JPH0242806B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hair protection agent other than a hair rinse, and more particularly to a hair protection agent other than a hair rinse that is excellent in protecting and strengthening hair, containing a specific keratin derivative and calcium ions or calcium ions and magnesium ions. Keratin derivatives such as keratin hydrolyzate,
It has a chemical structure similar to the keratin protein that makes up hair, and is known to have the effect of protecting hair and restoring damaged hair. , cold wave lotions, permanent wave hair protection agents, hair setting agents, and the like have been proposed by the present inventors. By the way, hair contains a large number of trace minerals, and it is known that the excess or deficiency of these minerals is related to a person's health condition. Of these minerals, calcium is the one that is contained in the largest amount. Medically, the normal and necessary content is 200 to 600 ppm. The present inventors conducted various studies based on the idea that such fluctuations in the amount of minerals contained in hair would affect not only the health condition of a person but also the condition of the hair itself. As a result of applying hair cosmetics to the hair, the minerals in the hair are reduced, especially the reduction of calcium and magnesium, and especially the reduction of calcium has a great effect on the hair, causing a decrease in the frizz of the hair, Pasatsuki,
It has been found that this causes problems such as poor combing and a decrease in strength. The reason that calcium, magnesium, etc. in the hair decreases when hair cosmetics are applied is due to the chelating agents contained in hair cosmetics, such as ethylenediaminetetraacetic acid (hereinafter referred to as EDTA). considered to be a thing. In other words, most hair cosmetics in the form of aqueous solutions or creams contain surfactants, and chelating agents are added to maintain the functionality of these surfactants and to improve the quality stability of the cosmetics themselves. . For example, chelating agents are added to shampoos to prevent lathering from decreasing due to calcium and magnesium contained in hot water or water during hair washing, and iron ions are added to the first agent for cold waves containing thioglycolic acid. Chelating agents are added to prevent the oxidation of thioglycolic acid and red to purple coloration.Chelating agents are always added to cream-like cosmetics to stabilize the emulsion, and the excess chelating agent As a result, even calcium and magnesium in the hair are lost.
As a result, the hair damage described above occurs. And the reason that a decrease in calcium and magnesium, especially a decrease in calcium, causes hair damage is that they exist as salt bridges and coordination complexes with the keratin proteins and pigment side chains of the fiber structure, and due to the structure of the hair. This is thought to be because it plays an important role. As a result of various studies based on such findings, the present inventors have found that when calcium or calcium and magnesium are used in coexistence with keratin derivatives, hair damage is more severe than when they are used separately. The inventors have discovered that it is possible to prevent hair loss and to restore damaged hair, and have completed the present invention. The keratin derivatives used in the present invention are obtained by hydrolyzing keratin, oxidizing keratin, converting it into an alkali salt if necessary, or reducing keratin and then chemically modifying its mercapto group to obtain a derivative. If so, it can be produced by any of the methods of converting it into an alkali salt. Examples of keratin raw materials include animal hair, hair, feathers, nails, horns, hooves, scales, etc.
Particularly preferred are wool, hair, and feathers. These keratins can be subjected to oxidation or reduction reactions as they are, but if necessary, they may be cut or crushed into appropriate sizes, or pretreated such as washing and degreasing. Decomposition of keratin is carried out by one of the following methods. (1) Hydrolysis reaction Hydrolysis with acid Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrobromic acid, and organic acids such as acetic acid and formic acid. Alternatively, a mixture of hydrochloric acid, acetic acid, etc. may be used. These are generally used at a concentration of 5 to 85% (by weight, hereinafter the same), but it is desirable that the hydrolysis reaction always be at a pH of 4 or less. The reaction temperature is preferably 40 to 100°C, but can be raised to 160°C under pressure. The reaction time is preferably 2 to 24 hours. The reactant can be neutralized with an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, or ammonia and used as is, but the reactant or neutralized product can be used by gel filtration, ion exchange resin, ultrafiltration, dialysis, or electrodialysis. It can also be used after being purified by methods such as. The products obtained by such acid hydrolysis produce better results than those obtained by alkaline hydrolysis because they do not cause any changes other than hydrolysis to the polypeptide chains of keratin. Hydrolysis with alkali As the alkali, inorganic alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, and lithium carbonate are used. These are generally 1
A concentration of ~20% is appropriate. If more alkali is used than necessary, the hue of the hydrolyzate solution will become brown to black, which is not preferable. Reaction at room temperature to 100℃
It is preferable to carry out the reaction at a temperature of 30 minutes to 24 hours, and care must be taken not to raise the temperature too much or make the reaction time longer than necessary. Hydrolysis with an alkali has the advantage that the keratin hydrolyzate is eluted as the reaction progresses, making the progress of the reaction visible. The reaction may be terminated when the reaction mixture becomes a homogeneous solution. After the reaction, it is preferable to neutralize with the above-mentioned acid or purify by gel filtration, ion exchange resin, ultrafiltration, dialysis, electrodialysis, etc. Hydrolysis using enzymes As the enzyme, acidic proteolytic enzymes such as pepsin, protase A, and protase B, and neutral proteolytic enzymes such as papain, bromelain, thermolysin, trypsin, pronase, and chymotrypsin are used. Fungi-produced neutral proteolytic enzymes such as subtilin and Staphylococcus protease can also be used. The pH during hydrolysis is preferably adjusted to a range of PH 1 to 4 in the case of an acidic proteolytic enzyme such as pepsin, and to a range of PH 4 to 10 in the case of a neutral enzyme such as papain. Generally, it is convenient to appropriately adjust the pH using a buffer such as an acetic acid/sodium acetate buffer or a phosphate buffer, or by adding an acid, an alkali, or the like. The reaction temperature is preferably 30 to 45°C, and the reaction time is generally 3 to 24 hours. In the hydrolysis reaction using enzymes, the amount of enzyme used,
The molecular weight of the hydrolyzate is greatly influenced by the reaction temperature and reaction time. Therefore, in order to obtain a keratin hydrolyzate with the desired molecular weight, the molecular weight distribution of the obtained hydrolyzate was investigated using the gel filtration method under various conditions such as the amount of enzyme used, reaction temperature, and reaction time. It is necessary to determine the optimal conditions for Enzyme-based hydrolysates have a narrower molecular weight distribution and produce less free amino acids than acid- or alkali-based hydrolysates, so they are very suitable for use in cosmetic formulations. The average molecular weight of the hydrolyzate obtained by these hydrolysis reactions is preferably 200 or more and 5000 or less. The adsorption ability of decomposed keratin products to hair is determined by its molecular weight, with molecular weights ranging from 300 to 600.
This is because those with a molecular weight of 5,000 or more are the easiest to adsorb, are easily soluble in water, and are easy to handle, while those with a molecular weight of more than 5,000 have little adsorption to hair and are difficult to handle. Further, it is preferable that the disulfide bonds in the keratin derivative remain as much as possible, and for this purpose, it is necessary to use highly pure keratin and to perform the hydrolysis reaction under mild conditions. (2) Oxidation reaction Keratin oxidation is carried out by various conventionally known keratin oxidation methods. The oxidizing agent is preferably an organic or inorganic oxidizing agent that acts on disulfide bonds (SS bonds) in the keratin structure, such as organic peracids, inorganic peroxoacids or salts thereof, halogens, hydrogen peroxide, etc. Examples include peroxides, oxygen acids, or salts thereof, and organic peracids such as peracetic acid, performic acid, and perbenzoic acid are particularly preferred. Note that peracetic acid and performic acid are prepared by adding hydrogen peroxide to acetic acid and formic acid in the reaction system. The oxidation reaction is carried out in a liquid medium using an oxidizing agent in an excess amount relative to the disulfide bonds in the keratin, usually at least two equivalents, preferably from 4 to 10 times the equivalent per disulfide bond. Although the reaction can be carried out under either acidic or alkaline conditions, it is preferably carried out under acidic, particularly weakly acidic conditions. Conditions such as reaction temperature and pressure vary depending on the oxidizing agent used, the type of keratin, etc., and are not particularly limited. Room temperature is generally sufficient, but heating can be used if necessary. Also, normal pressure is sufficient, but the reaction may be carried out under reduced pressure or increased pressure. The reaction mixture after oxidation is preferably purified by ultrafiltration, dialysis, gel filtration, ion exchange resin, or the like. By the above operation, the disulfide bonds of keratin are cleaved to generate sulfonic acid (-SO ₃ H). (3) Reduction reaction and chemical modification reaction The reducing agent used to reduce keratin is one that cleaves the disulfide bond in the structure to give a mercapto group (-SH); Organic or inorganic reducing agents of the nucleophilically acting type are preferred. Specifically, organic reducing agents such as mercaptoethanol, thioglycolic acid, benzyl mercaptan, 1,4-dithiothreitol, and tributylphosphine, sulfides such as sodium bisulfite and sodium hydrosulfide, and sodium borohydride, etc. Examples include inorganic reducing agents such as metal hydrides. The amount of reducing agent used is generally 2 to 10 times equivalent to the disulfide bonds in keratin.
The pH of the reaction system is preferably in the range of 7 to 12, particularly 9 to 11; anything outside this range is not preferred because hydrolysis occurs simultaneously. Room temperature is sufficient for the reaction temperature, but the reaction time can also be shortened by heating. The reaction time usually requires 2 to 3 hours or more.
It is also necessary that the mercapto groups produced by this reduction are not substantially oxidized, and for this reason it is preferable to carry out the operation in an inert gas atmosphere to give preferable results. The reductive decomposition product of keratin thus obtained is made into a derivative by chemically modifying its mercapto group. Examples of derivatives of the mercapto group include the following. −SCH ₂ COOH, −SCH ₂ CH ₂ COOH,

【formula】

【formula】

[Formula] −SO ₃ H, −SSO ₃ H, − SCH ₂ CH ₂ SO ₃ H,

【formula】

[Formula] − SCH ₂ CH ₂ SO ₂ CH ₂ COOH,

[Formula] In this, −SCH ₂ COOH,

【formula】

[Formula] etc. are particularly preferred. The chemical modification of the mercapto group is carried out based on conventionally known methods. The typical methods are as follows. Method using nucleophilic substitution reaction of SH group (In the formula, K is a keratin compound residue.) Compounds reacted by this method include, in addition to the above-mentioned compounds, halogen compounds such as iodoacetic acid, bromoacetic acid, and chloroacetic acid. Method using nucleophilic addition reaction to carbon-carbon double bond of SH group (In the formula, at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group having a carboxyl group or a sulfonic acid group therein, and the remainder represents an alkyl group or a hydrogen atom. K is as defined above. ) Compounds reacted by this method include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylcarboxymethylsulfone, vinylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methyl Examples include propanesulfonic acid. Method using substitution reaction between SH group and sulfite compound K-SH+NaHSO ₃ →K-S-SO ₃ H K-SH+Na ₂ SO ₃ →K-S-SO ₃ H (In the formula, K is the same as above. ) Method of oxidizing SH group to sulfonic acid group K-SH→K-SO ₃ H oxidation (In the formula, K is the same as above.) Examples of the oxidizing agent used in this reaction include halogen, permanganic acid, etc. Examples include salts, hydrogen peroxide, peracetic acid, and performic acid. The alkali salts of keratin oxidative decomposition products and keratin reduced derivatives include inorganic alkali metal salts such as sodium and potassium, ammonium salts, ethanolamine, diethanolamine,
Triethanolamine, 2-amino-2-methylpropanol, aminomethylcaptopropanediol, triisopropanolamine, glycine,
Examples include salts with organic bases such as histidine and arginine. Although these may be prepared in a separate system, it is also possible to mix an oxidative decomposition product of keratin or a reduced derivative of keratin with an alkaline substance to form a salt in the hair protection agent. Examples of the alkaline substances in this case include sodium hydroxide, potassium hydroxide, aqueous ammonia, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, aminomethylmercaptopropanediol, triisopropanolamine, glycine, Examples include arginine and histidine, and these are preferably added in an amount of 0.1 to 8 equivalents to the carboxyl group and sulfonic acid group in the oxidized keratin decomposition product or the reduced keratin derivative. Further, a part or a necessary amount of calcium and magnesium hydroxides may be used. In the hair protection agent of the present invention, the concentration of the keratin derivative is 1 to 30%, particularly 2 to 30% in the total composition.
is preferred. This is because if the concentration of the keratin derivative becomes higher than that, a flattening phenomenon will occur in the hair. The concentration of calcium ions in hair has a very strong ability to adsorb calcium ions, and adsorption can be seen from around 10 ppm, but the amount of calcium ions originally contained in hair varies greatly from person to person, and when used In order to prevent the influence of chelating agents added to various cosmetics, it is preferable to set the content to 50 to 10,000 ppm, taking into consideration usage conditions. When adding magnesium ions, the reason is the same as for calcium ions above (however, magnesium in hair is less than calcium).
It is preferable to set it to 5000 ppm. The form of calcium and magnesium added is
It is preferable that the salt be formed with the keratin derivative and dissolved in the hair protectant.For this purpose, calcium hydroxide or magnesium hydroxide may be added as part of the alkali used to neutralize the keratin derivative. Furthermore, calcium salts and magnesium salts that are soluble in water may be added. Such water-soluble calcium salts and magnesium salts include, for example, inorganic calcium salts such as calcium chloride, calcium nitrate, calcium carbonate, calcium bromide, calcium acetate, calcium lactate, calcium citrate, calcium malate,
Examples include organic calcium salts such as calcium tartrate, inorganic magnesium salts such as basic magnesium carbonate, potassium magnesium carbonate, potassium magnesium bicarbonate, and magnesium bromide, and organic magnesium salts such as magnesium acetate, magnesium citrate, and magnesium lactate. The hair protection agent of the present invention is prepared by blending a keratin derivative and calcium ions, or a keratin derivative, calcium ions, and magnesium ions in water or a base mainly composed of water.
A base whose main component is water is one in which alcohols or polyhydric alcohols such as ethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, and glycerin polyol are added to water to the extent that it does not inhibit the dissolution of the keratin derivative. say. Usually the amount of alcohol is 50% of the total composition
It is as follows. In addition to the above-mentioned components, the hair protectant of the present invention may appropriately contain emulsifiers, wetting agents, various anionic, cationic, and nonionic surfactants, preservatives, fragrances, colorants, chelating agents, and the like. Note that a chelating agent may be necessary to sequester heavy metals other than calcium ions and magnesium ions such as iron, and in that case, calcium and magnesium may be blended in an amount greater than the sequestering ability of the chelating agent. The hair protection agent of the present invention may be used alone, or may be used as a permanent waving agent (one containing thioglycolic acid as the main ingredient or one containing cysteine as the main ingredient), hair dye, bleaching agent, shampoo, etc.
It may be added to various hair cosmetics such as hair treatments, hair conditioners, and hair packs. When using a hair protectant alone, it may be used independently of the use of hair cosmetics, or it may be used before, during, or after the use of hair cosmetics. good. Next, the present invention will be explained with reference to reference examples and examples. Reference example 1 Production of keratin hydrolyzate (1) Acid hydrolysis Add 100 g of 35% hydrochloric acid to 100 g of wool in a three-necked flask.
was added and hydrolysis was carried out under stirring at 70°C for 15 hours. After hydrolysis, filter the reaction mixture and drain the liquid.
After neutralization with 2N sodium hydroxide, desalting was performed by gel filtration (using Sephadex G-102e manufactured by Pharmacia), and then concentrated to obtain a 30% aqueous solution of keratin hydrolyzate. The molecular weight of the keratin hydrolyzate thus obtained was measured by a gel filtration method and found to be an average molecular weight of 1000. (2) Alkaline hydrolysis 18 g of sodium hydroxide and 600 g of water were added to 100 g of wool, and the mixture was left at 40°C for 20 hours to perform hydrolysis. After hydrolysis, the reaction mixture was filtered and the liquid was treated with a weakly acidic cation exchange resin (Amberlite IRC-
50, trade name, Organo Co., Ltd.)) to neutralize it, and then concentrate it to obtain 30% of the keratin hydrolyzate.
% aqueous solution was obtained. The molecular weight of the keratin hydrolyzate thus obtained was measured by a gel filtration method and found to be an average molecular weight of 2,200. (3) Enzymatic hydrolysis 100 g of feathers was treated with superheated steam at 200° C. at 10 kg/cm ² in a high-pressure container for 30 minutes, and then released into the atmosphere to obtain a porous puffed feather product. To this was added 500 ml of 0.5N acetic acid-sodium acetate buffer (PH5.5), then 5 g of papain was added, and hydrolysis was carried out at 40°C for 24 hours. After hydrolysis, the reaction mixture is filtered,
After concentrating the liquid under reduced pressure to 300ml, a gel solution (using Pharmacia's Sephadex G-10) was obtained.
Desalting was carried out by , followed by concentration to obtain a 30% aqueous solution of keratin hydrolyzate. The molecular weight of the obtained keratin hydrolyzate was measured by a gel filtration method and found to be an average molecular weight of 1200. Reference Example 2 Production of keratin oxide (1) 100 g of wool was treated with superheated steam at 8 kg/cm ² and 220°C for 15 minutes in a high-pressure container, and then released into the atmosphere to obtain a porous expanded wool product. was dried and then ground. Separately, add 40ml of 35% hydrogen peroxide to 88%
After adding to 450ml of formic acid and stirring at room temperature for 1 hour,
The above-mentioned pulverized porous puffed wool product was added to this mixed solution. The mixture was stirred at room temperature for 20 hours to oxidize, and then filtered. The solution was purified by dialysis, neutralized with 2N sodium hydroxide, and then concentrated under reduced pressure to obtain a 30% aqueous solution of keratin oxide sodium salt. (2) The feathers were treated with superheated steam at 10 kg/cm ² and 200°C for 30 minutes in a high-pressure container, and then released into the atmosphere to obtain porous puffed feathers, which were dried and crushed. Separately, 50 ml of 35% hydrogen peroxide solution was added to 600 ml of glacial acetic acid, and after stirring at room temperature for 1 hour,
The porous puffed product of ground feathers was added to this mixed solution. The mixture was stirred at 40°C for 24 hours to oxidize, and then filtered. The solution was purified by dialysis, concentrated under reduced pressure, and then neutralized with triethanolamine.
30% of keratin oxide triethanolamine salt
An aqueous solution was obtained. Reference Example 3 Reduction of keratin (1) 100 g of wool was immersed in 8M urea solution 3 containing 80 g of thioglycolic acid and adjusted to pH 10 with sodium hydroxide, and reduction was carried out for 24 hours in a nitrogen stream.
When the reaction mixture was filtered to remove unreacted wool, it was found that 80% of the wool had been solubilized in the solution. Add 30 g of iodoacetic acid to the above solution at room temperature while stirring, add 20% aqueous sodium hydroxide solution as appropriate, and adjust the pH.
The reaction was carried out for 3 hours while maintaining the temperature at 8. The reaction solution was dialyzed, concentrated under reduced pressure, and then neutralized with monoethanolamine to obtain a 30% aqueous solution of S-carboxymethylkeratin monoethanolamine salt. The yield was 290g. (2) Reference example 3-100 feathers instead of wool in (1)
g and 30 g of maleic acid instead of iodoacetic acid.
and using triethanolamine instead of monoethanolamine, otherwise refer to Reference Example 3-
30% of S-(1,2-dicarboxyethyl)-keratin triethanolamine salt was prepared in the same manner as in (1).
% aqueous solution was obtained. The yield was 340g. (3) In Reference Example 3-(1), 60 g of mercaptoethanol was used instead of thioglycolic acid, 40 g of 1-chloro-2-hydroxypropane trimethylammonium chloride was used instead of iodoacetic acid, and neutralization with alkali was not performed. A 30% aqueous solution of S-(2-hydroxypropanetrimethylammonium chloride)keratin was obtained in the same manner as in Reference Example 3-(1) except for the above. The yield is
It was 340g. (4) S-(2-hydroxypropanetrimethylammonium chloride)keratin was prepared in the same manner as in Reference Example 3-(3) except that 120 g of crushed horse hoof was used instead of wool in Reference Example 3-(3). of 30
% aqueous solution was obtained. The yield was 370g. Example 1 Using the keratin derivative obtained in Reference Example 1-(1), a hair protectant having the composition shown in Table 1 was prepared. The blending amount is shown in parts by weight. The same applies hereafter. Note that 1-A, 1-B, 1-C, and 1-D are control products.

[Table] Mix 30g of the hair protection agent of each composition above and 70g of the first agent for permanent waves prepared separately,
After soaking a hair bundle weighing 1 g in the solution for 30 minutes and rinsing it, apply the second agent for permanent waves.
It was immersed in 100g of water for 15 minutes for neutralization. Sensory evaluations were made of the strength, suppleness, and combability of the hair after treatment. The results and the results of measuring the amount of calcium in the hair are shown in Table 2. Table 3 shows the composition of the permanent wave agent used. The evaluation criteria are as follows. ◎: Particularly good ○: Good △: Fair ×: Poor Calcium content was measured by atomic absorption spectrometry.

【table】

[Table] Example 2 A hair protectant having the composition shown in Table 4 was prepared,
The effect was confirmed as shown below. First, the hair of a panel of 10 women was washed with shampoo. After washing, 50g of a hair protectant with the above composition was sprinkled on the hair, and it was soaked into the hair well. After 5 minutes, it was washed with water to improve the curls, suppleness, and combing of the hair. A sensory evaluation of the ease of passage was performed. The results and the results of examining the average increase rates of calcium ions and magnesium ions are shown in Table 5. Note that calcium ions were measured in the same manner as described above, and magnesium ions were measured by atomic absorption spectrometry. The composition of the shampoo used is as shown below. Shampoo composition Sodium lauryl sulfate (35%) 25.0 Coconut fatty acid diethanolamide 5.0 EDTA 0.1 Purified water 69.9 In Table 4, the types of keratin derivatives are indicated by reference example numbers.

【table】

【table】

[Table] Example 3 A hair bundle weighing 1 g was mixed with 70 g of bleaching liquid and 2-2 of Example 2.
It was immersed for 1 hour at 25°C in a mixed solution with 30 g of the hair protectant of A to 2-I. For comparison, add 70g of decolorizer and water.
The hair bundle was immersed in a solution containing 30 g under the same conditions as above. After soaking, the hair's strands, suppleness, and combability were sensory evaluated. The results are shown in Table 6.
In addition, the calcium ion concentration and magnesium ion concentration in the hair were measured to determine the cysteic acid production rate in the hair. The results are shown in Table 6. Cysteinic acid production rate is determined by analyzing hair (amic acid analysis)
The amounts of cystine and cysteic acid were calculated using the following formula. Cysteic acid / Cystine + Cysteic acid x 100 The significance of determining the cysteic acid production rate is that cystine in hair changes to cysteic acid when it undergoes oxidation, so by determining the cysteic acid production rate, you can know the degree of hair damage. It is from. The composition of the decolorizing agent used is as follows. Decoloring agent composition 35% hydrogen peroxide 20.0 25% ammonia water 5.0 Polyoxyethylene cetyl ether 1.0 EDTA 0.1 Purified water 73.9

【table】

[Table] Example 4 Using the keratin derivative obtained in Reference Example 1-(2),
A hair protectant having the composition shown in Table 7 was prepared,
Thereafter, a permanent wave test was conducted on the hair bundle in the same manner as in Example 1. The result is the 8th
As shown in the table.

【table】

【table】

Claims (1)

[Scope of Claims] 1. At least one selected from keratin hydrolyzates, keratin oxides or alkali salts thereof, and mercapto group derivatives of reduced keratin or alkali salts thereof, in water or a base mainly composed of water. A hair protection agent other than a hair rinse, characterized in that it contains a keratin derivative and calcium ions or calcium ions and magnesium ions. 2 Average molecular weight of keratin hydrolyzate obtained by hydrolyzing keratin with acid, alkali or enzyme
200 to 5,000. The hair protectant according to claim 1. 3 The derivative at the mercapto group is -
SCH ₂ COOH, −SCH ₂ CH ₂ COOH,
[Formula] [Formula] [Formula] −SO ₃ H, −SSO ₃ H, − SCH ₂ CH ₂ SO ₃ H,
[Formula] [Formula] - SCH ₂ CH ₂ SO ₂ CH ₂ COOH The hair protection agent according to claim 1, which is at least one member selected from the group consisting of [Formula] - SCH 2 CH 2 SO 2 CH 2 COOH and [Formula]. 4 The amount of keratin derivative added is 1 to 1 for the entire composition.
30% by weight of the hair protectant according to claim 1, 2 or 3. 5 Calcium ion content is 50% of the total composition
~10000ppm Claims 1 and 2
The hair protectant according to item 3, item 3 or item 4. 6. The amount of magnesium ion added to the total composition
Claims 1 and 2 are 50 to 5000 ppm.
The hair protectant according to item 3, item 3 or item 4. 7 Claims 1, 2, 3, 4, 5, or The hair protectant according to item 6.