, 1 to indicate no change, 2 to indicate slight improvement compared to before treatment, 3 to indicate a clear improvement compared to before treatment, and 4 to indicate a significant improvement compared to before treatment.

[0062] Furthermore, the persistence of wave formation against shampoo washing was evaluated using the following method. Wave-formed hair was washed by massaging it with an aqueous solution containing 2% by weight of a shampoo mainly composed of sodium laureth sulfate (hereinafter referred to as "shampoo aqueous solution"), rinsed with 40°C running water for 30 seconds, the water on the hair was wiped off with a towel, and the hair was dried by applying 80°C hot air from a hairdryer at a distance of 30 cm or more. This process was repeated to verify whether the tactile sensation obtained immediately after wave formation changed, and the number of shampoo washes required to lose wave-forming power was determined. Wave-forming power was determined to have been lost when the distance between wave peaks became more than twice the distance immediately after formation.

[0063] In cases where the hair showed high resistance to shampoo washing, it was treated under accelerated degradation conditions. Specifically, the hair was immersed in a shampoo solution at 40°C for 2 hours, rinsed with 40°C running water for 30 seconds, then the moisture on the hair was wiped off with a towel, and the hair was dried with 80°C hot air from a hairdryer at a distance of 30 cm or more. It was confirmed that this treatment had the same effect on the hair as the 28 shampoo washes described above. Therefore, this accelerated degradation treatment was combined with the aforementioned normal shampoo washing treatment to determine the number of shampoo washes required to lose wave-forming ability.

[0064] The evaluation results are shown in Table 1. In Experimental Example 1, Experimental Example 2, and Comparative Example 1, good wave-forming ability of 20 mm or less was confirmed under all conditions. In Comparative Example 1, the effect lasted for 29 shampoo washes with a heating treatment at a hair surface temperature of 60°C and 57 shampoo washes with a heating treatment at a hair surface temperature of 80°C. However, in Experimental Example 1, the effect lasted for more than 38 shampoo washes with a heating treatment at a hair surface temperature of 60°C, and in Experimental Example 2, the effect lasted for more than 38 shampoo washes with a heating treatment at a hair surface temperature of 40°C. In other words, in Experimental Example 1 and Experimental Example 2, the persistence obtained with a heating treatment at a hair surface temperature of 40-60°C was higher than the persistence obtained in Comparative Example 1 with a heating treatment at 40-60°C, and was comparable to the persistence obtained in Comparative Example with a heating treatment at 80°C.

[0065] Furthermore, the tactile sensation of the hair immediately after wave formation in the experimental and comparative examples was examined. Under all conditions, the tactile sensation of the hair improved compared to before treatment. However, in Comparative Example 1, the tactile sensation of the hair was not permanent in treatments where the hair surface temperature was 60°C or lower, but was semi-permanent and lost with shampoo washing. The tactile sensation was not permanent unless the surface temperature was raised to 80°C. On the other hand, in Experimental Example 1, a heating treatment that raised the hair surface temperature to 60°C, and in Experimental Example 2, heating treatments that raised the hair surface temperature to 40°C and 60°C, resulted in a permanent tactile sensation against shampoo washing. Therefore, it was found that Experimental Examples 1 and 2 could achieve a significant hair treatment effect at lower temperatures than Comparative Example 1.

[0066] [Table 1]

[0067] 3. Evaluation of the hair treatment composition of the present invention (2): Evaluation of wave-forming ability and its persistence during treatment at room temperature Furthermore, the wave-forming ability and its persistence when hair was treated at room temperature were evaluated. Using the same method as in "2.", hair fixed to a measuring comb was immersed for 2 minutes in each hair treatment composition of Experimental Examples 1-7 or Comparative Examples 1-2. In the blank test, the hair was immersed in purified water for 2 minutes. The hair was removed and the moisture on the hair was wiped off with a towel. The hair fixed to the measuring comb was left at 15-20°C for 10 minutes, then immersed for 10 minutes in a second solution consisting of a 6% by mass sodium bromate aqueous solution, the measuring comb was removed from the hair, and it was dried at 15-20°C.

[0068] The evaluation results are shown in Tables 2 and 3. In Experimental Examples 1-6, good wave-forming ability of 20 mm or less was confirmed in the hair under all conditions, and the waves were maintained even after 5-10 shampoo washes. In Experimental Examples 3 and 4, no change was observed in the texture of the hair compared to before treatment, but improvements were seen in Experimental Examples 1 and 2, and Experimental Examples 5 and 6. The texture of the hair obtained in each experimental example was semi-permanent.

[0069] [Table 2]

[0070] [Table 3]

[0071] 4. Evaluation of the hair treatment composition of the present invention (3): Evaluation of curl-forming ability and its persistence 30-40 strands of healthy human hair (average length 25 cm) were immersed for 10 minutes in a 10% by mass aqueous solution of ammonium thioglycolate (pH 9.2) as the first perming agent, and then rinsed for 30 seconds with running water at 40°C. Afterward, the hair was immersed for 2 minutes in each of the hair treatment compositions from Experimental Example 1, Experimental Example 2, Experimental Example 3, Experimental Example 4, Experimental Example 5, Experimental Example 6, or Experimental Example 7. Blank test hair was immersed in purified water for 2 minutes. It was then rinsed for 30 seconds with running water at 40°C, and excess water was wiped off with a towel. The hair, wrapped three times around a 25 mm diameter cylindrical curling iron, was heated on the iron for 2 minutes after the hair surface temperature reached 180°C to form curls, then removed from the iron and left at room temperature for 7 minutes. Subsequently, the hair was immersed for 10 minutes in a second perming solution consisting of a 6% by mass sodium bromate aqueous solution, and then removed and dried at room temperature.

[0072] The diameter or circumference of curls formed on the hair was measured and evaluated as curl-forming strength. A smaller measurement indicates stronger curl-forming strength on the hair. In addition, the persistence of curl formation after shampooing was investigated using the same method as described above, and the tactile feel of the hair immediately after treatment was evaluated and scored.

[0073] The evaluation results are shown in Tables 4 and 5. In Experimental Example 3, no curl-forming ability was observed on the hair, but curl-forming ability was observed in Experimental Examples 1 and 2 and Experimental Examples 4-7. In particular, the curl-forming ability in Experimental Examples 1 and 2 was maintained even after more than 85 shampoo washes, demonstrating high persistence. Improvement in tactile sensation immediately after curl formation was observed under all conditions, but the improvement in tactile sensation was particularly significant in Experimental Examples 1 and 2.

[0074] The hair texture obtained in Experimental Examples 1 and 2 was permanent, and its persistence was remarkable compared to other experimental and comparative examples. The texture in Experimental Examples 1 and 2 did not deteriorate at all even after more than 100 shampoo washes.

[0075] [Table 4]

[0076] [Table 5]

[0077] Furthermore, Figure 1A shows photographs of hair immediately after treatment with each composition of Experimental Example 1, Experimental Example 2, Comparative Example 1 or Comparative Example 2, and as a blank test, purified water instead of the Experimental Examples or Comparative Examples, under the same conditions as described above. Figure 1B shows photographs of hair after 87 shampoo treatments, i.e., 3 accelerated degradation treatments and 3 normal shampoo treatments. A 15 mm diameter heating rod was used for heating the hair instead of a 25 mm diameter hair iron.

[0078] As shown in Figure 1A, in Experimental Example 1 (indicated as "Real 1" in the figure), Experimental Example 2 (indicated as "Real 2" in the figure), Comparative Example 1 (indicated as "Ratio 1" in the figure), and Comparative Example 2 (indicated as "Ratio 2" in the figure), the curl-forming power on the hair immediately after treatment was significantly stronger compared to the blank test (indicated as "Blank" in the figure). In Comparative Examples 1 and 2, the hair ends lost their manageability after the equivalent of 87 shampoos, while the hair treated in Experimental Examples 1 and 2 maintained the same quality as before shampooing even after the equivalent of 87 shampoos.

[0079] 5. Evaluation of the hair treatment composition of the present invention (4): Evaluation of hair straightening power and its persistence 30-40 strands of Japanese woman's curly hair (average length 25 cm) were immersed for 10 minutes in a 10% by mass ammonium thioglycolate aqueous solution (pH 9.2) perming solution, and then rinsed with 40°C running water for 30 seconds. After that, the hair was immersed for 2 minutes in the hair treatment composition of Experimental Example 1 or Experimental Example 2, rinsed again with 40°C running water for 30 seconds, and excess water was wiped off with a towel. Using a flat iron, the hair was straightened from root to tip over 1 minute, gradually pulling to remove the twists from the roots. Then, the iron was passed over the hair once from root to tip at a uniform speed for 3 seconds, heat was applied again from the roots, and it was left at room temperature for 7 minutes. After that, the hair was immersed for 10 minutes in a 6% by mass sodium bromate aqueous solution perming solution, and then removed and dried at room temperature.

[0080] As a result, the hair treated in Experimental Examples 1 and 2 had a soft finish. In particular, Experimental Example 2 exhibited both softness and strength, and the hair surface had a glossy appearance. When the durability of the hair straightening effect against shampoo washing was measured, both Experimental Examples 1 and 2 showed high durability of more than 85 washes.

[0081] Furthermore, the results of another hair straightening test are shown in Figure 2. Hair from an Ethiopian woman with a tendency towards strong curl was immersed for 30 minutes in a 10% by mass aqueous solution of ammonium thioglycolate (pH 9.2) as the first perming agent, and then rinsed for 30 seconds with running water at 40°C. After that, the hair was immersed for 3 minutes in each of the hair treatment compositions of Experimental Example 1, Experimental Example 2, or Comparative Example 2. As a blank test, purified water was used instead of Experimental Example or Comparative Example, and the hair was treated under the same conditions. The hair was rinsed for 30 seconds with running water at 40°C, and excess water was wiped off with a towel. Further moisture was removed with a low-temperature hairdryer, and the hair was slowly straightened with a 180°C iron.

[0082] Figure 2A shows a photograph of the condition of Ethiopian women's curly hair (20-30 strands, average length 15 cm) before treatment, and Figure 2B shows a photograph of the condition of the hair after treatment. Comparative Example 2 (indicated as "Ratio 2" in the figure) was in the same condition as the hair used in the blank test (indicated as "Blank" in the figure), but in Experimental Example 1 (indicated as "Actual 1" in the figure) and Experimental Example 2 (indicated as "Actual 2" in the figure), the curly hair was straightened. In particular, Experimental Example 1 showed good manageability at the ends of the hair, confirming an ideal hair straightening effect.

[0083] 6. Evaluation of the hair treatment composition of the present invention (5): Evaluation as a hair treatment agent at each treatment temperature on hair The hair treatment effects of the compositions from Experimental Examples 1 and 2 on healthy human hair or bleached hair were verified. 30 to 40 strands of healthy human hair or bleached hair (average length 25 cm) were bundled together, and the composition from Experimental Example 1, Experimental Example 2, or Comparative Example 2 was diluted to a concentration of 0.5% by mass of dicarboxylic acid and thiols (pH 7) and immersed for 3 minutes. Excess moisture was then wiped off. The hair was then treated to surface temperatures of 20°C, 60°C, 80°C, or 120°C.

[0084] In the treatment to heat hair to 20°C, the hair was tightly wrapped around a 15 mm heated rod, left at 20°C (room temperature) for 10 minutes, any excess moisture was wiped off with a towel, and after another minute, the hair was removed from the heated rod. In the treatment to heat hair to 60°C or 80°C, the hair was tightly wrapped around a 15 mm heated rod, heated for 10 minutes until the hair surface reached 60°C or 80°C, left for another minute to cool the heated rod, and then the hair was removed from the heated rod. In the treatment to heat hair to 120°C, the hair was wrapped three times around a 25 mm diameter cylindrical hair iron, heated for 10 minutes until the hair reached approximately 180°C to form curls, then removed from the hair iron and left at room temperature for 1 minute.

[0085] Each hair sample was immersed in a 40°C shampoo solution for 10 seconds, then rinsed with 40°C running water for 10 seconds, and finally towel-dried. The effect on the hair was evaluated based on overall findings including curl formation rate, curl retention, and tactile feel. The curl formation rate was calculated by measuring the distance from the starting point of the curl at the root of the hair bundle (curl diameter) to the tip of the second longest hair in the bundle, and then measuring the distance from the starting point to the tip of the hair in question with the bundle straightened (hair length). The curl formation rate was then calculated as (hair length - curl diameter) / hair length × 100.

[0086] The durability of curl formation was evaluated by immersing hair strands in a shampoo solution, rinsing with water, drying with a towel, and leaving them to dry at room temperature. One cycle was defined as the number of cycles required for the formed curls to no longer be maintained (the hair strands to no longer complete a full rotation). Furthermore, under conditions of bleached hair at 80°C, the durability was evaluated using the aforementioned tactile score.

[0087] Table 6 shows the evaluation results using healthy hair, and Table 7 shows the evaluation results using bleached hair. In Experimental Examples 1 and 2, a higher curl formation rate was measured in treatments where the hair surface temperature was 40-180°C compared to the comparative example. In Experimental Examples 1 and 2, the persistence of curl formation through at least two shampooing cycles was confirmed in treatments where the hair surface temperature was 20-80°C, whereas in Comparative Example 2, curl formation was lost after one shampooing cycle at all temperature conditions. Furthermore, Experimental Examples 1 and 2 improved the tactile feel of bleached hair. As described above, the effects of the hair treatment agent containing the composition of the present invention have been clarified.

[0088] [Table 6]

[0089] [Table 7]

[0090] Figure 3A shows a photograph of bleached hair immediately after 60°C treatment, and Figure 3B shows a photograph of bleached hair after shampooing, based on the conditions listed in Table 7. In addition to Experimental Example 1 (indicated as "Jitsu 1" in the figure), Experimental Example 2 (indicated as "Jitsu 2" in the figure), and Comparative Example 2 (indicated as "Ritsu 2" in the figure), Comparative Example 1 (indicated as "Ritsu 1" in the figure) was also used for treatment. Purified water was used in place of the Experimental Examples and Comparative Examples for the blank test (indicated as "Blank" in the figure). The bleached hair in the blank test showed damage due to bleaching. The bleached hair treated in Experimental Examples 1 and 2 was soft and strong, and the curl was maintained even after shampooing. On the other hand, in Comparative Examples 1 and 2, the curl on the bleached hair disappeared after shampooing.

[0091] 7. Evaluation of the hair treatment composition of the present invention (6): Evaluation of the composition obtained in the mixing step under each temperature condition as a hair treatment agent

[0092] The effectiveness of compositions obtained by mixing dicarboxylic acids and thiols at 20°C (room temperature), 60°C, or 80°C (Experimental Examples 8-14) and compositions obtained by mixing at 100°C (Experimental Examples 1 and 2) as hair treatment agents was investigated.

[0093] In Experimental Examples 8-11, hair treatment compositions were prepared using muconic acid and cysteamine. 1.42 g of muconic acid was added to 10 g of purified water, and 0.77 g of cysteamine was added. Experimental Examples 8 and 9 were heated to 20°C (room temperature), Experimental Example 10 to 60°C, and Experimental Example 11 to 80°C, and then mixed. Once the muconic acid and cysteamine were completely dissolved in the water, heating was stopped for Experimental Examples 10 and 11, and the mixtures were left to stand until they returned to room temperature. Purified water and, if necessary, ammonia water were added to adjust the pH to around 7, and then purified water was added to adjust the final concentration of muconic acid and cysteamine to 10% by weight. Since it was difficult to achieve a pH of 7 under the conditions of stirring at 20°C, Experimental Example 8 was adjusted to pH 6.5, and Experimental Example 9 was adjusted to pH 8.

[0094] In Experimental Examples 12-14, hair treatment compositions were prepared using adipic acid and cysteamine. 1.46 g of adipic acid was added to 10 g of purified water, and 0.77 g of cysteamine was added. Experimental Example 12 was heated to 20°C (room temperature), Experimental Example 13 to 60°C, and Experimental Example 14 to 80°C, and the mixtures were then mixed. Once the adipic acid and cysteamine were completely dissolved in the water, heating was stopped for Experimental Examples 13 and 14, and the mixtures were left to stand until they returned to room temperature. The pH was adjusted to around 7.0 with ammonia water, and purified water was added to adjust the final concentration of adipic acid and cysteamine to 10% by mass.

[0095] In addition to Experimental Examples 8-14, the hair treatment effects of the compositions in Experimental Example 1, which contained a complex obtained by mixing muconic acid and cysteamine at 100°C, and Experimental Example 2, which contained a complex obtained by mixing adipic acid and cysteamine at 100°C, were verified on healthy human hair and bleached hair. The compositions of each Experimental Example were used as liquids diluted to a concentration of 0.5% by mass of dicarboxylic acid and thiols. Healthy hair and bleached hair were used, and the hair was heated to a surface temperature of 80°C. Other evaluations were performed using the same method as in 5. Table 8 shows the evaluation results using healthy hair, and Table 9 shows the evaluation results using bleached hair. In the compositions using muconic acid (Experimental Examples 8-11 and 1), the hair texture was superior when the experimental examples obtained by mixing at 60°C or higher were used. In the compositions using adipic acid (Experimental Examples 12-14 and 2), the curl retention and hair texture were superior when the experimental examples obtained by mixing at 60°C or higher were used. As described above, the experimental results obtained with higher mixing temperatures tended to show better curl persistence and tactile scores, suggesting that higher mixing temperatures promote complex formation.

[0096] [Table 8]

[0097] [Table 9]

[0098] 8. Evaluation of the hair treatment composition of the present invention (7)

[0099] The wave-forming ability and its persistence, as well as the curl-forming ability and its persistence, were evaluated for Experimental Example 2 and Experimental Example 12. The evaluation method was the same as described above; the wave-forming ability and its persistence were compared using heating to a hair surface temperature of 40°C, and the curl-forming ability and its persistence were compared using heating to a hair surface temperature of 180°C.

[0100] The results are shown in Table 10. Experimental Example 2 showed good tactile properties during wave and curl formation, and these properties persisted even after multiple shampoo washes. On the other hand, Experimental Example 12 showed inferior tactile properties during wave and curl formation compared to Experimental Example 2, and its persistence after shampoo washes was lower.

[0101] [Table 10]

[0102] 9. Evaluation of the hair treatment composition of the present invention (8): Evaluation as the first perming agent in digital perms (perms using heated rods)

[0103] As Experimental Example 15, a hair composition was prepared by mixing adipic acid and cysteamine at 40°C. 1.46 g of adipic acid was added to 10 g of purified water, 0.77 g of cysteamine was added, and the mixture was mixed at 40°C. Once completely dissolved, it was left to stand until it returned to room temperature. The pH was adjusted to approximately 6.5 with ammonia water, and purified water was added to adjust the final concentration of adipic acid and cysteamine to 10% by mass. In addition to the composition of Experimental Example 15, the effects of perm solution No. 1 containing the compositions of Experimental Example 12 (mixed at 20°C (room temperature)), Experimental Example 13 (mixed at 60°C), Experimental Example 14 (mixed at 80°C), and Experimental Example 2 (mixed at 100°C) were evaluated.

[0104] For each experimental composition, an aqueous solution containing 10% by mass of ammonium thioglycolate was used to dilute the adipic acid and cysteamine to 0.5% by mass, and the pH was adjusted to 9 to create the first perming solution. 30-40 strands of healthy human hair (average length 25 cm) were immersed in each first solution for 10 minutes, rinsed with 40°C running water for 20 seconds, and then wrapped around a heated rod at 60°C four times. The hair was wrapped in felt to prevent drying and left for 10 minutes. After that, the hair was immersed in a second perming solution consisting of a 6% by mass sodium bromate aqueous solution for 10 minutes, removed from the rod, and dried at room temperature.

[0105] The evaluation results are shown in Table 11. In Experimental Examples 12 and 15, slight damage to the cuticle on the hair surface was observed, but in Experimental Examples 13, 14 and 2, no damage was observed, the texture was good, and shine was also seen on the hair treated in Experimental Examples 15 and 2. Furthermore, the curl-forming ability of the hair treated in Experimental Examples 13, 14 and 2 was less than 30 mm in diameter, and the persistence was confirmed for more than 33 shampoo washes in each case. As described above, the hair treatment compositions in Experimental Examples 13, 14 and 2, which contain a complex obtained by mixing adipic acid and cysteamine at 60-100°C, showed a significant hair quality improvement effect when used as the first agent in perming solutions, compared to Experimental Examples 12 and 15, which were mixed at 20-40°C.

[0106] [Table 11]

[0107] 10. Evaluation of the hair treatment composition of the present invention (9): Evaluation of shampoo containing the hair treatment composition of the present invention

[0108] The effectiveness of shampoos containing the hair treatment compositions of the experimental examples was verified. A shampoo stock solution was prepared containing 6% by weight of lauroyl methylalanine TEA, 3% by weight of lauryl betaine, 1% by weight of cocamide methyl MEA, 1% by weight of cocamide DEA, and 0.3% by weight of polyquaternium-10, and further containing 4% by weight of either Experimental Example 1 or Experimental Example 2. For the blank test, a shampoo stock solution containing purified water was used instead of the experimental examples.

[0109] To each of the following samples, approximately 10% by weight of the shampoo concentrate was added to warm water at approximately 40°C, and the mixture was stirred until it lathered to create the shampoo. A bundle of 30 to 40 strands of bleached human hair (average length 25 cm) was immersed in the shampoo solution, removed after 10 seconds, and the bundle was massaged with hands for approximately 10 seconds. The hair was then rinsed with running water at approximately 40°C for approximately 10 seconds. The hair was then towel-dried and dried with a hairdryer on the cool setting.

[0110] A cylindrical curling iron with a diameter of 25 mm was used to curl hair. The hair was wrapped around the iron three times, and after the surface temperature reached 180°C, it was heated for two minutes to form a curl. The curled hair was then rinsed with running water at approximately 40°C for about 10 seconds, the hair was towel-dried, and once dry, the curl formation rate was measured using the same method as described above. This was defined as the curl formation rate after the first shampoo. Furthermore, each strand of hair was subjected to two additional shampooing treatments using the same shampoo, and the curl formation rates for the second and third shampoos were measured.

[0111] The results are shown in Table 12. Significant curls were formed in hair treated with shampoos containing Experimental Example 1 or Experimental Example 2. With shampoos containing Experimental Example 1 or Experimental Example 2, the curls formed in the hair became stronger with increasing shampooing frequency. On the other hand, when using a shampoo in which the Experimental Example was replaced with purified water, almost no curls were formed.

[0112] Furthermore, hair treated with shampoo containing Experimental Example 1 or Experimental Example 2 was shiny and soft. This hair felt particularly good to the touch after being heated with a hair iron, and no damage from bleaching was felt.

[0113] [Table 12]

[0114] Furthermore, we present another verification result of the effectiveness of the shampoo containing the experimental examples of the present invention. Using the same method as described above, a shampoo stock solution containing Comparative Example 1 was prepared in addition to a shampoo stock solution containing Experimental Example 1 or Experimental Example 2. As a blank test, a shampoo stock solution containing purified water was used instead of the experimental examples or comparative examples. Hair was mixed with approximately 10% by weight of the shampoo stock solution in warm water at approximately 40°C, and stirred until foam was produced to make the shampoo. Bundles of 30 to 40 strands of bleached human hair (average length 25 cm) were immersed in the shampoo solution, removed after 10 seconds, and rinsed with running water at approximately 40°C for approximately 10 seconds.

[0115] The hair was wrapped around a 25 mm diameter hair curler and heated with a hairdryer for 3 minutes until the surface of the hair reached approximately 60°C. The hair was carefully removed from the curler, gently rinsed with a shower of warm water at approximately 40°C, towel-dried, and left to rest.

[0116] Table 13 shows the curl formation rate of the hair, and Figure 4 shows photographs of the hair condition. Hair treated with shampoo containing Experimental Example 1 (indicated as "Real 1" in the figure) and shampoo containing Experimental Example 2 (indicated as "Real 2" in the figure) showed a significantly higher curl formation rate compared to hair in the blank test (indicated as "Blank" in the figure) and hair treated with shampoo containing Comparative Example 1 (indicated as "Comparative 1" in the figure), and the curl was maintained even after showering with warm water.

[0117] [Table 13]

[0118] 11. Evaluation of the hair treatment composition of the present invention (10): Verification of the combination of dicarboxylic acid and thiols

[0119] Experimental Example 11, containing a complex of muconic acid and cysteamine, and Experimental Example 14, containing a complex of adipic acid and cysteamine, were used. Furthermore, Experimental Example 16, containing a complex of (E)-Oct-4-ene-1,8-dioic acid, a type of octenodioic acid, and cysteamine, was prepared. It was prepared under the same conditions as Experimental Example 11, except that 1.73 g of (E)-Oct-4-ene-1,8-dioic acid was added instead of muconic acid.

[0120] Furthermore, Experimental Example 17 was prepared using muconic acid and thiolactic acid, and Experimental Example 18 was prepared using muconic acid and thiomalic acid. Experimental Example 17 was prepared under the same conditions as Experimental Example 11, except that 1.06 g of thiolactic acid was added instead of cysteamine. Experimental Example 18 was prepared under the same conditions as Experimental Example 11, except that 1.50 g of thiomalic acid was added instead of cysteamine.

[0121] The hair treatment effects on healthy human hair or bleached hair were verified using the compositions of Experimental Examples 11, 14, and 16. Bundles of 30 to 40 strands of healthy human hair or bleached hair (average length 25 cm) were prepared, and the compositions of the Experimental Examples were immersed for 3 minutes in a liquid (pH 7) diluted to a concentration of 0.5% by mass of dicarboxylic acid and thiols. Excess moisture was then wiped off. The hair was tightly wrapped around a 15 mm heated rod, heated for 10 minutes until the hair surface reached 80°C, and then left for another minute to cool before the hair was removed.

[0122] Each hair sample was immersed in a 40°C shampoo solution for 10 seconds, then rinsed with 40°C running water for 10 seconds, and finally towel-dried. The effect on the hair was evaluated based on an overall assessment including curl formation rate, curl retention, and tactile feel. The curl formation rate was calculated by measuring the distance from the starting point of the curl at the root of the hair bundle (curl diameter) to the tip of the second longest hair in the bundle, and then measuring the distance from the starting point to the tip of the hair in question with the bundle straightened (hair length). The curl formation rate was calculated as (hair length - curl diameter) / hair length × 100.

[0123] To evaluate the persistence of curl formation, a hair strand was immersed in a shampoo solution, rinsed with water, excess water was wiped off with a towel, and left to dry at room temperature. This process was considered one cycle, and the number of cycles required before the formed curl was no longer maintained (the hair strand could no longer complete a full rotation) was measured.

[0124] Table 14 shows the evaluation results using healthy hair, and Table 15 shows the evaluation results using bleached hair. In experimental examples 11, 14, and 16, the hair condition was good, and highly persistent curls were formed on the hair.

[0125] [Table 14]

[0126] [Table 15]

[0127] Furthermore, the hair treatment agents were evaluated using Experimental Examples 11, 17, and 18, as well as a blank test (purified water), in the same manner as described above. The results are shown in Table 16. Experimental Example 11 showed a significant effect compared to Experimental Examples 17 and 18.

[0128] [Table 16]

[0129] Furthermore, the effects on bleached human hair were compared using Experimental Example 11 with muconic acid, Experimental Example 14 with adipic acid, and Experimental Example 16 with (E)-Oct-4-ene-1,8-dioic acid, along with Comparative Example 1 with fumaric acid, using the same method as in "10.". A shampoo concentrate containing each composition of Experimental Example 11, Experimental Example 14, Experimental Example 16, or Comparative Example 1 was prepared, and as a blank test, a shampoo concentrate containing purified water was used instead of the Experimental Examples or Comparative Examples. Hair was mixed with approximately 10% by weight of the shampoo concentrate in each case with warm water at approximately 40°C, and stirred until foam was formed to create the shampoo. Bundles of 30 to 40 strands of bleached human hair (average length 25 cm) were immersed in the shampoo solution, removed after 10 seconds, and rinsed with running water at approximately 40°C for approximately 10 seconds.

[0130] Hair was wrapped around a 25 mm diameter hair curler and heated with a hairdryer for 3 minutes until the hair surface reached approximately 60°C. The hair was carefully removed from the curler, gently rinsed with a shower of approximately 40°C warm water, towel-dried, left to stand, and the curl formation rate was measured. The results are shown in Table 17. When using the compositions of Experimental Examples 11, 14, and 16, a significantly higher curl formation rate was obtained compared to Comparative Example 1.

[0131] [Table 17]

[0132] 12. Evaluation of the hair treatment composition of the present invention (11): Effect of pH in the mixing step on the hair treatment effect of the composition

[0133] As Experimental Example 19, a hair treatment composition was prepared using muconic acid and cysteamine. Of the three isomers of muconic acid, the trans,trans type muconic acid was used. 1.42 g of muconic acid was added to 10 g of purified water, and ammonia water was added to adjust the pH to 4.2. The mixture was then heated to 80°C, and after confirming that the muconic acid had dissolved, 0.77 g of cysteamine was added. The mixture was heated while mixing until it boiled (to 100°C), and the boiling state (100°C) was maintained for 3 minutes to obtain a complex. Heating was stopped, and the mixture was allowed to stand at room temperature. After confirming that there were no undissolved particles, the pH was adjusted to around 7.0 with ammonia water, and purified water was added to adjust the final concentration of muconic acid and cysteamine to 10% by mass.

[0134] As Experimental Example 20, a hair treatment composition containing muconic acid and cysteamine was prepared. Of the three isomers of muconic acid, trans,trans muconic acid was used. 1.42 g of muconic acid was added to 10 g of purified water, and ammonia water was added to adjust the pH to 9.0. The mixture was then heated to 80°C, and after confirming that the muconic acid had dissolved, 0.77 g of cysteamine was added and heated while mixing until it boiled (to 100°C), and the boiling state (100°C) was maintained for 3 minutes. Heating was stopped, and the mixture was allowed to stand at room temperature. After confirming that there were no undissolved particles, the pH was adjusted to around 7.0 with ammonia water, and purified water was added to adjust the final concentration of muconic acid and cysteamine to 10% by mass.

[0135] The hair treatment effects on healthy human hair were verified using the compositions of Experimental Examples 19 and 20. 30 to 40 strands of healthy human hair or bleached hair (average length 25 cm) were bundled together. The compositions of the experimental and comparative examples were diluted to a concentration of 0.5% by mass of dicarboxylic acid and thiols (pH 7) and immersed for 3 minutes. Excess water was then wiped off. The hair was tightly wrapped around a 15 mm heated rod, heated for 10 minutes until the hair surface reached 60°C, and then left for another minute to cool before the hair was removed. The hair was then immersed in a 40°C shampoo solution for 10 seconds, rinsed with 40°C running water for 10 seconds, and then towel-dried to calculate the curl formation rate. The evaluation results are shown in Table 18. Comparing the effects of Experimental Example 19 and Experimental Example 20, Experimental Example 19 showed greater curl retention. Therefore, it was shown that the complex obtained by mixing in an acidic environment exhibits a higher hair treatment effect.

[0136] [Table 18]

[0137] 13. Evaluation of the hair treatment composition of the present invention (12)

[0138] As Experimental Example 21, a hair treatment composition was prepared by mixing cysteamine and muconic acid in a molar ratio of 2:1. Of the three isomers of muconic acid, trans,trans muconic acid was used. 1.42 g of muconic acid was added to 10 g of purified water and dissolved with ammonia water. After heating to 80°C and confirming that the muconic acid was dissolved, 2.27 g of cysteamine hydrochloride was added and heated while mixing until boiling (to 100°C), and the boiling state (100°C) was maintained for 1 hour to react the muconic acid and cysteamine. Heating was stopped and the mixture was allowed to stand at room temperature, and after confirming that there were no undissolved particles, the pH was adjusted to around 7.0 with ammonia water, and purified water was added to adjust the final concentration of muconic acid and cysteamine to 10% by mass.

[0139] Experimental Example 22 was prepared under the same conditions as Experimental Example 21, except that the reaction time between muconic acid and cysteamine was set to 6 hours. Experimental Example 23 was prepared under the same conditions as Experimental Example 21, except that cis,cis muconic acid was used instead of trans,trans muconic acid. Experimental Example 24 was prepared under the same conditions as Experimental Example 22, except that cis,cis muconic acid was used instead of trans,trans muconic acid.

[0140] Experimental Example 25 is a hair treatment composition obtained by mixing cysteamine and muconic acid in a molar ratio of 3:1. It was prepared under the same conditions as Experimental Example 24, except that 3.40 g of cysteamine hydrochloride was added to 1.42 g of cis,cis-type muconic acid. Experimental Example 26 is a hair treatment composition obtained by mixing cysteamine and muconic acid in a molar ratio of 1:1. It was prepared under the same conditions as Experimental Example 24, except that 1.13 g of cysteamine hydrochloride was added to 1.42 g of cis,cis-type muconic acid. Experimental Example 27 is a hair treatment composition obtained by mixing cysteamine and muconic acid in a molar ratio of 1:2. It was prepared under the same conditions as Experimental Example 24, except that 0.57 g of cysteamine hydrochloride was added to 1.42 g of cis,cis-type muconic acid.

[0141] The hair treatment effects on healthy human hair were verified using the compositions of Experimental Examples 21-27 in the same manner as in "12.". The manufacturing conditions and curl formation rates for each experimental example are shown in Table 19. Good hair treatment effects were obtained in all experimental examples using any isomer of muconic acid, but it was shown that a complex with a high effect could be obtained even with a short reaction time when trans,trans-muconic acid was used. Furthermore, a complex with a high effect was obtained when cysteamine:muconic acid was mixed in a molar ratio of 1:1 to 3:1. However, when Experimental Example 25, which was mixed in a molar ratio of 3:1, a thiol-derived malodor remained on the hair, and the texture of the hair treated with Experimental Example 25 was slightly worse compared to Experimental Example 24 or Experiment 26.

[0142] [Table 19]

Claims

1. It is a complex consisting of a dicarboxylic acid and a thiol. the dicarboxylic acid is one or more selected from the group consisting of muconic acid, adipic acid, octenedioic acid, and cosmetically acceptable salts thereof; The complex, wherein the thiols are one or more selected from the group consisting of aminothiols and cosmetically acceptable salts thereof.

2. 2. The complex of claim 1, wherein the dicarboxylic acid is muconic acid or a cosmetically acceptable salt thereof.

3. 3. The complex according to claim 1 or 2, wherein the thiol is cysteamine or a cosmetically acceptable salt thereof.

4. The complex according to any one of claims 1 to 3, comprising the dicarboxylic acid and the thiols in a molar ratio of thiols / dicarboxylic acid=0.01 to 100.

5. The complex according to claim 4, wherein the molar ratio of thiols to dicarboxylic acids is 1 or more.

6. A hair treatment composition comprising the complex described in any one of claims 1 to 5 as an active ingredient.

7. A hair straightener, a hair quality improving agent for dyeing or bleaching, a hair quality improving agent for wave perm or straight perm, a shampoo, a hair treatment agent, and / or a hair styling agent, comprising the complex according to any one of claims 1 to 5.

8. The hair quality improving agent for a wave perm or straight perm according to claim 7, which is not a first or second agent for a wave perm or straight perm.

9. An application step of applying the complex according to any one of claims 1 to 5 to hair; The hair treatment method includes at least a heating step of heating the hair after the application step.

10. The heating step is a step of heating the hair so that the surface temperature of the hair is 40 to 180°C. The hair treatment method according to claim 9.

11. The heating step is a step of heating the hair so that the surface temperature of the hair is 40 to 60°C. The hair treatment method according to claim 9.

12. The hair treatment method according to any one of claims 9 to 11, excluding a method in which the complex is applied to hair as a first or second agent for a wave perm or a straight perm.

13. The hair treatment method according to any one of claims 9 to 12, wherein the hair treatment method is intended for one or more purposes selected from the group consisting of hair straightening, improving hair quality during dyeing and bleaching, improving hair quality during wave perm and straight perm, shampooing, and hair treatment.

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