JPH0160005B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hair cosmetic composition containing a cationized keratin derivative, and more specifically to a hair cosmetic composition other than pre-shape treatment.
Reductive decomposition products of keratin substances or reductive decomposition products of keratin hydrolysates (hereinafter referred to as "keratein")
Some or all of the sulfhydryl groups of the following formula,

【formula】

A cationized keratin derivative obtained by reacting a group represented by [Formula] or CH ₂ =CH- (in the formula, X represents a halogen atom) with a cationizing agent having a quaternary nitrogen in one molecule. It relates to a hair cosmetic composition characterized by containing the following. Hair is the most important cosmetically important part, and various cosmetic treatments are performed on it, and various hair cosmetics are used. In this specification, hair cosmetics is a general term for cosmetics applied to hair excluding pre-shampoo treatments, such as shampoos, hair rinses, after-shampoos, conditioners, hair conditioners, Hair styling agents such as setting lotion, blow styling lotion, hair spray, hair dye, bleach, permanent wave first agent, permanent wave second agent, hair dye; hair liquid, hair tonic, etc. are included. All of the hair cosmetics that have been provided hitherto have some drawbacks and are not satisfactory. For example, shampoo is a decomposition product of dirt from the outside world that adheres to hair and sebum secreted from the scalp.
It is used to remove dirt such as oxides, and its base material is anionic surfactant, nonionic surfactant, amphoteric surfactant, etc. When hair is washed with shampoos containing these bases, sebum and other oils present on the surface of the hair are washed away excessively, making the hair feel very bad after washing.
Combs and brushes become difficult to pass through. In addition, when the hair is completely dry, it is difficult to manage, and especially in the winter when the humidity is low, static electricity is easily generated when brushing, causing phenomena such as hair flies. It has the disadvantage of making it difficult to pass through, and is also a cause of split ends and hair breakage. In order to solve this problem, there is a method of adding oil to the general shampoo base and supplementing the oil when washing the hair.
Various oil agents are conventionally known and are added to ordinary shampoos. However, in the shampoo formulation system, the entire system is emulsified or solubilized by surfactants, and a sufficient amount of oil is added to the scalp and hair without impairing the stability of the system. It was difficult to do so. Furthermore, when a large amount of oil is added, the amount of oil adsorbed to the hair increases, but the shampoo's original functions of lathering and detergency become extremely poor, resulting in a significant loss of commercial value. On the other hand, in recent years, many shampoo compositions containing cationic polymers and the like have been proposed for the purpose of imparting a rinsing effect to hair after washing. However, although these have a conditioning effect, they have poor foaming properties and cleaning power, become colored or discolored over time, have excellent foam properties but have poor conditioning effects, and are expensive. There were drawbacks such as high price. Hair rinse is a shampoo whose main base is anionic surfactant, which prevents the harmful effects that occur when washing hair.
For example, it prevents hair from losing its flexibility, becoming dull or difficult to comb, hair damage, split ends, hair breakage, etc., and has a hair conditioning effect. In other words, it is used for the purpose of imparting softness, suppleness, and a moist feel to the hair, and improving combability, etc., and contains quaternary ammonium salts, which are cationic surfactants, and liquid paraffin. It is composed of oil components such as , higher alcohol, etc. However, quaternary ammonium salts are unstable because they do not have the ability to stably emulsify and disperse a sufficient amount of oil components to be effective.
When a nonionic surfactant is added to improve this problem, the original rinsing effect is reduced. Therefore, it has been proposed to obtain a stable hair rinse agent by adding other compounds, such as an anionic active agent, an anionic polymer compound, a cationic polymer compound, and collagen hydrolyzate, in place of the above-mentioned oil component. ing. However, these methods are still unsatisfactory. Hair setting agents such as setting lotions and hair sprays are used for the purpose of preventing hair sets from collapsing due to high humidity, wind, etc. Conventional hair setting agents contain acrylic acid as a fixing agent that exhibits set retention power. Resin-like components such as ester-methacrylic acid ester copolymer and polyvinylpyrrolidone-vinyl acetate copolymer are used. However, since the resinous component has poor cleaning properties,
Even if you wash your hair with shampoo, it cannot be completely removed from the hair, and the components remaining on the hair surface may increase the friction coefficient of the hair, cause split ends and hair breakage due to brushing, and reduce the texture of the hair. It is known that undesirable phenomena such as As a method to overcome these drawbacks, attempts have been made to add nonionic surfactants, wetting agents, etc. to resinous components to increase their water solubility. However, although this method improves the cleansing properties, it has the disadvantage that the hair setting agent's ability to hold hair under high humidity is significantly reduced, impairing the original performance of the hair setting agent. Permanent wave agent 1 and agent 2 are used in the so-called permanent wave method, which reduces and oxidizes hair to shape the hair.
Permanent Wave 2nd agent, which is mainly composed of a reducing agent such as thioglycolic acid and cysteine and an alkaline substance, is used to open disulfide (-S-S-) bonds in hair, and is used to close the above-mentioned bonds. The main component is an oxidizing agent such as bromate, perborate, or hydrogen peroxide. However, permanent wave first agent and second agent
According to the permanent wave method that uses agents, the hair is exposed to adverse conditions of oxidation and reduction.
Phenomena such as a decrease in the strength and deterioration of the texture occur, and such hair is difficult to brush or comb when grooming the hair to style it.
Difficulty occurs, resulting in peeling of the hair epidermis, split ends, and cut hair, resulting in damage. Hair deterioration caused by the permanent wave first agent is caused by the keratin that makes up the hair being cut by the permanent wave first agent and eluted as proteins and amino acids.To improve this deterioration, It is necessary to supplement the protein components thus lost. Therefore, attempts have been made to incorporate collagen hydrolyzate into the first agent, but this is easily removed by rinsing or washing the hair after cold wave treatment, resulting in insufficient effects. I couldn't get it. In addition, the deterioration caused by the second permanent wave agent is caused when the hair swollen by the first permanent wave agent is damaged by the action of the oxidizing agent, and methods for preventing this damage include adding an oil agent to the composition, A method of adding a wetting agent or the like has been used, but this method has also been unsatisfactory. Hair dyes, bleaches, and hair dyes are used for the purpose of dyeing gray hair black to maintain youthfulness, or to create a make-up or to harmonize clothing and hair, and generally use oxidative dyes. It can be roughly divided into those that use bleaching agents, those that use acid dyes and dye with solvents and auxiliary agents, those that use hair coloring agents, and those that use iron-pyrogallol. Among these, oxidative hair dye dyes hair by penetrating a low-molecular-weight oxidative dye intermediate into the hair and oxidatively polymerizing it within the hair to produce a pigment, while bleach dyes melamine with alkaline hydrogen peroxide. It decomposes oxidatively to bleach and dye hair. but,
These dyes involve chemical changes and cause significant damage to the hair. Additionally, hair dyes that use coloring agents such as acid dyes and pigments (called temporary hair dyes) simply have the coloring agents attached to the hair, so they will come off when you wash your hair, etc. . Therefore, dyeing must be repeated at regular intervals, but in this case the dye accumulates and damages the hair surface. Furthermore, hair dyes contain a polymer resin as a binder, but if this adheres to the hair surface, it will be difficult to comb or brush through the hair, causing damage to the hair. In order to prevent such hair damage, oils, wetting agents, etc. have been added to hair dyes, but these effects are temporary and insufficient, and further improvements have been desired. On the other hand, keratin, a fibrous protein that is distributed in the epidermis of higher animals and has biological protective functions, contains 18 kinds of amino acids (ararin, arginine, aspartic acid, cystine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, methionine, phenylalanine, proline, serine, threonine, tryptophan, tyrosine, valine)
It is composed of a large amount of cystine, with an average of 10~
One disulfide bond per 20 amino acid residues (-
It is characterized by the presence of S—S—) and a crosslinked structure. Keratin is distributed in hair, nails, wool, feathers, horns, etc., and since it is the main component of hair, nails, etc., it is thought to have a good affinity with hair, skin, etc., and is used in cosmetics, etc. It has been considered to do so.
However, keratin itself is insoluble in ordinary solvents, and the actual situation is that its range of use is extremely limited. In order to use keratin in cosmetics, etc., it is first necessary to dissolve it in some kind of solvent, such as water, and for this purpose, the crosslinked disulfide bonds must be cleaved. Methods of cleavage include reduction and oxidation, and upon reduction, the disulfide bond becomes a sulfhydryl group (-SH) and the product is called keratein. On the other hand, upon oxidation, the disulfide bond becomes a sulfonic acid group (-SO ₃ H, and the product is called a keratose. The linear protein obtained in this way should essentially be soluble in water. Due to hydrogen bonds, ionic bonds, hydrophobic bonds, etc. between proteins, they are poorly soluble in water and organic polar solvents, and even if they are dissolved, only an extremely dilute solution can be obtained. As a result of intensive research to solve the above drawbacks, we found that some or all of the sulfhydryl groups in keratein have the following formula:

【formula】

By reacting a group represented by [Formula] or CH ₂ = CH - (in the formula, X represents a halogen atom) with a cationizing agent having a quaternary nitrogen in one molecule, water and water become hydrophilic. cationic keratin derivatives that are readily soluble in mixed solvents with organic solvents (patent application
No. 55.98255 and No. 55-98256) and this cationized keratin derivative can be blended into a pre-suppressant composition to obtain an excellent pre-suppressant composition that solves the conventional drawbacks (Patent Application No. 1983-
No. 163784 and No. 55-162900) and filed a patent application. The present inventor further investigated the uses of cationized keratin derivatives and found that the conventional drawbacks could be overcome by incorporating the cationized keratin not only in pre-shampoo compositions but also in other hair cosmetics. The present invention was completed based on the discovery that the performance could be improved. The cationized keratin derivative of the present invention (hereinafter referred to as "cationized keratin") has keratein, which is a reduced decomposition product of a keratin substance or its hydrolyzate, in its molecule.

【formula】

It is produced by adding a cationizing agent having a group represented by the formula: or CH ₂ =CH- (where X is the same as above) and a quaternary nitrogen. The keratin material that is the starting material for obtaining keratein includes animal hair, hair, feathers, nails, horns, hooves, scales, etc. Among them, wool, feathers, and hair are preferred. These keratin substances can be subjected to the reduction treatment as they are, but it is also possible to use a keratin substance that has been subjected to a hydrolysis treatment prior to the treatment. The keratin material may be crushed or cut to an appropriate size as necessary.
Pretreatment such as washing, degreasing, heating at high temperature and then rapidly releasing it into the atmosphere to cause swelling may be performed. Hydrolysis treatment can be performed using any of acids, alkalis, and enzymes. The conditions for hydrolysis treatment are not particularly limited, but if the molecular weight of the hydrolyzate is 500~
10,000, particularly preferably 1,000 to 5,000. Even if the molecular weight is less than 500, the effect is only inferior, and although it is sufficient to use a large amount, there is a drawback that it is difficult to use.
Among the above hydrolysis methods, the method using enzymes is particularly preferred because the molecular weight distribution of the decomposed product is narrow and uniform, and free amino acids are less produced. Reduction treatment of keratin materials (including their hydrolysates) is carried out, for example, by treatment with a reducing agent in water or a mixed solvent of water and a hydrophilic organic solvent, and the disulfide bonds ( ―
S—S—) is cleaved into a sulfhydryl group (—SH) to obtain keratein. Reducing agents include any reducing agent capable of cleaving disulfide bonds in keratin materials to sulfhydryl groups. Such reducing agents include thiol derivatives of alcohols or carboxylic acids such as 2-mercaptoethanol and thioglycolic acid, phosphorus compounds such as tri-n-butylphosphine and triphenylphosphine, and organic reducing agents such as ascorbic acid. and inorganic reducing agents such as sodium bisulfite and sodium sulfite. Examples of hydrophilic organic solvents include methanol,
Examples include ethanol, n-propanol, isopropanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, dimethyl formamide, dimethyl sulfoxide, hexamethyl phosphoric triamide and the like. There is no strict limit to the amount of the reaction solvent, as long as it is sufficient to uniformly carry out the reduction reaction, and the amount used is usually 10 to 100 times the weight of the keratin material. The amount of reducing agent used is generally 2 to 10 equivalents to the disulfide bonds in the keratin material that is the raw material. In addition, the pH of the reaction system is usually 2~
12, particularly preferably in the range of 6 to 11. Furthermore, regarding the reaction temperature, room temperature is usually sufficient, but if necessary, heating can be applied to shorten the reduction time. As for the reaction time, it is necessary to sufficiently complete the reduction reaction, and it usually takes 2 to 3 hours or more, depending on the reaction temperature. Note that the reduction reaction is preferably carried out in an inert gas atmosphere such as nitrogen.
This is because the sulfhydryl group produced by the reduction reaction is extremely easily oxidized and is also unstable to oxygen in the air. The thus obtained keratein is treated with a quaternary ammonium salt type cationizing agent as described above to remove the sulfhydryl group or the sulfhydryl group and other functional groups present in the molecule, such as hydroxyl group, amino group, A cationizing agent is added to carboxyl groups, etc. Examples of the quaternary ammonium salt type cationizing agent used in the method of the present invention include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium chloride,
Examples include allyltrimethylammonium chloride and the corresponding bromides and iodides, with glycidyltrimethylammonium chloride being the most common. The addition reaction between the reductively decomposed product of the keratin material and the cationizing agent is carried out by adding the cationizing agent to the reaction mixture that has been subjected to the reduction treatment as described above. The cationizing agent first causes an addition reaction to the sulfhydryl group among the functional groups of the reductive decomposition product, but when the cationizing agent is added in an amount equivalent to or more than the sulfhydryl group, other functional groups other than the sulfhydryl group are added. For example, hydroxyl groups, amino groups, carboxyl groups, etc. also cause addition reactions. The amount of the cationizing agent to be added is suitably 0.1 to 6 times equivalent, more preferably 0.5 to 2 times equivalent, relative to the sulfhydryl groups present in the reductively decomposed product of the keratin material. If it is less than 0.1 times equivalent, it may not be possible to obtain a material with sufficient solubility in water or a mixed solvent of water and a hydrophilic organic solvent, and if it is more than 6 times equivalent, the original properties of the keratin material may be impaired. I don't like it. The reaction temperature is selected to be any temperature from room temperature to 90°C, or the higher the temperature, the more the addition reaction of the cationizing agent is accelerated. In addition, the system during addition reaction
Regarding pH, there is no need to particularly adjust the pH after the reduction reaction is completed. i.e. PH2-12 range, usually PH
It is done in the range of 6 to 11. As the addition reaction of the quaternary ammonium salt type cationizing agent to the reductive decomposition product of keratin progresses, the reductive decomposition product dissolves in the reaction medium, and ultimately the insoluble matter is less than 30% of the reductive decomposition product of keratin. becomes. Therefore, by removing this insoluble matter by filtration, centrifugation, etc., and distilling off the solvent, a solution of cationized keratin can be obtained. The cationized keratin solution obtained in this way can be used as a solution after removing low-molecular impurities such as reducing agents by ultrafiltration or dialysis, but it can also be cationized by freeze-drying or other methods. Recovering keratin as a solid is more convenient in terms of utilization, storage, and transportation. Typical examples of the cationized keratin of the present invention include the following groups in which some or all of the sulfhydryl groups of keratein are: [In the formula, the three R's are the same or different and represent a lower alkyl group or an aryl group, X represents a halogen atom, and represents a hydrogen atom or a hydroxyl group.]
Specific examples include cationized keratin modified with a cationized group represented by S-(β-hydroxy-γ-trimethylammoniopropyl)keratein and S-(γ-trimethylammoniopropyl).
-trimethylammoniopropyl)keratein. The hair cosmetic of the present invention is produced as follows. (1) Shampoo: Except for blending one or more anionic surfactants and cationized keratin as essential ingredients in the composition, other known shampoo composition constituents may be appropriately blended according to conventional methods. Manufactured by. Among the anionic surfactants that are the base of the shampoo, the following are preferred. Straight chain or branched chain alkylbenzene sulfonate having an alkyl group with an average carbon number of 10 to 16.Has a straight chain or branched chain alkyl group having an average carbon number of 8 to 20, and an average of 0.5 to 8 moles in one molecule. Polyoxyalkylene alkyl sulfate salt with ethylene oxide and/or propylene oxide added to it; Alkyl sulfate salt having an alkyl group with an average of 10 to 20 carbon atoms; Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule Alkanesulfonate having an average of 10 to 20 carbon atoms per molecule; Alkyl ethoxycarboxylate having an average of 10 to 20 carbon atoms and an average of 0.5 to 8 moles of ethylene oxide added to each molecule. (In the formula, R represents an alkyl group or alkenyl group having 6 to 20 carbon atoms, and X ₁ and Y ₁ each represent an ion.) The counter ion of these anionic surfactants is sodium. , alkali metal ions such as potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ions; alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms (e.g. monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). Among these exemplified anionic surfactants, particularly preferred are linear or branched alkyl sulfate salts having an average of 10 to 16 carbon atoms, or polyoxyethylene having an average of 8 to 20 carbon atoms in the alkyl group. Alkyl sulfate salt (average number of moles added)
0.5 to 8), or olefin sulfonate having an average carbon number of 10 to 16. In the shampoo of the present invention, the blending amount of the anionic surfactant is preferably 5 to 30% by weight (hereinafter simply expressed as %), particularly preferably 10 to 25%, and the amount of cationized keratin is 0.01 to 10%, particularly 0.5 to 25%. It is preferably 3%. Contains 0.01% cationized keratin
If it is less than
If it exceeds 10%, the hair becomes sticky under high humidity conditions, which is undesirable. Other components that may be incorporated into the shampoo of the present invention include amphoteric surfactants, nonionic surfactants, cationic surfactants, propylene glycol, glycerin, etc. in amounts that do not impair the effects of the present invention. Dissolving agent such as urea: ethyl alcohol,
Viscosity modifiers such as isopropyl alcohol, hydroxyethyl cellulose, methyl cellulose, and higher alcohols: Includes fragrances, pigments, ultraviolet absorbers, antioxidants, preservatives, pearlizing agents, lotioning agents, etc., and these are added as necessary. be able to. The thus-obtained shampoo of the present invention not only has excellent hair conditioning and hair washing effects, but is also more effective than conventional shampoos when accidentally getting into the eyes during hair washing or rinsing. The pain is mild and the effect on the conjunctiva and iris is mild. (2) Hair rinse: Prepared by dissolving or dispersing cationized keratin in a suitable solvent such as water, ethanol, glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, isopropanol, polyethylene glycol, or the like. The hair rinse of the present invention can obtain an excellent rinsing effect without using a conventionally used cationic surfactant, and furthermore, when used in combination with the cationic surfactant, it can be used in combination with a conventional hair rinse. It provides a superior hair rinse effect. In the hair rinse of the present invention, the amount of cationized keratin blended is preferably 0.01 to 10%, particularly 0.03 to 3%. Contains 0.01% cationized keratin
If it is less than 10%, the effect cannot be fully exhibited, and if it exceeds 10%, the hair becomes sticky under high humidity, which is undesirable. In addition to the cationized keratin and solvent described above, the hair rinse agent composition of the present invention can contain known ingredients used in general hair rinse agents, including anionic surfactants and nonionic surfactants. It is particularly preferable to incorporate a surfactant selected from surfactants and amphoteric surfactants as an auxiliary component. These surfactants include the following: (a) Anionic surfactant Straight-chain or branched alkylbenzene sulfonate having an alkyl group with an average carbon number of 10 to 16 Having a straight-chain or branched alkyl group or alkenyl group with an average carbon number of 8 to 20, average within one molecule
Alkyl or alkenyl ethoxy sulfate with 0.5 to 8 moles of ethylene oxide added Alkyl or alkenyl sulfate having an alkyl or alkenyl group having an average of 10 to 20 carbon atoms Olefin sulfone having an average of 10 to 20 carbon atoms per molecule Acid salt Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule Saturated or unsaturated fatty acid salt having an average of 10 to 20 carbon atoms in one molecule An average of 10 to 20 carbon atoms (particularly preferably 12 to 20 carbon atoms) 16)
an alkyl or alkenylethoxycarboxylic acid salt having an alkyl group or an alkenyl group and an average of 0.5 to 8 moles of ethylene oxide added to each molecule; an α-sulfo fatty acid salt or ester represented by the following formula; [In the formula, Y ₂ is an alkyl group having 1 to 3 carbon atoms or a counter ion, M ₁ is a counter ion, and R ₂ is an alkyl group having 1 to 3 carbon atoms.
20 (particularly preferably 12 to 16) alkyl or alkenyl groups. ] Counter ions for the anionic activator include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, and alkanolamines having 1 to 3 alkanol groups having 2 or 3 carbon atoms ( Examples include monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.). (b) Nonionic surfactant Polyoxyethylene alkyl or alkenyl ether having a primary or secondary alkyl group or alkenyl group with an average carbon number of 8 to 20 and added with 3 to 12 moles of ethylene oxide Average carbon number having 8 to 12 alkyl groups, and 3 to 12 alkyl groups;
Polyoxyethylene alkyl phenyl ether with 12 moles of ethylene oxide added Higher fatty acid alkanolamide or its alkylene oxide adduct represented by the formula below [In the formula, R ₃ represents H or CH ₃ , and R ₄ is an alkyl group or alkenyl group having 10 to 20 carbon atoms. n is an integer of 1 to 3, and m is an integer of 0 to 3. ) (c) Amphoteric surfactant Alkylamine oxide represented by the formula below (In the formula, R ₅ is an alkyl group or alkenyl group having 10 to 20 carbon atoms, and R ₆ and R ₇ are 1 to 20 carbon atoms.
3, and may be the same or different) Among these, those in which R ₅ has 12 to 16 carbon atoms and R ₆ and R ₇ are methyl groups are preferred. [In the formula, R ₉ represents an alkyl group or alkenyl group having 10 to 20 carbon atoms, R ₁₀ and R ₁₁ represent an alkyl group having 1 to 4 carbon atoms, p is an integer of 1 to 3, and X ₂
(represents COO or -SO ₃ group) Among these, those in which R ₉ has 12 to 16 carbon atoms, R ₁₀ and R ₁₁ are methyl groups, and p is 3 are preferred. Imidazoline type compound represented by the following formula [In the formula, R ₁₂ is a fatty acid radical with an average carbon number of 10 to 20, R ₁₃ is hydrogen, Na or CH ₂ COOMe (Me:
H, Na, organic base), R ₁₄ is COOMe,
CH ₂ COOMe or

[Formula] (Me is the same as above), R ₁₅ represents a hydroxyl group, an acid salt, an anionic surfactant sulfate or a sulfate] Among these, those in which R ₁₂ has 12 to 16 carbon atoms are preferred. (d) Cationic activator The cationic activator used in the present invention is not particularly limited, and any agent that can be incorporated into a hair rinse agent may be used, but the following formula:
(1), (In the formula, 1 to 2 of R ₁₆ , R ₁₇ , R ₁₈ and R ₁₉ represent a long-chain alkyl group or a long-chain hydroxyalkyl group with 8 to 20 carbon atoms, and the rest represent a long-chain hydroxyalkyl group with 1 to 3 carbon atoms.
represents an alkyl or hydroxyalkyl group or a benzyl group, and X ₃ represents a halogen atom or an alkyl sulfate group having 1 to 2 carbon atoms.
In particular, distearyldimethylammonium chloride, stearyltrimethylammonium methosulfate, stearyltrimethylammonium chloride, stearyldimethylbenzylammonium chloride, lauryldiethylbenzylammonium chloride, lauryltrimethylammonium bromide, distearylmethylhydroxymethyl chloride, cetyltrimethylammonium chloride, etc. preferable. Among the above surfactants, anionic surfactants,
In particular, alkyl ethoxy sulfates having a linear or branched alkyl group with an average carbon number of 12 to 16 and 1 to 4 moles of ethylene oxide added to each molecule, or an alkyl ethoxy sulfate having an average carbon number of 12 to 16 Straight chain or branched alkyl sulfates are preferred. These surfactants are used in hair rinse compositions.
Good results are obtained by adding 0.01 to 10%, preferably 0.5 to 5%. Furthermore, the hair rinse of the present invention includes, as optional ingredients, hydrocarbons such as liquid paraffin, petrolatum, solid paraffin, esters such as isopropyl myristate, lanolin, purified lanolin,
Lanolin derivatives such as lanolin fatty acids, silicone derivatives such as dimethylpolysiloxane, methylphenylpolysiloxane, organo-modified polysiloxane, polyethylene glycol, polypropylene glycol or their polymers, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl ether phosphorus Oil agents such as acids; polymeric substances such as hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, cationized cellulose, and cationized polymers; bactericides, preservatives, fragrances, pigments, etc. may be added and blended as appropriate. can. (3) Hair setting agent (setting lotion, hair spray, etc.): Prepared by dissolving cationized keratin in a polar solvent such as water, ethyl alcohol, propyl alcohol, etc. according to a conventional method. The amount of cationized keratin contained in the hair setting agent of the present invention is preferably 0.01 to 10%, particularly 0.1 to 5%. The hair setting agent of the present invention may further include optional ingredients according to the purpose within the limits that do not impede the effects of the present invention, such as oily substances such as higher alcohols and higher fatty acid esters; polyoxyethylene as an emulsifier and solubilizer. Nonionic surfactants such as lauryl ether, polyoxyethylene sorbitan monolaurate, and polyoxyethylene hydrogenated castor oil;
Moisturizers such as glycerin and propylene glycol;
Flavors, pigments, etc. can be added and blended. The hair setting agent of the present invention can be applied directly to the hair as it is, or it can be applied as a mist using a pump spray or the like, or it can be applied in the form of a mist using a pump spray or the like.
It can also be applied in the form of a mist or foam by filling a container with a propellant such as liquid hydrocarbon or carbon dioxide gas. The thus obtained hair setting agent of the present invention forms a uniform and strong film after drying, has excellent hair setting power even under high humidity conditions, and has an anionic surfactant that is currently widely used. When hair is washed with a shampoo containing the agent, it can be easily removed from the hair, making it an excellent product that satisfies both the requirements of setting power and cleansing properties. (4) Permanent wave first agent: Prepared by blending cationized keratin into the permanent wave first agent composition, which is based on a reducing substance. The amount of cationized keratin in the permanent wave first agent (hereinafter referred to as "first agent") of the present invention is preferably 1 to 20%, particularly 2 to 5%. If the amount is less than this, the object of the present invention will not be fully achieved, while if it is more than this, cationized keratin will excessively adhere to the hair, causing problems such as stickiness under high humidity. As the reducing substance that is the base of the first agent of the present invention, any conventionally used reducing substance can be used,
Among these, ammonium salts of thioglycolic acid and hydrochloride of cysteine are particularly preferred. The first agent of the present invention is produced by mixing and blending the above-mentioned components by a method known per se. In addition, it also includes conventionally used pigments, fragrances, oil components, clouding agents, water-soluble silicones, Organic salts, urea, etc. can also be added depending on the purpose. (5) Permanent wave second agent: Prepared by blending cationized keratin into the permanent wave second agent composition which is based on an oxidizing substance. The amount of cationized keratin in the permanent wave second agent of the present invention (hereinafter referred to as "second agent") is preferably 0.01 to 10%, particularly 0.1 to 5%, and The compounding amount is the second
It is preferably 1 to 30%, particularly 3 to 20%, although it varies depending on whether or not the agent is dissolved in a solvent and the degree of dilution when used diluted. Furthermore, as the oxidizing substance which is the base of the second agent in the present invention, any commonly used oxidizing substance can be used, such as alkali metal bromates such as sodium bromate and potassium bromate, hydrogen peroxide, peroxide, etc. Examples include sodium carbonate and sodium perborate, among which alkali metal bromates are particularly preferred. In addition to the above-mentioned essential ingredients, the second agent of the present invention includes:
Anionic surfactants, amphoteric surfactants, nonionic surfactants in amounts that do not impair the effects of the present invention,
Optional components such as cationic surfactants, cationic polymer compounds, water-soluble silicones, urea, appropriate oils, wetting agents, fragrances, and pigments can be added and blended. Among these optional components, cationic polymer compounds include cationic cellulose derivatives, cationic starch, diallyl quaternary ammonium salts or copolymers of diallyl quaternary ammonium salts and acrylamide, polyglycols, polyamine condensates, methacryloxy Examples include copolymers of ethyltrimethylammonium salt or methacryloxyethyltrimethylammonium salt and polyvinylpyrrolidone, among others, cationic cellulose represented by the product name "Polymer JR", and cationic cellulose represented by the product name "Marquat 100" Particularly effective are diallyl quaternary ammonium salts and diallyl quaternary ammonium salt/acrylamide copolymers represented by the trade name "Marquat 550." The amount of these cationic polymer compounds added is preferably 0.01 to 5%, particularly 0.05 to 2%. The second agent thus obtained is a 5% aqueous solution of the second agent.
The pH is adjusted to 9 or less, preferably 3.5 to 6.5. (6) Hair dye: Prepared by blending cationized keratin into a hair dye base using a conventional method. The content of cationized keratin in the hair dye of the present invention is preferably 0.1 to 10%, particularly 0.5 to 5%. If the amount is less than 0.1%, the effect cannot be fully exhibited, and if it is more than 10%, no further increase in effect is observed, and on the contrary, the hair becomes sticky even under high humidity, which is preferable. do not have. Since cationized keratin is water-soluble, it can be added and blended as is. The hair dye base of the hair dye composition of the present invention is not particularly limited, and any known base can be used. for example,
The following is an explanation of oxidative hair dyes and temporary hair dyes as examples. (i) Oxidative hair dye A dye intermediate, an oxidizing agent and, if necessary, a coupler or modifier are blended. Dye intermediates include p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, 4,4'-diaminodiphenylamine, p-aminophenol, p-methylaminophenol. , o-phenylenediamine, toluene-3,4-diamine, o-aminophenol, p-chloro-o-phenylenediamine, p-amino-o-cresol, o-chloro-
Examples include para or ortho components such as p-phenylenediamine, phloroglucin, pyrogallol, 3,3'-iminodiphenyl, diphenylamine, 2,6-diaminopyridine, and p-aminophenylsulfamic acid. In addition, Katsupura (modifier) includes m-phenylenediamine, toluene-2,4-diamine, p-methoxy-m-phenylenediamine, m-aminophenol, α-naphthol, resorcinol, hydroquinone, catechol, etc. Examples include meta components and phenols. As an oxidizing agent, hydrogen peroxide is usually used, but sodium perborate, urea peroxide, sodium percarbonate, sodium peroxide tripolyphosphate, sodium peroxide pyrophosphate, sodium orthophosphate peroxide, and sodium silicate peroxide Examples include hydrogen adducts, sodium sulfate, sodium chloride, hydrogen peroxide adducts, and the like. In addition, direct dyes, especially nitro-p-phenylenediamine, p-nitro-o-phenylenediamine, 2-amino-4-nitrophenol, which do not participate in the pigment-forming reaction but affect the color tone of the hair, are used. , 2-amino-5-nitrophenol, 4-amino-2-
Nitro dyes such as nitrophenol, and if necessary, picramic acid, picric acid, and 1,4-diaminoanthraquinone can be blended. Furthermore, nonionic surfactants and cationic surfactants are added in amounts that do not impair the effects of the present invention, solvents such as propylene glycol and glycerin, lower alcohols such as ethyl alcohol and isopropyl alcohol, hydroxyethyl cellulose and methyl cellulose. , cationic polymer compounds, viscosity modifiers such as higher alcohols, wetting agents, protein denaturants such as urea, fragrances, pigments, ultraviolet absorbers,
Antioxidants, preservatives, pearlizing agents, lotioning agents, etc. can be added. The oxidative hair dye of the present invention can be prepared by mixing the above ingredients and cationized keratin in a conventional manner to form a powder or cream preparation, and either as a one-piece preparation that is added to water or a shampoo base at the time of use, or as an oxidative hair dye. Preferably, the dye and the oxidizing agent are separated, one or both of them is blended with cationized keratin, and a powder, cream, or liquid preparation is prepared, which is then mixed at the time of use to form a combination preparation. (ii) Temporary hair dye Dyes and pigments are not particularly limited, but include pigments such as titanium oxide and carbon black, triphenylmethane dyes, azo dyes, quinoline dyes, xanthene dyes, acridine dyes, azine dyes, oxazine dyes, Examples include tar-based dyes such as indigoid dyes, anthraquinone dyes, stilbene dyes, and thiazole dyes. In addition, examples of the resin include copolymers of acrylic esters and methacrylic esters, N,
Copolymers of N'-dimethylaminoethyl methacrylate modified with monochloroacetic amine salt and methacrylic acid ester, vinylpyrrolidone vinyl acetate copolymers, etc. are used. Temporary hair dyes are prepared by dissolving and dispersing cationized keratin, resins, dyes, pigments, etc. in a dispersion medium such as water, amyl alcohol, isopropanol, ethanol, acetone, or the like. These include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, polyhydric alcohols such as propylene glycol, glycerin, and polyethylene glycol, and higher-grade alcohols such as isostearyl alcohol and oleyl alcohol. Alcohol, fatty acids such as lanolin fatty acids, coconut fatty acids,
Components of known temporary hair dye compositions such as esters such as isopropyl myristate, hydrocarbons such as liquid paraffin, cationic polymer compounds, amines, fragrances, etc. can be blended depending on the purpose. . The temporary hair dye containing cationized keratin can be in any form, such as a mascara type, a spray type, or a lotion type. The hair cosmetic of the present invention obtained as described above eliminates the drawbacks of conventional hair cosmetics, has an excellent conditioning effect, prevents hair damage and deterioration, and has a good feel when used. It is excellent. Next, the present invention will be explained with reference to reference examples and examples, but the present invention is not limited to these examples. Reference example 1 10g of wool fiber was immersed in 700g of 50% n-propanol aqueous solution to which 0.02M Tris buffer was added,
After adding 4 ml of tri-n-butylphosphine as a reducing agent, the pH was adjusted to 8.0 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature for 24 hours under a nitrogen stream. Next, add glycidyltrimethylammonium chloride to the reaction system.
When 1.5 g is added and stirred at 70°C for 5 hours, about 85% of the wool fibers are solubilized in the reaction solution. Insoluble portions were removed by filtration, and the resulting solution was subjected to ultrafiltration (using a membrane with a molecular weight cutoff of 1000) to remove low-molecular impurities such as reducing agents, and the entire system was concentrated to about 150 ml. By freeze-drying this, 8.1 g of solid powder was obtained. The molecular weight of the obtained powder solid was determined to be 39,000 by gel filtration method (using Cephadex G-75). In addition, the powder solid was hydrolyzed in 6N hydrochloric acid at 110℃ for 24 hours, and the decomposed product was analyzed for amino acids (Hitachi Automatic Amino Acid
Analyzer Type KLA-5) was performed and compared with the amino acid analysis results of raw wool.As shown in the table below, the amino acid composition and content other than cystine was almost the same for both, but regarding cystine, wool Although 5.5 mol of cystine was observed in 100 mol of amino acids, it was not observed at all in the powdered solid, indicating that glycidyltrimethylammonium chloride had been added. Therefore, the molecular weight and amino acid analysis results of the obtained powder solid indicate that the main chain peptide bonds of the keratin protein have not undergone any changes such as hydrolysis, and the disulfide bonds have been cleaved to form β-hydroxy-γ-trimethylammoniopropyl. A group is added, that is, S-(β
-Hydroxy-γ-trimethylammoniopropyl) keratein.

【table】

[Table] Reference example 2 10.0 g of wool fiber was immersed in 600 g of an aqueous solution containing 0.02 M Tris buffer, and 6.0 ml of 2 was added as a reducing agent.
- After adding mercaptoethanol, the pH was adjusted to 8.5 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature for 24 hours under a nitrogen stream. Next, 2.0 g of glycidyltrimethylammonium chloride was added to the reaction system and stirred at 50°C for 6 hours, so that about 80% of the wool fibers were dissolved in the reaction solution. Insoluble parts were removed by filtration, and from the resulting aqueous solution of the cationized keratin compound, low-molecular impurities such as reducing agents were removed by ultrafiltration, and about 1/5 of the aqueous solution of the cationized keratin compound was removed. Concentrated into By freeze-drying this, 7.5 g of a cationized keratin compound derivative was obtained. The average molecular weight of this product was determined by gel filtration method and was found to be 41,000. Reference Example 3 In Reference Example 2, a 50% n-propanol aqueous solution was used as the reaction solvent, and tris-n was used as the reducing agent.
-Reference example 2 except for using 4 ml of butylphosphine
The same operation as above was performed to obtain 7.8 g of a cationized keratin derivative having an average molecular weight of 40,000. Reference example 4 10g of wool fiber added with 0.02M Tris buffer
Immerse in 700g of 30% ethanol aqueous solution, add 4ml of tri-n-butylphosphine as a reducing agent, adjust the pH to 8.0 with 1N hydrochloric acid, and perform the reduction reaction at room temperature for 24 hours under a nitrogen stream. . Next, 2.5 g of allyltrimethylammonium chloride was added to the reaction system and stirred at 70°C for 5 hours.
85% is solubilized in the reaction solution. The insoluble portion was removed by filtration, and the resulting liquid was subjected to ultrafiltration (molecular weight cutoff).
1000 membrane) to remove low-molecular impurities such as reducing agents, and concentrated to approximately 150 ml. By freeze-drying this, 8.2 g of cationized keratin with an average molecular weight of 39,000 was obtained. Reference Example 5 Feathers were heated in a high-pressure container with 6 kg/cm ² of superheated steam at 240°C for 6 minutes, and then rapidly released into the atmosphere. 10.0 g of the porous puffed product was heated in a 0.02 M Tris buffer. 700g of 30% ethanol aqueous solution
After adding 4 ml of tri-n-butylphosphine as a reducing agent, the pH was adjusted to 8.0 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature under a nitrogen stream for 24 hours.
Next, 2.5 g of allyltomethylammonium chloride was added to the reaction system and reacted at 70°C for 5 hours, and about 90% of the puffed feathers were dissolved in the reaction solution. Insoluble parts are removed by filtration, and the resulting liquid is subjected to ultrafiltration to remove low-molecular impurities such as reducing agents.
It was concentrated to about 150ml. By freeze-drying this, cationized keratin with an average molecular weight of 38,000 is produced.
Obtained 8.5g. Reference example 6 10g of wool fiber in 1% sodium sulfite aqueous solution
Soak in 300g and PH with 5N sodium hydroxide aqueous solution
After adjusting to 6.7, add 0.2g of papain and incubate at 60℃.
After 15 hours of hydrolysis, approximately 80% of the wool fibers were removed.
was solubilized. Insoluble materials are removed by filtration, and sulfites in the resulting solution are removed by ultrafiltration using a membrane with a molecular weight cutoff of 500.The aqueous hydrolyzate solution is concentrated and freeze-dried to reduce the molecular weight. 7.7 g of 2000 hydrolyzate was obtained. This is an aqueous solution containing 0.02M Tris buffer.
After dissolving in 450 g of the solution and adding 4.5 ml of 2-mercaptoethanol as a reducing agent, the pH was adjusted to 8.5 with 1N hydrochloric acid, and the reduction reaction was carried out at room temperature under a nitrogen stream for 13 hours. Next, 16 g of glycidyltrimethylammonium chloride was added to the reaction system, and the mixture was stirred at 50°C for 6 hours. Low-molecular impurities such as reducing agents were removed from the resulting reaction solution by ultrafiltration, and the aqueous solution was reduced to about 1/5.
Concentrated into By freeze-drying this,
6.2g of cationized keratin was obtained. Reference Example 7 After heating wool under pressure in a high-pressure container with 4 kg/cm ² of saturated steam for 8 minutes, it was rapidly released into the atmosphere.
A porous puffed product was obtained. 10 g of this expanded product was immersed in 300 g of a 75% phosphoric acid aqueous solution and stirred at 120 to 130° C. for 5 hours to perform a hydrolysis reaction. Cool this and
After removing the insoluble portion by filtration, 4 to 5 times the amount of water was added, and the insoluble portion was further removed by centrifugation. Next, after adding calcium carbonate and adjusting the pH to 6.7,
The molecular weight is 2000 by removing the precipitate and drying it.
8.5 g of hydrolyzate was obtained. This is an aqueous solution containing 0.02M Tris buffer.
Disperse in 500g and add 4ml of tri-n as reducing agent.
-After adding butylphosphine, PH with 1N hydrochloric acid
8.0, and the reduction reaction was carried out for 24 hours under a nitrogen stream. Next, 20 g of glycidyltrimethylammonium chloride was added to the reaction system, and the mixture was stirred at 50°C for 6 hours. Low-molecular impurities such as reducing agents are removed from the resulting reaction solution by ultrafiltration, the aqueous solution is concentrated,
6.7 g of cationized keratin was obtained by freeze-drying. Reference Example 8 In Reference Example 6, 10g of puffed feather product was used instead of wool fiber, and 20g of 2-chloro-2-hydroxypropyltrimethylammonium chloride was used instead of glycidyltrimethylammonium chloride.
Cationized keratin was obtained by reacting in the same manner. Example 1 Shampoo: Using the cationized keratin synthesized in Reference Examples 1 to 8, a shampoo composition having the following composition was prepared and its performance evaluation test was conducted. The results are shown in Table 1. Incidentally, performance evaluation in the examples was carried out by the following method. (1) Foaming test method 0.1% lanolin was added as an artificial stain to a 1% aqueous solution of shampoo composition, and a flat propeller was used to
Stir in a cylinder for 5 minutes at a temperature of 1000 rpm and invert every 10 seconds. After stirring,
Evaluation was made based on the amount of foam after 30 seconds. (2) Feel of foam Wet 30g of human hair with 40℃ water and soak it with 20g of water. Next, hair is washed using 1 g of the shampoo composition, and the feel of the foam is evaluated by sensory evaluation by 20 female panelists. Evaluation item: “Slippage of foam” refers to how easily your fingers run through your hair when washing your hair.
Evaluate as follows. Evaluation Criteria〇 Better foam slippage than the standard product △ Slightly better than the standard product (PH7.2) (3) Combing power Moisten 30g of human hair with 40℃ water and add 20g of water. Shampoo - wash your hair using 1g of composition,
Repeat the rinsing operation twice and leave it in a deflated state.
Place it on a strain gauge and use a comb to measure the force applied at that time (when wet). Dry it with a hair dryer, leave it in a constant temperature and humidity room at 20°C and 65% relative humidity overnight, then place it on a strain gauge, and measure the force applied at that time with a comb (when drying). (4) Hair fly Observe whether the hair fly phenomenon occurs due to static electricity when measuring the drying state of the comb. Rating 〇 Hair flies occur. × 〃 Doesn't happen. Composition: Surfactant (Table 1) 15% Cationized keratin (Table 1) 3% Water Balance result:

[Table] Example 2 Hair Rinse: Using the cationized keratin synthesized in Reference Example 3, a hair rinse with the following formulation was prepared.
Hair was treated with 500 ml of a 50-fold dilution of these hair rinses, rinsed twice with warm water, and air-dried. Composition (A) and composition (B) were determined by Sietsufue's paired comparison method using 20 panelists. and (C) and evaluated on a five-point scale. The results are shown in Table 2. Composition: (A) Distearyldimethylammonium chloride
2.0(%) Monostearyltrimethylammonium chloride 0.5 Cationized keratin of Reference Example 3 0.1 Water Balance (B) Distearyldimethylammonium chloride
2.0(%) Monostearyltrimethylammonium chloride 0.5 Collagen alkaline hydrolyzate (MW.800~
1000) 0.1 Water balance (C) Distearyldimethylammonium chloride
2.0(%) Monostearyltrimethylammonium chloride 0.5 Water Result:

【table】

[Table] Example 3 Hair conditioner: Using the cationized keratin and silicone derivatives synthesized in Reference Examples 6 to 8, a hair conditioner having the composition shown below was manufactured, and its hair protection effect was investigated. The hair protection effect can be determined by dispersing 5g of hair conditioner in 500ml of ion-exchanged water, soaking a 20cm long hair strand (5g in weight) for 5 minutes, then rinsing with running water for 5 minutes, drying, and using a nylon brush. This was done by combing the hair 500 times and measuring the weight of the hair that was generated during that time. Composition: Cationized keratin (Table 3) 1.0% Silicone derivative (Table 3) 3.0% Water Balance Results:

【table】

[Table] Example 4 Hair setting agent: A hair setting agent having the following composition was manufactured and its setting retention power was examined. The results are shown in Table 4. Composition: Cationized keratin (Table 4) 1% Ethanol 10 Water-soluble silicone ^* [(Polyether modified silicone oil) In the following formula, n ₃ = 25, m ₄ = 10, l ₂
= l ₃ = 20] 0.5 Fragrance 0.1 Water Balance ^* Polyether-modified silicone oil: Curl holding power (%) = Lo - Lt / Lo - Ls × 100 Lo = 14 (cm) Ls = Curl length (cm) immediately after hanging under 95% humidity Lt = 30 when hanging under 95% humidity Curl length after minutes (cm)

[Table] Example 5 Blow-finishing agent: A blow-finishing agent with the following composition was produced, and an evaluation panel consisting of 30 women aged 18 to 35 compared its set-holding power, finish feel, and residual feeling after hair washing. Evaluation was made using the paired comparison method. This result is the fifth
Shown in the table. Composition: Cationized keratin of Reference Example 1 2% 2-amino-2-methyl-1-propanol
1 Ethanol 10 Water-soluble silicone (same as Example 4) 0.5 Fragrance 0.1 Water Balance (comparative product) Vinyl acetate-crotonic acid copolymer 2% Triisopropanolamine 1 Acid hydrolyzate of collagen (MW.20000)
0.3 Ethanol 10 Water Result:

[Formulation 1 (product of the present invention)]

Thioglycolic acid ammonium salt 7.0% Cationized keratin from Reference Example 6 3.0 Water (ammonia water/for pH adjustment) 90.0 [Formulation 2 (comparative product)] The cationized keratin in Formulation 1 was replaced with water. (2) Permanent wave 2nd agent: Sodium bromate 5.0% Water 95.0 Test method: (1) Wave degree and wave holding power measurement test (iv) 20 hairs were made into a bundle, and a wave measuring plate (diameter 2 mm, length It was fixed to the cylinder of a plate (a plate with 1.5 cm thin cylinders arranged and fixed in two rows). This was immersed in the first agent of formulations 1 to 4 at 30°C for 10 minutes, and then in the second agent at 30°C for 10 minutes. After rinsing thoroughly with water, remove it from the wave measurement plate.
The degree of wave was calculated using the following formula in still water. The hair used was virgin hair with a length of 20 cm that had been washed and dried with a 0.5% aqueous solution of sodium lauryl sulfate. Wave degree (%) = X-Z/X-Y x 100
Length Y of the hair fixed between AB: Distance between AB Z: Distance between the points of the hair in contact with AB in still water after being removed from the measurement plate (ii) Hair used in (i) was washed by immersing it in a 0.5% aqueous solution of sodium lauryl sulfate for 1 minute and gently moving it, rinsing thoroughly, and air-drying it for one day.
This operation was repeated four times, and after the fifth wash, the hair was thoroughly rinsed with water, and the above-mentioned Z was measured in still water to determine the degree of wave, which was compared with the degree of wave before hair washing and was taken as the wave holding power. Wave holding power (%) = Wavy degree after 5 times of hair washing / Wave degree before hair washing ×
100 (2) Adsorption property The hair used for wave degree measurement was observed under a scanning electron microscope to determine the presence or absence of adsorbents on the hair surface. The results were evaluated by dividing the degree of adsorption into three levels. The evaluation criteria are shown below.

[Table] (3) Tactile evaluation Hair bundles made of Japanese virgin hair were formulated from 1 to
It was immersed in the first agent No. 4 at 30°C for 10 minutes, and then in the second agent at 30°C for 10 minutes. After rinsing thoroughly with water and air-drying the hair tresses, 20 women evaluated the texture on a five-point scale. The evaluation standard is good (5
The results were expressed as a geometric mean value. Result:

〔composition〕

(First agent formulation) Thioglycolic acid 7.0% Polyoxyethylene hydrogenated castor oil 1.0 Fragrance 0.2 Ammonia water, water balance (pH adjusted to 9.0 with ammonia water) (Second agent formulation) Second agent base sodium bromate 5.0(%) Ampholytic surfactant ("Milanol C2M-SF" manufactured by Milanol) 0.5 Cationized cellulose ("Polymer JR400")
(Manufactured by UCC) 0 or 0.5 Fragrance 0.1 Cationized keratin (Table 7) 2.0 Water Balance [Hair weight measurement method] Virgin hair 10 cm long was washed with a 0.5 aqueous solution of sodium lauryl sulfate and air-dried, and this was used as the test hair. And so. Approximately 1 g of this hair was bundled, placed in a desiccator using phosphorus pentoxide as a drying agent, and further dried under reduced pressure for one week.The weight of the hair at the time was defined as the absolute dry weight of virgin hair. Next, add this hair to the first
After soaking in the agent for 10 minutes at 30℃, rinse thoroughly with water.
Then, it was immersed in a second permanent wave agent at 30°C for 10 minutes. After thoroughly rinsing with water, the hair was air-dried and dried again in the same manner as described above, and the weight was taken as the absolute dry weight of permanent wave hair. 〔Evaluation criteria〕

〔Evaluation criteria〕

Evaluation Details ◎ Hair weight increased from before treatment. 〇 Hair weight decreased by 0-3% compared to before treatment. × The hair weight decreased by 3% or more compared to the hair weight before treatment. Hair dye treatment method: A mixture of equal amounts of the first liquid and the second liquid was used as a hair dye, and diluted so that the bath ratio was 1:5. Hair was immersed in this solution for 30 minutes at room temperature to dye the hair.
The hair dye was then washed off with tap water at 40°C and washed with a 0.5% aqueous solution of sodium lauryl sulfate.
After further soaking in 1N acetic acid aqueous solution, heat at 40℃ again.
Washed with tap water. Result:

【table】

[Table] Example 9 Hair Dye: A mascara type temporary hair dye composition (hair colorant) having the following composition was prepared. Apply 0.5g of this to 1g of gray hair, and after air-drying, a panel of 10 experts will apply it to give it shine and shine.
Sensory evaluation was conducted regarding slippage and feel preference. The results are shown in Table 9. Composition: (%) Polymer resin ^* 12.0 Pigment (carbon black) 1.0 Cationized keratin (Table 9) 1.0 Fragrance 0.1 Ethanol Balance ^* Polymer resin: Monochloroacetic acid amine of N,N'-dimethylaminoethyl methacrylate Copolymer of salt modified product and methacrylic acid ester Results:

[Table] ○ indicates good, △ indicates somewhat good, and × indicates bad. )
Example 10 Hair liquid: (Composition) A Cationized keratin (obtained in Reference Example 3)
1.0% B Polyoxypropylene (30) butyl ether
15.0 C Ethanol 40.0 D Water 44.0 (Manufacturing method) The above A to D are mixed and each component is completely dissolved to obtain a hair liquid. Example 11 Hair tonic: (Composition) % A Cationized keratin (obtained in Reference Example 4)
0.5 B PCA-Al 0.5 C Ethanol 55.0 D Water 44.0 (Production method) The above ingredients A to D are mixed and stirred until uniform to obtain a hair tonic.

Claims (1)

[Scope of Claims] 1. Hair cosmetics other than pre-champion treatment, in which part or all of the sulfhydryl groups of the reductive decomposition product of keratin substances or the reductive decomposition product of keratin hydrolyzate have the following formula:
A cation obtained by reacting a group represented by [Formula] [Formula] or CH ₂ = CH - (in the formula, X represents a halogen atom) with a cationizing agent having a quaternary nitrogen in one molecule. A hair cosmetic composition characterized by containing a chemically modified keratin derivative.