Hair modification method

Abstract

To provide a novel method for modifying hair and a novel hair cosmetic usable in the method.SOLUTION: A method for modifying hair includes a step of allowing a flavonoid having a LogP of 0 or more to adsorb onto hair under pH conditions ranging from 3.0 to 7.0.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel method for modifying hair and a novel hair cosmetic that can be used in the method.

Background Art

[0002] In recent years, various hair care products for modifying hair have been proposed. For example, in Patent Document 1, a hair cosmetic containing a specific cationized ascorbic acid derivative or a salt thereof as an antioxidant has been proposed for the purpose of providing a persistent antioxidant effect on hair. In Patent Document 2, a method for preventing damage to hair damaged by active oxygen by the synergistic antioxidant effect of a combination of carboxymethylphenylaminocarboxypropylphosphonic acid methyl (MCAP) and rosmarinic acid, rutin, etc. is known. In Patent Document 3, it is known to use a specific cationic polymer as an antioxidant or a free radical scavenger to reduce hair damage. Furthermore, in Patent Document 4, it is also known that a conjugate of luteolin having an antioxidant effect and cyclodextrin is used for the care, maintenance, and improvement of the general state of hair.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention relates to a novel method for modifying hair and a novel hair cosmetic that can be used in the method.

Means for Solving the Problems

[0005] The present invention relates to the following [1] to [3]. [1] A method for modifying hair, comprising a step of adsorbing a flavonoid having a LogP of 0 or more to hair under the conditions of pH 3.0 to 7.0. [2] A hair cosmetic comprising a flavonoid-cyclodextrin inclusion compound in which a flavonoid having a LogP of 0 or more is included by cyclodextrin, and having a pH of 3.0 to 7.0. [3] A method for producing a hair cosmetic having a pH of 3.0 to 7.0, comprising a step of adding a flavonoid-cyclodextrin inclusion compound in which a flavonoid having a LogP of 0 or more is included by cyclodextrin.

Effects of the Invention

[0006] According to the present invention, it is possible to provide a novel method for modifying hair and a novel hair cosmetic that can be used in the method.

Modes for Carrying Out the Invention

[0007] As a result of intensive studies on the above problems by the present inventors, it was newly found that hair can be suitably modified by adsorbing a flavonoid having a LogP of 0 or more to hair under the conditions of pH 3.0 to 7.0. This is presumably related to the hydrophobicity of the flavonoid.

[0008] The method for modifying hair of the present invention includes a step of adsorbing a flavonoid having a LogP of 0 or more onto hair under the conditions of pH 3.0 to 7.0, preferably 6.5 or less, more preferably 6.0 or less, still more preferably 5.5 or less, and still more preferably 5.0 or less. Also, the lower limit value can be pH 3.0 or more, 3.5 or more, 4.0 or more, etc. From the viewpoint of adsorbing the flavonoid onto hair, the value of LogP is preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1. Examples of flavonoids having a LogP of 0 or more include isoquercitrin (LogP: 0.69), quercetin-4'-glucoside (LogP: 0.32), hesperetin-7-glucoside (LogP: 0.6), naringenin-7-glucoside (LogP: 0.6), myricetin (LogP: 1.2), quercetin (LogP: 1.82), naringenin (LogP: 2.4), etc. LogP (octanol / water partition coefficient) in this specification represents the ratio of the equilibrium concentrations of a substance dissolved in two phases of octanol and water, and the larger this value is, the more lipophilic it indicates. The LogP value can be measured according to the flask shaking method described in Japanese Industrial Standard Z7260-107.

[0009] In the method of the present invention, the hair is not limited, and the method of the present invention can be widely used from less damaged hair to highly damaged hair (damaged hair). Examples of hair modification in the method of the present invention include improvement of hair ximii, smoothness, frizz, and stiffness, and suppression of hair damage, fading, discoloration, color fading, color burning, frizz, and stiffness caused by oxidation, ultraviolet rays, sunlight, etc.

[0010] Examples of the method for adsorbing onto hair in the method of the present invention include an adsorption method using a hair cosmetic having a pH of 3.0 to 7.0 containing a flavonoid having a LogP of 0 or more. For example, known hair cosmetics such as shampoos, rinse-off treatments, conditioners such as leave-on treatments, hair mists, press styling agents such as bedhead straighteners, hair sprays, hair waxes, hair creams, hair gels, hair mousses, and other styling agents, hair dyes for gray hair, hair color bleaches, coloring agents such as perm solutions, etc. can be used for adsorption.

[0011] The present inventors have newly found that, in the mode of formulating a flavonoid having a LogP of 0 or more in an aqueous hair cosmetic, it is preferable to formulate it as a flavonoid (LogP of 0 or more)-cyclodextrin inclusion compound in which the flavonoid having a LogP of 0 or more is included by cyclodextrin and to set a specific pH. Since flavonoids having a LogP of 0 or more are hydrophobic, they are poorly soluble in aqueous hair cosmetics. However, as shown in the examples described later, when the solubility in water is improved using enzyme-treated rutin (α-glucosylrutin) or enzyme-treated isoquercitrin to which sugar is bound, it was found that the adsorption amount to hair significantly decreases. On the other hand, it was newly found that the solubility in water and the adsorptivity to hair can be compatible by inclusion with cyclodextrin, and in particular, the flavonoid-cyclodextrin inclusion compound obtained by the enzyme method described later is preferable.

[0012] The reason why the solubility in water and the adsorptivity to hair can be achieved simultaneously by encapsulating flavonoids with a LogP of 0 or more with cyclodextrin is considered as follows. Cyclodextrin (CD) has a cylindrical shape with one end narrowed like an open-bottomed bucket, with a hydrophobic interior and a hydrophilic exterior. Incorporating molecules into the hydrophobic cavity of cyclodextrin is called encapsulation (Chemistry and Education, 38(2)158 - 162, 1990). Similarly, in the flavonoid-cyclodextrin inclusion compound, the flavonoid is encapsulated in the interior of the cyclodextrin by weak bonds (van der Waals forces and hydrophobic bonds). However, since the flavonoid inclusion complex is not a strong bond like a covalent bond, if a more easily bondable substance exists in the external environment, it is presumed that the encapsulated flavonoid will be decomplexed from the cyclodextrin and adsorbed efficiently to the hair. Also, among the flavonoid-cyclodextrin inclusion compounds, the mechanism why those obtained by the enzyme method described later are preferred is unclear, but it is considered as follows. When a flavonoid-cyclodextrin inclusion compound is prepared by a method other than the enzyme method, such as stirring and mixing (dissolution method, etc.), the sites where the flavonoid is encapsulated with cyclodextrin are randomly encapsulated with the A-C ring, B ring, and sugar moiety of the flavonoid (PLoS One, 10(3), e0120858.), but when the inclusion compound is prepared by the enzyme method, since the flavonoid is encapsulated at a specific position (Carbohydrate Polymer Technologies and Applications, 2, 100046., Molecules, 27(17), 5395.), it is presumed that it will be adsorbed to the hair more efficiently. Hereinafter, the embodiments of hair cosmetics using a flavonoid-cyclodextrin inclusion compound obtained by encapsulating a flavonoid with a LogP of 0 or more with cyclodextrin will be described, but the modification method of the present invention is not limited to this embodiment.

[0013] The hair cosmetic of this embodiment contains a flavonoid-cyclodextrin inclusion compound in which a flavonoid having an antioxidant ability with a LogP of 0 or more is included by cyclodextrin. Examples of the flavonoid-cyclodextrin inclusion compound include isocitrin-cyclodextrin inclusion compound, hesperetin-7-glucoside-cyclodextrin inclusion compound, and naringenin-7-glucoside-cyclodextrin inclusion compound. From the viewpoint of adsorbing the flavonoid to the hair, the flavonoid-cyclodextrin inclusion compound obtained by the enzyme method described later is preferable. As a commercially available flavonoid-cyclodextrin inclusion compound, for example, Sampure CEN (IQC-γCD inclusion compound, manufactured by Sun Chemical Corporation) can be preferably used.

[0014] Examples of the cyclodextrin in the flavonoid-cyclodextrin inclusion compound include β-cyclodextrin (β-CD), branched β-cyclodextrin (branched β-CD), γ-cyclodextrin (γ-CD), and the like.

[0015] The content of the flavonoid-cyclodextrin inclusion compound in the hair cosmetic of this embodiment can be 0.01 to 10% by mass, 0.05 to 5% by mass, 0.1 to 1% by mass, and the like.

[0016] The water content in the hair cosmetic of this embodiment can be 10 to 99% by mass, and can be 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, and the like.

[0017] The hair cosmetic of this aspect can optionally contain components used in hair cosmetics, such as amidoamines such as dimethylaminopropylamide stearate, aliphatic alcohols, aromatic alcohols, amino acids, amino acid derivatives, vitamins, sphingosines and ceramides, silicone components, organic acids, and the like. Here, as the organic acid, an organic acid having 10 or less carbon atoms is preferable, such as an acid having a short-chain alkyl group having 10 or less carbon atoms such as alkyl phosphoric acid, alkyl sulfonic acid, and alkyl sulfuric acid; acidic amino acids such as L-glutamic acid and L-aspartic acid; pyroglutamic acid; aromatic acids such as benzoic acid and p-toluenesulfonic acid; hydroxy acids; dicarboxylic acids, and the like. Examples of the hydroxy acid include hydroxymonocarboxylic acids such as glycolic acid, lactic acid, glyceric acid, gluconic acid, and pantothenic acid; hydroxydicarboxylic acids such as malic acid and tartaric acid; and hydroxytricarboxylic acids such as citric acid. Examples of the dicarboxylic acid include oxalic acid, malonic acid, maleic acid, succinic acid, glutaric acid, and the like.

[0018] In addition, the hair cosmetic of this embodiment can optionally contain medicinal components such as (1) blood circulation promoters, (2) anti-inflammatory agents, (3) local irritants, (4) hair follicle activators, (5) hair matrix cell differentiation and proliferation promoters, (6) moisturizing agents, (7) keratolytic agents, (8) anti-seborrheic agents, (9) antibacterial agents, (10) anti-androgen agents, and (11) potassium channel openers. (1) Blood circulation promoters refer to one or more selected from nicotinic acid derivatives, acetylcholine, carpronium chloride, diphenhydramine hydrochloride, γ-oryzanol, sericetin, nicorandil, pinafidil, phthalides, centella extract, carrot extract, ginkgo extract, cinchona extract, and torreya extract. Here, examples of nicotinic acid derivatives include nicotinamide, benzyl nicotinate, nicotinic acid dl-α-tocopherol, etc. (2) Anti-inflammatory agents refer to one or more selected from licorice extract, glycyrrhetinic acid and its derivatives, fat-soluble glycyrrhetinic acids, azulene, guaiazulene, antihistamines, hydrocortisone acetate, prednisolone, saffron extract, chamomile extract, miscanthus extract, birch extract, Japanese butterbur extract, peach leaf extract, common yarrow extract, aster extract, loquat leaf extract, and bletilla extract. Here, examples of antihistamines include diphenhydramine, clemastine fumarate, etc., examples of glycyrrhetinic acid derivatives include dipotassium glycyrrhetinate, monoammonium glycyrrhetinate, etc., and examples of fat-soluble glycyrrhetinic acids include glycyrrhetinic acid (β-glycyrrhetinic acid), glycyrrhetinic acid glycerin, stearyl glycyrrhetinate, etc. (3) Local irritants include one or more selected from camphor, capsicum tincture, nonyl vanillylamide, ginger tincture, Dutch pepper, cantharis tincture, peppermint oil, and wasabi radish extract.(4) Examples of the hair follicle activator include N-acetyl-L-methionine, Tamasa kizurafuji, cephalanthin, disodium adenosine triphosphate, potassium aspartate, photosensitive dye 301, pentadecaglyceride, ethyl pantothenate, Tikusetsuninjin, biotin, mononitroguayacol sodium, yeast extract, garlic component, pearl protein extract, wheat germ extract, placenta extract, royal jelly, etc. Among these, Tamasa kizurafuji, cephalanthin, disodium adenosine triphosphate, pentadecaglyceride, ethyl pantothenate, Tikusetsuninjin, biotin, mononitroguayacol sodium, placenta extract, and royal jelly are preferable. (5) Examples of the hair matrix cell differentiation and proliferation promoter include flavanol derivatives described in JP-A-8-157334. Among them, trans-3,4'-dimethylflavanol and trans-4'-chloro-3-methylflavanol are preferable. (6) Examples of the humectant include Houttuynia cordata extract, oat extract, soluble collagen, glycerin, chondroitin sulfate, tuberose polysaccharide, propylene glycol, eucalyptus extract, Cordyceps sinensis extract, Sedum sarmentosum extract, barley extract, orange extract, grape extract, guaraná extract, seaweed extract, button mushroom extract, ginger extract, duke extract, myrica flower extract, yokukinin extract, etc. (7) Examples of the keratolytic agent include aspirin, glycolic acid, etc. (8) Examples of the anti-seborrheic agent include sulfur, lecithin, cashew extract, thioxolone, etc. (9) Examples of the antibacterial agent preferably include isopropylmethylphenol, benzalkonium chloride, octopirox, zinc pyrithione, hinokitiol, etc. (10) Examples of the anti-androgen agent include cyproterone acetate, 11α-hydroxyprogesterone, flutamide, 3-deoxyadenosine, chloromadinone acetate, ethinyl estradiol, spironolactone, epitestosterone, aloe, sansho, otaneninjin, etc. (11) Examples of the potassium channel opener include minoxidil, cromakalim, diazoxide and its derivatives, pinacidil, etc.

[0019] In addition, the hair cosmetic of this aspect may contain rhamnose. The content of rhamnose in the hair cosmetic of this aspect is preferably 0.001 to 15% by mass, more preferably 0.01 to 6% by mass, still more preferably 0.1 to 2% by mass.

[0020] From the viewpoint of adsorbing flavonoids to hair, the pH of the hair cosmetic of this aspect is 3.0 to 7.0, preferably 6.5 or less, more preferably 6.0 or less, still more preferably 5.5 or less, and even more preferably 5.0 or less. Also, the lower limit value can be 3.0 or more, 3.5 or more, 4.0 or more, etc.

[0021] The hair cosmetic of this aspect includes a step of adding a flavonoid-cyclodextrin inclusion compound in which a flavonoid having a LogP of 0 or more is included by cyclodextrin during the manufacturing process, and can be prepared in the same manner as a known manufacturing method except that the pH of the hair cosmetic is set to 3.0 to 7.0.

[0022] The flavonoid-cyclodextrin inclusion compound according to the hair cosmetic of this aspect can be prepared by a known manufacturing method, and can be prepared, for example, by the dissolution method or the enzyme method shown below.

[0023] Dissolution method As a method for producing a flavonoid-cyclodextrin inclusion compound by the dissolution method, a cyclodextrin can be mixed with a flavonoid at a certain ratio in a water / organic solvent in which the flavonoid is dissolved to prepare an inclusion compound of the flavonoid and the cyclodextrin.

[0024] Enzyme method As a method for producing a flavonoid-cyclodextrin inclusion compound by an enzymatic method, it can be prepared by the method described in Patent No. 6616046 or the like. That is, it is a method of treating a flavonoid having a rhamnoside structure with an enzyme having rhamnosidase activity under the conditions of pH 3 to 7 in the presence of cyclodextrin. By the enzymatic method, rhamnose is eliminated from the flavonoid having a rhamnoside structure, and an inclusion compound of a flavonoid having no rhamnoside structure and cyclodextrin can be obtained.

[0025] The enzymatic method can be carried out by standing or stirring in a solvent such as water. In order to prevent oxidation or browning during the reaction, the air in the headspace of the reaction system may be replaced with an inert gas such as nitrogen, or an antioxidant such as ascorbic acid may be added to the reaction system. The enzymatic reaction can be terminated by a known method such as a method of inactivating the enzyme by heating the reaction solution. After the enzymatic reaction is completed, it can be filtered and dried. Further purification can also remove rhamnose and the like and then dry it.

[0026] In the enzymatic method, examples of the flavonoid having a rhamnoside structure as a raw material include those selected from flavones, flavonols, flavanones, flavanols, and isoflavones having a rhamnoside structure. For example, when preparing an isocitrin-cyclodextrin inclusion compound, a hesperetin-7-glucoside-cyclodextrin inclusion compound, or a naringenin-7-glucoside-cyclodextrin inclusion compound as a flavonoid-cyclodextrin inclusion compound, rutin, hesperidin, or naringin is used as the flavonoid having a rhamnoside structure as a raw material.

[0027] In the enzymatic method, the amount of cyclodextrin to be present is not particularly limited, but in the reaction system, it is preferably 0.01 to 60% by mass, more preferably 1 to 50% by mass, and even more preferably 3 to 40% by mass. When two or more kinds of cyclodextrins are used, the amount refers to the total amount.

[0028] In the enzymatic method, for flavonoids having a rhamnoside structure, the molar ratio of cyclodextrin to be added (added cyclodextrin / flavonoid) is preferably 0.01 or more, more preferably 0.9 or more, still more preferably 1.0 or more, and from the viewpoint of economy, preferably 10.0 or less, more preferably 6.0 or less, still more preferably 4.0 or less, and even more preferably 3.0 or less, from the viewpoints of efficiency and economy.

[0029] In the enzymatic method, the molar ratio of rhamnose produced to flavonoid monoglucoside after rhamnose is eliminated from the flavonoid having a rhamnoside structure as the raw material (produced rhamnose / flavonoid monoglucoside) is preferably 0.5 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 2 or less, more preferably 1.2 or less. That is, it can be 0.5 to 2.0, 0.7 to 1.2, 0.8 to 1.2, etc. Note that flavonoid monoglucoside refers to flavonoids in which one glucose is added to the aglycone of flavonoids such as isoquercitrin, hesperetin-7-glucoside, and naringenin-7-glucoside.

[0030] In the enzymatic method, the enzyme having rhamnosidase activity is not limited to its origin, and enzymes derived from all origins such as animals, plants, and microorganisms can be used. Furthermore, it may be a genetically engineered enzyme. Also, the form of the enzyme is not particularly limited. Specific examples of the enzyme having rhamnosidase activity include hesperidinase, naringinase, β-glucosidase, pectinase, and the like. The amount of the enzyme having rhamnosidase activity used varies depending on the type of enzyme used, reaction conditions, the type of flavonoids having a rhamnoside structure as a raw material, etc. For example, in the case of hesperidinase, naringinase, and β-glucosidase, it is preferably 0.01 to 1000 U per 1 g of flavonoids having a rhamnoside structure. The reaction conditions can be selected for the reaction temperature and the pH of the reaction solution according to the characteristics of the enzyme used, but it is preferably pH 3 to 7, and more preferably pH 3.5 to 6.5. Also, an enzymatic reaction can be carried out at pH 7 or lower after dissolving flavonoids having a rhamnoside structure in the alkaline range. Examples of the solvent used in the reaction system include an aqueous medium. In this specification, an aqueous medium refers to water or an aqueous solution of an organic solvent. Examples of water include tap water, distilled water, ion-exchanged water, and purified water. The organic solvent is not particularly limited as long as it can be uniformly mixed with water. Ethanol is preferred as the organic solvent. The reaction temperature is preferably 10 to 80°C, and more preferably 40 to 75°C. Also, the reaction time varies depending on the type of enzyme, etc., but for example, it can be 1 to 100 hours, and 2 to 24 hours is preferred. The purification method is not particularly limited, and purification can be carried out by a resin treatment step (adsorption method, ion exchange method, etc.), a membrane treatment step (ultrafiltration membrane treatment method, reverse osmosis membrane treatment method, zeta potential membrane treatment method, etc.), and electrodialysis, salting out, acid precipitation, recrystallization, solvent fractionation method, etc.

[0031] The conversion rate of the inclusion compound produced by the enzymatic method is preferably 10 to 100%, more preferably 40 to 100%, still more preferably 70 to 100%, and even more preferably 90 to 100%. The conversion rate (%) indicates the conversion rate from the flavonoid having a rhamnoside structure to the flavonoid having no rhamnoside structure, and can be calculated by HPLC analysis (peak area of the flavonoid having no rhamnoside structure × 100 / (peak area of the flavonoid having a rhamnoside structure + peak area of the flavonoid having no rhamnoside structure)).

Examples

[0032] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited in any way by these examples. Unless otherwise specified, “%” means “mass %”. shall be assumed.

[0033] Preparation Example 1: Isoquercitrin 100 g of rutin (manufactured by Alps Pharmaceutical Co., Ltd.) was added to 1000 L of an aqueous solution, and the mixture was adjusted to 70° C. and pH 4.5. Then, while stirring, 0.3 g of naringinase (5000 u / g manufactured by Amano Enzyme Inc.) was added. After a 24-hour enzymatic reaction, the precipitate was recovered, recrystallized, and dried to obtain 72 g of isoquercitrin with a content of 96% or more. Using reagent isoquercitrin (Wako), it was confirmed that the content was the same by HPLC.

[0034] (Isoquercitrin concentration analysis method, isoquercitrin content / conversion value calculation method) HPLC (SHIMADZU) analysis (HPLC conditions: column: CAPCELLPAK C18 SIZE 4.6 mm × 250 mm (SHISEIDO), eluent: 20 - 40% (v / v) acetonitrile / 0.1% phosphoric acid aqueous solution, flow rate: 0.4 ml / min, column temperature: 70°C, wavelength: 351 nm (isocquercitrin), reagent isocquercitrin (Wako), compared the calibration curves to calculate the isocitric acid concentration, and calculated the flavonoid content in the hair cosmetics of the examples. Note that the enzymatically treated isocquercitrin was expressed as an isocquercitrin equivalent value. Specifically, it was calculated as follows. Enzymatically treated isocquercitrin: The sum of the peak areas by HPLC analysis (same conditions as isocquercitrin concentration analysis) and the peak area comparison of the calibration curve of the reagent isocquercitrin were used to calculate the isocquercitrin equivalent value. Note that instead of isocquercitrin, hesperetin-7-glucoside, enzymatically treated hesperidin, etc. (wavelength 285 nm), naringenin-7-glucoside, enzymatically treated naringin, etc. (wavelength 285 nm) can also be analyzed in the same HPLC method as the hesperetin-7-glucoside concentration (converted value) and the naringenin-7-glucoside concentration (converted value).

[0035] Examples 1 - 3, Comparative Examples 1 - 3 50 ml aqueous solution (0.1 M citric acid buffer pH 5) and the components shown in Table 1 were mixed so that the quercetin-glucoside concentration (converted concentration) was 0.01% (quercetin converted concentration 0.065%) respectively to prepare hair cosmetics.

[0036] The details of the components used in Table 1 are shown below. (1) Quercetin (FUJIFILM Wako Pure Chemical Corporation) (2) IQC: Isocquercitrin obtained in Preparation Example 1 (3) Quercetin-4'-glucoside (Merck KGaA) (4) Enzymatically treated isocquercitrin (Sunmerin AO-3000, San-Ei Gen F.F.I., Inc.) (5) RTN: Rutin (Alps Pharmaceutical Co., Ltd.) (6) Enzymatically treated rutin (αG rutin, Toyo Seito Co., Ltd.)

[0037] Adsorption rate of flavonoids to hair Normal hair (1 g of human black hair, 10 cm, product number BS - B - A, manufactured by Bureau Veritas Co., Ltd.) and the hair cosmetics of each example and comparative example prepared above were placed in a 50 ml tube (manufactured by Falcon). After addition, they were immersed for 30 minutes (rotated 5 times per minute with TUBE ROTATOR TR - 35 (manufactured by AS ONE Corporation)). Then, the concentration of each in the solution was measured (HPLC analysis), and the adsorption rate was calculated by the following formula (Formula 1). The results are shown in Table 1. For each sample, the analysis was performed 3 times, and the average value is shown in Table 1. (Formula 1) Adsorption rate (%) = Concentration in terms of quercetin - glucoside (initial solution - solution after immersion) × 100 / (Concentration of quercetin - glucoside in the initial solution)

[0038] [Table 1]

[0039] As shown in Table 1, it was found that the adsorption rate to hair increases by using flavonoids with a LogP value of 0 or more.

[0040] Preparation Example 2: Isoquercitrin - γ - cyclodextrin inclusion compound (enzymatic method) To a 1000 ml beaker, 80 g of rutin (manufactured by Alps Pharmaceutical Co., Ltd.) and 170 g of γ-cyclodextrin (manufactured by Pearl Ace Co., Ltd., Dexy Pearl γ-100) were added, water was added to make 1000 g, and it was adjusted to 70 °C and pH 4.5. Then, while stirring, 0.16 g of naringinase (Amano Enzyme Inc., 5000 u / g) was added and reacted for 24 hours. After analyzing and confirming the conversion rate (%) of more than 98% = ((peak area of isocquercitrin) × 100 / (peak area of rutin + peak area of isocquercitrin)) by HPLC, a dried product of the inclusion compound of isocquercitrin-γ-cyclodextrin was obtained by spray drying (220 g, isocquercitrin content of 18% or more, molar ratio of rhamnose / isocquercitrin produced 0.8 - 1.2). The fact that isocquercitrin and γ-cyclodextrin are included was confirmed by differential scanning calorimetry (DSC), nuclear magnetic resonance (NMR), and Fourier transform infrared spectrophotometry (FT-IR) (Carbohydrate Polymer Technologies and Applications 2 (2021): 100046).

[0041] Preparation Example 3: Isocquercitrin-γ-cyclodextrin inclusion compound (dissolution method) 4 g of isocquercitrin (Adjustment Example 1) and γ-cyclodextrin (manufactured by Pearl Ace Co., Ltd.) were mixed at a mol ratio of 1:5 (total mass 60 g), water was added thereto to make 1000 ml, and it was heated to about 85 °C and stirred for 1 hour to dissolve the solid components. Then, it was returned to room temperature, filtered through filter paper, and freeze-dried to prepare 54 g of a powdery isocquercitrin-γ-cyclodextrin inclusion compound.

[0042] Examples 4 to 27, Comparative Examples 4 to 15 Adsorption amount of flavonoid on colored hair, coloring rate after sunlight irradiation, and resistance when passing through a comb after sunlight irradiation Instead of healthy hair, colored hair (human hair medium brown (14LV) 1g, 10cm, product number BR-2-A, manufactured by Viewrax Co., Ltd.) was used, and the adsorption rate of flavonoids to hair was measured in the same manner as in Table 1, except that the components and immersion time described in Tables 2 and 3 were used. After immersion, the colored hair was washed with distilled water (50 mL × 4 times) and then dried (1g), and irradiated with sunlight (for 7 days in summer). Then, using a digital microscope (Keyence, VHX-6000), the residual ratio of purple coloring was compared by calculating the area ratio of purple coloring (comparing the areas before and after sunlight irradiation by color area calculation). Furthermore, using 1g of dry hair before and after sunlight irradiation, a comb-through test was conducted. That is, the resistance when passing a comb was measured (apparatus: static and dynamic friction measuring machine TL201Tt (manufactured by Trinity Lab Co., Ltd.), starting from 6 cm from the tip of the hair bundle as the starting point, measuring the resistance when passing the comb under the conditions of a jig for fixing the comb, speed: 20 mm / s, distance: 7 cm, and comparing the maximum resistance (gf). Note that the smaller the gf value, the smoother the hair. These results are shown in Tables 2 and 3. Each sample was analyzed 3 times, and the average values are shown in Tables 2 and 3.

[0043] The details of the components used in Tables 2 and 3 are shown below. (1) IQC-γCD inclusion compound (enzymatic method): The isocitrusin-γ-cyclodextrin inclusion compound obtained in Preparation Example 2 (2) IQC-γCD inclusion compound (dissolution method): The isocitrusin-γ-cyclodextrin inclusion compound obtained in Preparation Example 3 (3) IQC + γCD: Isocitrusin (Preparation Example 1) and γ-cyclodextrin (manufactured by Pearl Ace Co., Ltd.) (4) IQC: Isocitrusin (Preparation Example 1) (5) Enzymatically treated isocitrusin (Sammyrin AO-3000, San-Ei Gen F.F.I.)

[0044]

Table 2

[0045]

Table 3

[0046] Although not shown in the table, the same results were obtained when the components shown below were used instead of the respective components shown in Tables 2 and 3. (1) A mode in which hesperetin-7-glucoside-βCD inclusion compound (enzymatic method) or naringenin-7-glucoside-βCD inclusion compound (enzymatic method) is used instead of IQC-γCD inclusion compound (enzymatic method). (2) A mode in which hesperetin-7-glucoside-βCD inclusion compound (dissolution method) or naringenin-7-glucoside-βCD inclusion compound (dissolution method) is used instead of IQC-γCD inclusion compound (dissolution method). (3) A mode in which hesperetin-7-glucoside + βCD or naringenin-7-glucoside + βCD is used instead of IQC + γCD. (4) A mode in which hesperetin-7-glucoside or naringenin-7-glucoside is used instead of IQC. (5) A mode in which enzymatically treated hesperidin (αG hesperidin, Toyo Sugar Refining Co., Ltd.) or enzymatically treated naringin (αG naringin, Toyo Sugar Refining Co., Ltd.) is used instead of enzymatically treated isoquercitrin.

[0047] As shown in Tables 2 and 3, in each example, it was adsorbed on colored hair and showed an effect of preventing fading by sunlight and an effect of improving smoothness. At that time, it was found that the IQC-γCD inclusion compound (enzymatic method) was most improved. These results are considered to be due to the fact that, depending on the adsorption amount of antioxidant isoquercitrin on hair, fading of colored hair by sunlight was prevented, and deterioration of hair components such as keratin fibers in hair (lipids, proteins, etc.) by sunlight was prevented, so the smoothness when passing through a comb was improved.

[0048] Examples 28 to 39, Comparative Examples 16 to 21 Damaged hair and flavonoid adsorption amount Healthy hair (1 g, 10 cm of human black hair, product number BS-B-A, manufactured by Viewrax Co., Ltd.) (undamaged), hair that had been subjected to 15 cycles of damage treatment (washed with a neutral detergent for 5 minutes (0.1%, manufactured by Procter & Gamble, Joy) ⇒ washed with distilled water ⇒ rinsed with distilled water ⇒ dried (using a dryer for 10 minutes) ⇒ brushed) (damaged), and hair that had been subjected to 30 cycles of the above damage treatment (severely damaged) were used, and the adsorption rate of flavonoids to the hair was measured in the same manner as in Table 1, except that the components described in Table 4 were used. Note that all the components in Table 4 are the same as those in Tables 2 and 3. The results are shown in Table 4. The analysis was performed three times for each sample, and the average value is shown in Table 4.

[0049]

Table 4

[0050] Although not shown in the table, similar results were obtained when the following components were used instead of the components shown in Table 4. (1) A mode in which a hesperetin-7-glucoside-βCD inclusion compound (enzymatic method) or a naringenin-7-glucoside-βCD inclusion compound (enzymatic method) is used instead of the IQC-γCD inclusion compound (enzymatic method). (2) A mode in which a hesperetin-7-glucoside-βCD inclusion compound (dissolution method) or a naringenin-7-glucoside-βCD inclusion compound (dissolution method) is used instead of the IQC-γCD inclusion compound (dissolution method). (3) A mode in which hesperetin-7-glucoside + βCD or naringenin-7-glucoside + βCD is used instead of IQC + γCD. (4) A mode in which hesperetin-7-glucoside or naringenin-7-glucoside is used instead of IQC. (5) A mode in which enzymatically treated hesperidin (αG hesperidin, manufactured by Toyo Seito Co., Ltd.) or enzymatically treated naringin (αG naringin, manufactured by Toyo Seito Co., Ltd.) is used instead of enzymatically treated isoquercitrin.

[0051] As shown in Table 4, in each example, the adsorption capacity of isocitric acid increased as the damage became greater. That is, it was found that the adsorption amount of isocitric acid increased in response to the deterioration of hair constituent components (lipids, proteins, etc.), such as keratin fibers of hair, depending on the number of times of detergent washing, brushing, etc. At that time, the IQC-γCD inclusion compound (enzymatic method) had the greatest adsorption capacity.

[0052] Examples 40 to 49, Comparative Examples 22 to 23 Damaged hair and flavonoid adsorption amount (difference in pH) The procedure was the same as in Table 4 except that the hair cosmetic was adjusted to the pH shown in Table 5. That is, healthy hair (1 g, 10 cm of human black hair, product number BS-B-A, manufactured by Bureau Lux Co., Ltd.) (undamaged), and the healthy hair was subjected to damage treatment (washed with a neutral detergent for 5 minutes (0.1%, manufactured by P&G Joy) ⇒ washed with distilled water ⇒ rinsed with distilled water ⇒ dried (for 10 minutes with a dryer) ⇒ brushed) 15 times (during damage)). The adsorption rate of flavonoids to the hair was measured in the same manner as in Table 1. However, the pH during immersion was 3 - 5 with 0.1 M citrate buffer and pH 6 - 8 with 0.1 M phosphate buffer. These results are shown in Table 5. For each sample, the analysis was performed 3 times, and the average value is shown in Table 5.

[0053]

Table 5

[0054] As shown in Table 5, in each example, differences in adsorption rates were observed due to differences in the pH of the hair cosmetics. It was found that at pH 3-7, the adsorption amount increased significantly compared to pH 8, and the adsorption amount increased as the pH decreased from pH 7 to pH 3. One of the reasons is thought to be that flavonoids are easily decomposed by alkalis (Experimentally Learned Chemistry (5) Measuring by Color. Annals of Tokyo Woman's Christian University. Science Department Report = Science reports of Tokyo Woman's Christian University / Edited by the Editorial Committee of the Tokyo Woman's Christian University Collection 63 (2013): 1961-1975.). Although not shown in the table, among various flavonoids, the IQC-γCD inclusion compound (enzymatic method) had the highest adsorption power.

[0055] (Formulation Example) The formulation examples of the cosmetics of the present invention are given below. The present invention is not limited by these formulation examples in any way. Note that all blending amounts are expressed as mass % with respect to the total amount of the product.

[0056]

Table 6

[0057]

Table 7

[0058]

Table 8

[0059] The hair cosmetics of Formulation Examples 1 to 3 were all excellent in improving hair damage.

Industrial Applicability

[0060] According to the present invention, a novel hair modification method and a novel hair cosmetic that can be used in the method can be provided.

Claims

1. A method for modifying hair, comprising a step of adsorbing a flavonoid having a LogP of 0 or more to the hair under the conditions of pH 3.0 to 7.

0.

2. The method according to claim 1, comprising one or more hair modifications selected from the group consisting of improvement of hair dryness, stickiness, roughness, suppression of hair damage, fading, discoloration, color fading, color burning, stickiness, and roughness.

3. A hair cosmetic comprising a flavonoid-cyclodextrin inclusion compound in which a flavonoid having a LogP of 0 or more is included by cyclodextrin, and having a pH of 3.0 to 7.

0.

4. The hair cosmetic according to claim 3, wherein the inclusion compound includes an inclusion compound obtained by treating a flavonoid having a rhamnoside structure with an enzyme having rhamnosidase activity in the presence of cyclodextrin under reaction conditions of pH 3 to 7, and the cyclodextrin includes one or more selected from the group consisting of β-cyclodextrin, branched β-cyclodextrin, and γ-cyclodextrin.

5. The hair cosmetic according to claim 3, wherein the inclusion compound includes one or more selected from the group consisting of isoquercitrin-cyclodextrin inclusion compound, hesperetin-7-glucoside-cyclodextrin inclusion compound, and naringenin-7-glucoside-cyclodextrin inclusion compound.

6. The hair cosmetic according to claim 3, having a pH of 3.0 to 6.

5.

7. The hair cosmetic according to claim 3, which is used for one or more hair modifications selected from the group consisting of improvement of hair dryness, stickiness, roughness, suppression of hair damage, fading, discoloration, color fading, color burning, stickiness, and roughness.

8. A method for producing a hair cosmetic having a pH of 3.0 to 7.0, comprising a step of adding a flavonoid-cyclodextrin inclusion compound in which a flavonoid having a LogP of 0 or more is included by cyclodextrin.

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