JP2019199443A - Hair cosmetics - Google Patents

Abstract

To provide hair cosmetics that impart excellent luster, moisturizing feel and tension to the hair, improve hair combing properties, and can finish the hair with a smooth feel.SOLUTION: The hair cosmetic composition is composed of 0.05 to 20% by mass of at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof, and 3.5 to 10% by mass of 1,3-butylene glycol. A hydrolyzed cuticle protein is obtained by hydrolyzing wool-derived cuticle protein with hydrochloric acid and thioglycolic acid, the total amount of cystine and cysteine as constituent amino acids in amino acid analysis is 12 mol% or more as half cystine, and preferably the number average molecular weight of the peptide moiety is 100 to 3,000.SELECTED DRAWING: None

Description

The present invention relates to a cosmetic containing a hydrolyzate of a cuticle protein and a derivative thereof. More specifically, the present invention provides an excellent harshness when applied to hair, and further provides gloss, smoothness and moisturizing feeling. The present invention relates to a hair cosmetic containing a hydrolyzed cuticle protein and derivatives thereof and a polyhydric alcohol, which is excellent in the imparting effect.

Hydrolyzed proteins and their derivatives obtained by hydrolyzing proteins derived from natural products such as collagen, keratin, silk, soybeans, and wheat are useful as surfactants and emulsifiers that are highly safe and less irritating. Conventionally, it has been widely blended in cosmetics as a cosmetic base material.

Among the above protein sources, keratin contains a large amount of cystine as a constituent amino acid, and its hydrolyzed protein binds strongly to keratin cystine in hair, so it is particularly effective in repairing damaged hair and has high tensile strength. Since it has the function of enhancing the moisturizing property, smoothness and gloss of the hydrolyzed protein, it is widely used in various cosmetics for hair.

In addition, hydrolyzed keratin derivatives that have enhanced hair adsorbability and hair softening properties can also be used for hair conditioning by adsorbing to the hair to make it softer and moisturize and gloss. Since it is excellent in the action which protects hair and protects hair, the use as cosmetics for hair, such as a shampoo, a hair conditioner, and a hair treatment, is proposed (patent document 1 etc.).

Since the cuticle protein of wool contains a large amount of cystine, the hydrolyzed cuticle protein that hydrolyzes this protein binds strongly with cystine in hair keratin, repairs damaged hair, and pulls the hair Since it is superior to conventional hydrolyzed keratin in the action of enhancing moisture and imparting moisture retention, smoothness, luster, etc., hair cosmetics containing hydrolyzed cuticle protein or hydrolyzed cuticle protein derivatives Use as a cosmetic base has been proposed (Patent Documents 2 and 3).

However, hydrolyzed cuticle protein and its derivatives have high adsorptive power to hair and skin, and are excellent in the action of repairing the hair when applied to damaged hair, but contain hydrolyzed cuticle protein and its derivatives. Hair cosmetics are not satisfactory in terms of effects such as moisturizing, smoothness and glossiness on hair, and it is hoped that hair cosmetics containing hydrolyzed cuticle protein and its derivatives that exhibit superior effects will be developed. It was rare.

Japanese Patent Laid-Open No. 02-045409 JP-A-2005-247692 Japanese Patent No. 4344644

Therefore, the present invention solves the problems in the prior art as described above, has an excellent adsorptivity to hair, is particularly excellent in the repair effect of damaged hair, and is moisturizing and smooth to hair. Another object of the present invention is to provide a hair cosmetic containing a hydrolyzed cuticle protein and a derivative thereof having an excellent effect in terms of imparting gloss.

As a result of intensive studies to solve the above problems, the present inventors have obtained at least one 0.05 selected from the group consisting of a hydrolyzed cuticle protein and a derivative thereof obtained by hydrolyzing a cuticle protein derived from a natural product. Hair cosmetics containing ˜20% by mass and 1,3-butylene glycol 3.5 to 10% by mass exhibit a high restoration effect on damaged hair, and are moisturizing, smooth and glossy. The present invention has been completed by finding out that excellent effects can be achieved in terms of imparting.

That is, the present invention contains (A) 0.05 to 20% by mass of at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof, and (B) 3.5 to 10% by mass of 1,3-butylene glycol. The present invention is based on the hair cosmetics characterized in that, and in the present application, this is the invention according to claim 1.

The hydrolyzed cuticle protein of component (A) and its hydrolyzed protein are obtained by hydrolyzing wool-derived cuticle protein with hydrochloric acid or hydrochloric acid and thioglycolic acid, and cysteine and cysteine as constituent amino acids in amino acid analysis. The total amount of cystine is 12 mol% or more as half cystine, and the number average molecular weight of the peptide moiety is 100 to 3,000, which is industrially easily available, and exhibits a repair effect especially on damaged hair, This is preferable because it enhances the tensile strength of the hair and imparts moisture retention, smoothness and gloss to the hair synergistically with the component (B). In the present application, this is the invention according to claim 2.

As the derivative of the hydrolyzed cuticle protein of the component (A), acylated derivatives, quaternary ammonium derivatives, silylated derivatives, alkylglycerylated derivatives, 2-hydroxyalkylated derivatives and ester derivatives of the hydrolyzed cuticle protein are industrially available. The hair cosmetic composition according to claim 1 or 2, wherein the derivative of the hydrolyzed cuticle protein is at least one selected from the group consisting of the derivatives. The invention according to claim 3.

By setting the content of 1,3-butylene glycol of the component (B) in the hair cosmetic to 3.5 to 7% by mass, there is less stickiness and excellent moisturizing property, smoothness and gloss imparting. The hair cosmetic composition according to claim 4 is characterized in that the content of the component (B) is 3.5 to 7% by mass.

The hair cosmetic composition of the present invention is obtained by hydrolyzing a cuticle protein derived from a natural product, at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof, and 0.05 to 20% by mass; -It contains 3.5 to 10% by mass of butylene glycol, and exhibits a high restoration effect on damaged hair, and can impart moisture retention, smoothness and gloss. Therefore, particularly when used as a shampoo, a hair conditioner, or a cosmetic for improving the condition of hair such as a hair treatment or a hair mist, the effects of the present invention are remarkably exhibited.

Next, the form for implementing this invention is demonstrated. First, the hydrolyzed cuticle protein of component (A) and its derivative used in constructing the hair cosmetic composition of the present invention will be described, and then 1,3-butylene as components (A) and (B). The form of the hair cosmetic containing glycol will be described.

[Hydrolyzed cuticle protein and its derivatives]
The origin of the cuticle protein used as the raw material for the hydrolyzed cuticle protein to be contained in the hair cosmetic composition of the present invention is not particularly limited, but uses a cuticle protein separated from wool that is industrially easily available. It is preferable. The cuticle part is separated from the wool and subjected to hydrolysis, but the method for separating the cuticle part from the wool is not particularly limited, and the screen is treated and centrifuged by mechanically stirring the wool in formic acid or a surfactant aqueous solution. A known method such as a method of separating dry wool by a specific gravity difference in an air flow after pulverization can be employed.

The method for hydrolyzing the obtained cuticle protein is not particularly limited. However, in order to leave the disulfide bond of cystine on the side chain of the hydrolyzed cuticle protein, for example, hydrochloric acid and a reducing agent described in JP-A-03-007595 It is preferable to employ a method in which hydrolysis and oxidation reaction with an enzyme are performed after hydrolysis according to.

Hydrolyzed cuticle protein can control the molecular weight of the peptide produced by changing the amount of hydrochloric acid, heating temperature, decomposition time, etc. at the time of decomposition, but when the cuticle protein is hydrolyzed to its constituent amino acids. Has a number average molecular weight of about 100, and if the hydrolyzed cuticle protein has a number average molecular weight of more than about 3,000, the hair may become stiff or the hair may become sticky under high humidity. Since there is a possibility that the peptide may associate during storage and cause turbidity and precipitation, the hydrolyzed cuticle protein contained in the hair cosmetic composition of the present invention has a number average molecular weight of about 100 to about 3,000. Are preferred, with about 100 to about 500 being more preferred.

The cosmetic base material of the present invention contains at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof. Examples of the hydrolyzed cuticle protein derivative include acylated derivatives and quaternary ammonium. Derivatives, silylated derivatives, alkyl glycerylated derivatives, 2-hydroxyalkylated derivatives, ester derivatives and the like. These hydrolyzed cuticle proteins and derivatives thereof may be used alone or in combination of two or more.

As the acylated derivative, at least a part of the terminal amino group of the hydrolyzed cuticle protein main chain and the amino group of the amino acid side chain has the following general formula:

[In formula (I), R ¹ represents a linear or branched alkyl or alkenyl group of 7 to 31 carbon atoms. ]
A group to which a group represented by The acylated derivative can be obtained by reacting a hydrolyzed cuticle protein with a C8-C32 linear or branched saturated or unsaturated fatty acid or an acid chloride derivative of a resin acid under alkaline conditions.

Examples of the straight chain or branched chain saturated or unsaturated fatty acid or resin acid having 8 to 32 carbon atoms include, for example, lauric acid, myristic acid, coconut oil fatty acid, isostearic acid, stearic acid, undecylenic acid, lanolin fatty acid, and resin. Examples include acids and hydrogenated resin acids.

In the acylated derivative of the hydrolyzed cuticle protein, the number average molecular weight of the hydrolyzed protein portion is preferably about 100 to about 3,000 for the same reason as the hydrolyzed cuticle protein. More preferably, it is 100 to about 500.

As the quaternary ammonium derivative, at least a part of the terminal amino group of the hydrolyzed cuticle protein main chain and the amino group of the amino acid side chain may be represented by the following general formula (II):

[In the formula (II), R ² , R ³ and R ⁴ may be the same or different, and one or two of R ^{2 to} R ⁴ are an alkyl group having 1 to 22 carbon atoms or 2 to 2 carbon atoms. 22 alkenyl groups, and the remainder represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a benzyl group. B represents a saturated hydrocarbon having 2 to 3 carbon atoms or a saturated hydrocarbon having a hydroxyl group having 2 to 3 carbon atoms, and X represents a halogen atom. ]
A group to which a group represented by A quaternary ammonium derivative is obtained by reacting a hydrolyzed cuticle protein with a quaternary ammonium compound under alkaline conditions.

Specific examples of the quaternary ammonium compound include glycidyl ammonium salts such as glycidyl stearyl dimethyl ammonium chloride, glycidyl coconut alkyl dimethyl ammonium chloride, glycidyl lauryl dimethyl ammonium chloride, glycidyl trimethyl ammonium chloride, 3-chloro-2- Hydroxypropylstearyldimethylammonium chloride, 3-chloro-2-hydroxypropyl coconut oil alkyldimethylammonium chloride, 3-chloro-2-hydroxypropyllauryldimethylammonium chloride, 3-chloro-2-hydroxypropylethyldimethylammonium chloride, 3- 3-halo-2-hydroxy such as chloro-2-hydroxypropyltrimethylammonium chloride B pills ammonium salts, 2-chloroethyl trimethyl ammonium chloride such as 2-halo - ethylammonium salt, 3-halo, such as 3-chloropropyl trimethyl ammonium chloride - such as propyl ammonium salts.

Also in this quaternary ammonium derivative of the hydrolyzed cuticle protein, the number average molecular weight of the hydrolyzed protein portion is about 100 when the cuticle protein is hydrolyzed to its constituent amino acids, and the number of hydrolyzed cuticle proteins When the average molecular weight is greater than about 3,000, the hair may become stiff or the hair may become sticky under high humidity, and the peptide may associate during storage to cause turbidity or precipitation. Therefore, it is preferably about 100 to about 3,000, more preferably about 100 to about 500.

As the silylated derivative, at least a part of the terminal amino group of the hydrolyzed cuticle protein main chain and the amino group of the amino acid side chain may be represented by the following general formula (III):
[In the formula (III), R ⁵ represents an alkyl group having 1 to 3 carbon atoms, D is a bond, methylene, propylene, —CH ₂ OCH ₂ CH (OH) CH ₂ — or — (CH ₂ ) ₃ It is a group represented by OCH ₂ CH (OH) CH ₂ —. ]
A group to which a group represented by This silylated derivative can be hydrolyzed under alkaline conditions with cuticle protein and the following general formula (IV)

Wherein (IV), ^{R 5} represents an alkyl group having 1 to 3 carbon atoms. ]
Or the following general formula (V)

Wherein (V), ^{R 5} represents an alkyl group having 1 to 3 carbon atoms. ]
It is obtained by reacting a silylating agent represented by

In addition to the hydrolyzed cuticle protein in which the general formula (II) is bonded to an amino group, the silylated derivative used in the present invention includes a silicone resin that is a polymer of a peptide in which the general formula (II) is bonded to an amino group. Also included are those containing hydrolyzed cuticle protein.

Also in this silylated derivative of hydrolyzed cuticle protein, the number average molecular weight of the peptide portion is about 100 when the cuticle protein is hydrolyzed to its constituent amino acids, and the number average molecular weight of the hydrolyzed cuticle protein is about 100. If it is greater than 3,000, the hair may become stiff or the hair may become sticky under high humidity, and the peptide may associate during storage to cause turbidity or precipitation. It is preferably 100 to about 3,000, more preferably about 100 to about 500.

Examples of the alkyl glycerylated derivative include at least a part of the terminal amino group of the hydrolyzed cuticle protein main chain and the amino group of the amino acid side chain, represented by the following general formula (VI):

[In the formula (VI), R ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group. ]
A group to which a group represented by This alkylglycerylated derivative is hydrolyzed under alkaline conditions with cuticle protein and the following general formula (VII)

[In Formula (VII), R ⁶ represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, or a phenyl group. ]
It is obtained by reacting an alkyl glycerylating agent represented by the formula:

The temperature when the hydrolyzed cuticle protein and the alkyl glyceryl agent are reacted is preferably 30 ° C to 80 ° C, more preferably 40 ° C to 70 ° C. Below the above temperature, the reactivity between the hydrolyzed cuticle protein and the alkyl glyceryl agent becomes poor, and above the above temperature, the hydrolyzed cuticle protein is not suitable as a cosmetic base material because it causes remarkable coloring and unpleasant odor, Reactivity cannot be expected by increasing the heating temperature.

The reaction time for reacting the hydrolyzed cuticle protein with the alkyl glyceryl agent varies depending on the temperature, pH, and concentration of the hydrolyzed cuticle protein, but preferably 1 to 10 hours, more preferably 2 to 8 hours. When the reaction time is shorter than the above time, the unreacted alkyl glyceryl agent remains, and when the reaction time is longer than the above time, the hydrolyzed cuticle protein tends to be colored or unpleasant.

And also in this alkyl glycerylated derivative of the hydrolyzed cuticle protein, the number average molecular weight of the peptide portion is preferably about 100 to about 3,000 for the same reason as the hydrolyzed cuticle protein, about 100 More preferably, it is about ~ 500.

As the 2-hydroxyalkylated derivative, at least a part of the terminal amino group of the hydrolyzed cuticle protein main chain and the amino group of the amino acid side chain may be represented by the following general formula (VIII):

[In Formula (VIII), R ⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group. ]
A group to which a group represented by This 2-hydroxyalkylated derivative is hydrolyzed under alkaline conditions with the following cuticle protein and the following general formula (IX)

[In Formula (IX), R ⁷ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a phenyl group. ]
It is obtained by reacting a 2-hydroxyalkylating agent represented by the formula:

The temperature when the hydrolyzed cuticle protein and the 2-hydroxyalkylating agent are reacted is preferably 30 ° C to 80 ° C, more preferably 40 ° C to 70 ° C. Below the temperature, the reactivity between the hydrolyzed cuticle protein and the 2-hydroxyalkylating agent becomes poor. Above the temperature, the hydrolyzed cuticle protein produces a marked coloration and unpleasant odor, which is suitable as a cosmetic base material. In addition, the reactivity cannot be improved by increasing the heating temperature.

The reaction time for reacting the hydrolyzed cuticle protein with the 2-hydroxyalkylating agent varies depending on the temperature, pH and concentration of the hydrolyzed cuticle protein, but preferably 1 to 10 hours, more preferably 2 to 8 hours. preferable. When the reaction time is shorter than the above time, unreacted 2-hydroxyalkylating agent remains, and when the reaction time is longer than the above time, the hydrolyzed cuticle protein tends to cause coloring and unpleasant odor.

And also in the 2-hydroxyalkylated derivative of this hydrolyzed cuticle protein, the number average molecular weight of the peptide portion is preferably about 100 to about 3,000 for the same reason as the hydrolyzed cuticle protein, More preferably from about 100 to about 500.

Examples of the ester derivative of the hydrolyzed cuticle protein include an ester with an alcohol having 1 to 22 carbon atoms in the carboxyl group of the hydrolyzed cuticle protein, for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, lauryl ester, cetyl ester, Examples include 2-ethylhexyl ester, 2-hexyldecyl ester, stearyl ester, isostearyl ester, oleyl ester and the like.

This ester derivative is to be refluxed at the boiling point of the added lower alcohol for about 1 to 10 hours together with the alcohol to be esterified in the lower alcohol such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and the like. Obtained by. At this time, it is preferable to carry out under the condition that the liquid hardly contains water. When a large amount of water is contained, esterification does not proceed sufficiently. In order to promote esterification, it is preferable to add a small amount of an acid such as anhydrous hydrochloric acid or sulfuric acid as a catalyst.

The solution of the ester derivative of the hydrolyzed cuticle protein obtained as described above is decolorized with activated carbon or the like, or sodium hydroxide, potassium hydroxide or the like when an acid such as anhydrous hydrochloric acid or sulfuric acid is used as a catalyst. Neutralization with alkali, and in order to obtain an appropriate concentration, a treatment such as distillation of excess lower alcohol by distillation and filtration.

And also in this ester derivative of the hydrolyzed cuticle protein, the number average molecular weight of the peptide portion is preferably about 100 to about 3,000, for the same reason as the hydrolyzed cuticle protein, about 100 to about 3,000. More preferably, it is 500.

[Hair cosmetic form]
The hair cosmetic composition of the present invention is constituted by containing at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof, and 1,3-butylene glycol. For example, shampoo, hair conditioner, hair treatment, system treatment, hair mist, split hair coat, hair cream, permanent wave first and second agent, hair straightener, set lotion, hair wax, styling agent, hair dye , Hair dyes, liquid hair conditioners, hair nourishing and hair restoring agents, and the like.

The preferred range of the amount of the hydrolyzed cuticle protein and its derivative (the content in the cosmetic) as the component (A) of the present invention varies depending on the type of cosmetic and is particularly limited. Although it is not a thing, 0.05-20 mass% is preferable in cosmetics in many cases, and 0.5-10 mass% is especially preferable in many cases. When the amount in the cosmetic is less than the above range, the effect of repairing damaged hair, enhancing the tensile strength of hair, and providing moisture retention, smoothness, gloss, etc. are fully manifested. There is a risk that it will be impossible. Further, even if the blending amount of the hydrolyzed cuticle protein and its derivative exceeds the above range, the effect corresponding to the blended protein is not improved.

The preferred range of the blending amount (content in cosmetics) of 1,3-butylene glycol, which is component (B) of the present invention, into hair cosmetics varies depending on the type of cosmetics and is particularly limited. However, 3.5 to 10% by mass in cosmetics is often preferable, and 3.5 to 7% by mass is particularly preferable in many cases. When the blending amount in the cosmetic is less than the above range, there is a possibility that preferable effects such as moisturizing property, smoothness and gloss imparting when applied to the hair cannot be sufficiently exhibited. Moreover, even if the blending amount of 1,3-butylene glycol exceeds the above range, there is a risk of giving an unpleasant feel such as hair stickiness.

In addition to the hydrolyzed cuticle protein and its derivative as component (A) and 1,3-butylene glycol as component (B), the hair cosmetic of the present invention includes components that are usually used in cosmetics, such as oily Raw materials, surfactants, moisturizers, polymer compounds, antioxidants, drugs, protein hydrolysates other than cuticle proteins derived from wool and their derivatives, amino acids, pH adjusters, preservatives, thickeners, pigments and fragrances Further, a sequestering agent or the like can be appropriately blended.

Examples of oily raw materials include olive oil, coconut oil, macadamia nut oil, tea seed oil, castor oil, oils such as tri (caprin / capry) glyceryl, jojoba oil, carnauba wax, candelilla wax, lanolin, beeswax and other waxes, Hydrocarbons such as liquid paraffin, paraffin, petrolatum, ceresin, microcrystalline wax, squalane, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, cetyl alcohol, stearyl alcohol, isostearyl Higher alcohols such as alcohol, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, diisostearyl malate, tri-2-ethylhexanoin, methylpolysiloxa , Methyl phenyl polysiloxanes, silicones such as decamethylcyclopentasiloxane or the like.

Examples of surfactants include anionic surfactants such as higher fatty acid soaps, polyoxyethylene alkyl ether sulfates, acyl-N-methyl taurate salts, N-acyl amino acid salts, alkyl phosphate ester salts, and alkyltrimethyl chlorides. Cationic surfactants such as ammonium and dialkyldimethylammonium chloride, amphoteric surfactants such as alkyldimethylaminoacetic acid betaine, alkylamidoaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxyimidazolinium betaine, polyoxy Nonionic surfactants such as ethylene alkyl ether, polyethylene glycol fatty acid ester, polyhydric alcohol fatty acid ester, and polyether-modified silicone are listed.

The hair cosmetic composition of the present invention can be expected to have a high moisturizing effect on the hair, but if further effects are required, other moisturizing agents can be appropriately blended. Examples of such a humectant include sodium lactate, sodium pyrrolidone carboxylate, and sodium hyaluronate.

Examples of the polymer compound include carboxyvinyl polymer, sodium carboxymethyl cellulose, xanthan gum, polyvinyl alcohol, and polymer dimethylpolysiloxane.

Examples of the antioxidant include vitamin E, tannin, BHT (butylhydroxytoluene) and the like.

Examples of other drugs include hair-growth drugs, dandruff and itching drugs, and the like.

Examples of protein hydrolysates and derivatives thereof include protein hydrolysates such as milk protein, silk protein, wheat protein, rice protein, pea protein, collagen, keratin, soybean, sesame, conchiolin, marine collagen, and derivatives thereof. Can be mentioned.

Examples of amino acids include amino acids such as glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine, lysine, asparagine, aspartic acid, glutamine, glutamic acid, cystine, cysteine, methionine, tryptophan, proline, histidine, and derivatives thereof. Is mentioned.

Examples of the pH adjuster include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like.

Examples of the preservative include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and phenoxyethanol.

Examples of thickeners include gum arabic, gum tragacanth, cablo gum, guar gum, pectin, agar, quince seed, starch, alge colloid, xanthan gum, dextran, succinoglucan, collagen, gelatin, casein, albumin, carboxymethyl starch, methylcellulose , Ethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, sodium arginate, polyvinyl methyl ether, carboxyvinyl polymer, sodium polyacrylate, polyethylene acrylate, poly Acrylamide, cationic polymer, etc. It is below.

Examples of the dye include tar dyes, natural dyes, inorganic pigments, and polymer powders. Examples of the fragrances include natural fragrances, synthetic fragrances, and blended fragrances.

Examples of the sequestering agent include disodium edetate, phosphoric acid, ascorbic acid, gluconic acid, sodium polyphosphate, sodium metaphosphate, and the like.

The agent system of the hair cosmetic of the present invention is arbitrary, and any of a solution system, a solubilization system, an emulsification system, a gel system, a powder dispersion system, a water-oil two-layer system, and the like can be used. The component (A) and the component (B), and the optional blending component can be blended.

Next, the present invention will be described more specifically with reference to examples. However, this invention is not limited only to those Examples. The hydrolyzed cuticle protein and its derivatives used in Examples and Comparative Examples were produced according to the method disclosed in Patent Document 2. Further, in the following examples and comparative examples,% indicating the concentration of the solution or dispersion is mass%.

Example 1 and Comparative Examples 1-2
Three types of hair rinses shown in Table 1 were prepared, and the smoothness of the hair after treatment was evaluated. In Example 1, a hydrolyzed cuticle protein having an average number molecular weight of 448 and a cystine amount of 12.5 mol% as half cystine and 1,3-butylene glycol were blended, and Comparative Example 1 was blended with a hydrolyzed cuticle protein. In Comparative Example 2, instead of hydrolyzed cuticle protein, the number average molecular weight derived from wool is about 450, and the amount of cystine is 6.3 mol% as half cystine. It is a hair rinse containing a certain hydrolyzed keratin and 1,3-butylene glycol. In addition, the compounding amount of each component in Table 1 is based on mass%, and the component content is not solid content, and the solid content concentration is shown in parentheses after the component name. These also apply to Table 3, Table 5, Table 7, Table 8, Table 10, Table 12, Table 14, Table 16, and Table 17 showing the subsequent compositions.

* 1 is Promois WK (trade name) manufactured by Seiwa Kasei Co., Ltd.

Prior to the treatment with the hair rinse, damaged hair that was subjected to bleaching treatment to make the degree of hair damage constant was prepared as the hair for treatment. That is, a hair bundle having a length of about 15 cm and a weight of about 2 g was immersed in 0.5% sodium polyoxyethylene (3) lauryl ether sulfate heated to 40 ° C. and shaken with a heat-retaining shaker for 30 minutes. Thereafter, the hair bundle was washed for 5 minutes in running tap water. Next, as a bleaching treatment, this hair bundle was immersed in a 1: 1 (weight ratio) mixture of 6% hydrogen peroxide solution and 2% ammonia water for 30 minutes at 30 ° C., and then for 5 minutes in running tap water. Washing was performed, followed by immersion in ion exchange water at room temperature for 5 minutes for washing. Next, this hair bundle is immersed in a 0.1 M citric acid-0.2 M disodium hydrogen phosphate buffer solution at pH 3 for 5 minutes, rinsed in running tap water for 5 minutes, and immersed in ion exchange water for 5 minutes at room temperature for cleaning. Repeated twice. After this bleaching operation was repeated 5 times, the hair bundle was subjected to a hair rinse treatment.

The hair was cut out from the hair bundle of the damaged hair that had been bleached, and the root and the tip of the hair were aligned on a slide glass, and 20 hairs in a length of 4 cm and a width of 1 cm were fixed with a double-sided tape. Twelve slide glasses to which the hair was fixed were prepared, and those having a similar average friction coefficient before the treatment were divided into four pieces each for the above three types of hair rinse treatments.

For hair rinsing treatment, 0.5 g of hair rinsing is uniformly applied to each slide glass on which the hair is fixed, covered with a wrap film, heated in a constant temperature bath at 40 ° C. for 10 minutes, and then in running tap water. It was washed for 10 seconds and dried with a hair dryer. This hair rinse treatment was repeated 10 times, and then stored overnight in a constant humidity bath with a relative humidity of 40%, and the smoothness of the hair was measured.

The smoothness of the hair subjected to the above treatment was evaluated by measuring the friction force using a friction tester KES-SE manufactured by Kato Tech Co., Ltd. In this apparatus, smoothness (roughness) is expressed by the average deviation of the coefficient of friction felt by a friction element moving a certain distance on the surface of the sample. The unit is dimensionless, and the smaller the value, the “smooth”. It is shown that. The measurement of the friction force is 5 per slide glass on which hair is fixed under the conditions of humidity 43 ± 1%, temperature 20 ± 1 ° C., static friction load 25 gf, measurement distance 20 mm, measurement speed 0.5 mm / sec. Measured once. Since the slide glass which fixed 4 hairs per hair rinse is processed, the average value of the measurement result of 20 times was described as follows. The results are shown in Table 2.
0.106-0.110: △
0.101-0.105: ○
0.095-0.100: ◎

The average deviation of the coefficient of friction indicating the evaluation of the smoothness of the hair was the smallest for the hair treated in Example 1. From this result, in the hair rinse of Example 1, the hydrolytic cuticle protein and 1,3-butylene glycol, which are uniformly and strongly adsorbed on the hair surface, act synergistically to provide an excellent effect of smoothing the hair surface. The effect of blending hydrolyzed cuticle protein with hair rinse without 1,3-butylene glycol and hydrolyzed keratin with the same number average molecular weight as 1,3-butylene glycol It was clearly superior to hair rinses formulated in combination.

Example 2 and Comparative Examples 3-4
Three types of shampoos having the compositions shown in Table 3 were prepared, the hair was washed with each shampoo, and the gloss, moistness, smoothness and combability of the washed hair were evaluated.

In Example 2, a hydrolyzed cuticle protein having a number average molecular weight of 1254 and 1,3-butylene glycol are blended. In Comparative Example 3, the hydrolyzed cuticle protein is blended, and 1,3-butylene glycol is not blended. Comparative product 4 is a blank product containing only 1,3-butylene glycol and not hydrolyzed cuticle protein.

Prior to the treatment of the hair with the shampoo, three hair bundles each having a length of 18 cm and a weight of 1 g were prepared, and each hair bundle was used with 2 g of each of the shampoos of Example 2 and Comparative Examples 3 to 4. The bundle was washed, rinsed in running hot water and dried with a hair dryer. After repeating this washing, rinsing, and drying process with a hair dryer 10 times, the 10 best female panelists gave the best 2 points for hair gloss, moisture, smoothness, and combability. The good one was evaluated as 1 point, the third best one was evaluated as 0 point, and the average value was expressed as follows. The results are shown in Table 5.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 4, the hair treated with the shampoo of Example 2 in which hydrolyzed cuticle protein and 1,3-butylene glycol were blended was blended with hydrolyzed cuticle protein and 1,3-butylene glycol. Compared to the hair treated with the shampoo of Comparative Example 3 and the hair treated with Comparative Example 4 containing no hydrolyzed cuticle protein, the evaluation values were higher in all the evaluation items. When 3-butylene glycol was blended, it was clear that the effect of imparting gloss, moisture, smoothness and good combability to the hair was high.

Example 3 and Comparative Examples 5-6
Three types of hair setting agents having the compositions shown in Table 5 were prepared and evaluated for the gloss, moistness, elasticity and smoothness of the hair when applied to the hair.

In Example 3, N- [2-hydroxy-3- (3-dihydroxymethylsilylpropoxy) propyl] hydrolyzed cuticle protein and 1,3-butylene glycol, which are silylated derivatives of hydrolyzed cuticle protein having a number average molecular weight of 448 Comparative Example 5 is a comparative product in which the hydrolyzed cuticle protein silylated derivative is blended and 1,3-butylene glycol is not blended. Comparative Example 6 is blended only with 1,3-butylene glycol. The blank product does not contain a hydrolyzed protein silylated derivative.

* 2 is Promois WG (trade name) manufactured by Seiwa Kasei Co., Ltd.

The treatment of the hair with the hair setting agent was performed as follows. That is, three hair bundles having a length of 20 cm and a weight of 1 g are prepared, washed with a 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate, rinsed with water, and air-dried at room temperature. Wound around the rod. 2 ml each of the hair setting agents of Example 3 and Comparative Examples 5 to 6 were applied to the hair bundle wound around the rod and dried in a hot air dryer at 90 ° C. The hair after drying was removed from the rod, and 10 female panelists were allowed to evaluate the gloss, moistness, elasticity and smoothness of the hair according to the same evaluation criteria as in Example 2, and the average value was expressed as follows. The results are shown in Table 6.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 6, N- [2-hydroxy-3- (3-dihydroxymethylsilylpropoxy) propyl] hydrolyzed cuticle protein and 1,3-butylene glycol were treated with the hair setting agent of Example 3. The hair was blended with a silylated derivative of the hydrolyzed cuticle protein, and the hair was the same as the hair treated with the hair setting agent of Comparative Example 5 not blended with 1,3-butylene glycol, N- [2-hydroxy-3- (3-dihydroxymethylsilylpropoxy) propyl] hydrolyzed cuticle protein and 1,3, which have high evaluation values for gloss, moistness and smoothness, are silylated derivatives of hydrolyzed cuticle protein -When blended with butylene glycol, it has the effect of imparting luster, moisture and smoothness to the hair. To be excellent in was evident.

Example 4 and Comparative Examples 7-8
Three types of hair rinses having the composition shown in Table 7 were prepared, and each hair rinse was used for permanent wave-treated hair, and evaluated for gloss, moist feeling, elasticity, smoothness, and combability.

In Example 4, N- [2-hydroxy-3- (trimethylammonio) propyl] hydrochloride cuticle protein, which is a quaternary ammonium derivative of a hydrolyzed cuticle protein having a number average molecular weight of 448, and 1,3- Butylene glycol is blended, Comparative Example 7 is a comparative product that is blended with the quaternary ammonium derivative of the hydrolyzed cuticle protein and is not blended with 1,3-butylene glycol, and Comparative Example 8 is 1,3-butylene glycol. Is a blank product containing only the quaternary ammonium derivative and not containing the quaternary ammonium derivative of the hydrolyzed cuticle protein.

* 3 is a promotion SILK-1000 (trade name) manufactured by Seiwa Kasei Co., Ltd.

Prior to the treatment with the hair rinse, three hair bundles consisting of 30 hairs having a length of 15 cm are prepared, and the damaged hair subjected to the bleach treatment in the same manner as in Example 1 in order to make the damage degree of the hair constant. Produced. Next, 5 g each of the permanent wave first agent having the composition shown in Table 8 is uniformly applied to these hair bundles, allowed to stand at 25 ° C. for 15 minutes, washed in running tap water, and dried with a towel. Gently remove and apply 5g each of permanent wave second agent consisting of 6% aqueous sodium bromate solution, let stand at 25 ° C for 15 minutes, wash in running tap water, and lightly remove moisture with a towel. Further, it was dried with a hair dryer. A hair bundle obtained by repeating this bleaching treatment and permanent wave treatment twice was subjected to a hair rinse treatment.

About the hair rinse-treated hair, the glossiness, moisturization, elasticity, smoothness and combability of the hair are evaluated by 10 female panelists based on the same evaluation criteria as in Example 2, and the average value is expressed as follows: did. The results are shown in Table 9.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 9, the hair treated with the hair rinse of Example 4 containing N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed cuticle protein and 1,3-butylene glycol was used as described above. Compared to the hair treated with the hair rinse of Comparative Example 7 in which a quaternary ammonium derivative of hydrolyzed cuticle protein was blended and 1,3-butylene glycol was not blended, the beam was the same, but gloss and moist feeling The evaluation value concerning smoothness and combing property is high, and it is clear that when the quaternary ammonium derivative of the hydrolyzed cuticle protein is combined with 1,3-butylene glycol, the effect on hair is excellent. Met.

Example 5 and Comparative Examples 9-10
Three types of hair styling gels having the composition shown in Table 10 were prepared, and each hair styling gel was used for a washed hair bundle, and the gloss, moisture, smoothness, combing property and wave of the hair after the treatment were processed. The feel was evaluated.

In Example 5, N- [2-hydroxy-3-chloride] which is an N- (3-coconut oil alkyldimethylammonio-2-hydroxypropyl) derivative of a hydrolyzed cuticle protein having a hydrolyzed protein moiety having a number average molecular weight of 1254. ((Coconut oil alkyldimethylammonio) propyl) hydrolyzed cuticle protein and 1,3-butylene glycol were blended, and Comparative Example 9 was N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed A comparative product containing a degradation cuticle protein and no 1,3-butylene glycol. Comparative Example 10 contains only 1,3-butylene glycol and a quaternary ammonium derivative of hydrolyzed protein. There is no blank product.

* 4 is Acurin 22 (trade name) manufactured by Rohm and Hard (USA).

Prior to the treatment with the hair styling gel, three hair bundles having a length of 30 cm and a weight of 2.5 g were prepared, and these hair bundles were washed with a 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate. Rinse in running water and air dry at room temperature. The hair bundle was wound around a curling rod having a diameter of 25 mm, and 2 g each of the hair styling gels of Example 5 and Comparative Examples 9 to 10 were applied to the hair bundle wound around the rod and dried with a hair dryer. After drying, the hair bundle is removed from the rod, and the glossiness, moisturization, smoothness, combing and wave feel of the hair are evaluated by 10 female panelists according to the same evaluation criteria as in Example 2, and the average value is determined. It was written as follows. The results are shown in Table 11.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 11, treated with the hair styling gel of Example 5 containing N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed cuticle protein and 1,3-butylene glycol. The hair obtained was a hair styling gel of Comparative Example 9 containing N- [2-hydroxy-3- (coconut oil alkyldimethylammonio) propyl] hydrolyzed kerachi and no 1,3-butylene glycol. Compared to the treated hair, the gloss, moisture, smoothness, combing and wave feel are all highly evaluated, and the hydrolyzed cuticle protein N- (3-coconut oil alkyldimethylammonio-2-hydroxy) Propyl) derivative and 1,3-butylene glycol, The effect of more than if no case was clear that imparts to the hair.

Example 6 and Comparative Examples 11-12
Three types of hair styling agents (hair liquids) having the compositions shown in Table 12 were prepared and evaluated for hair gloss, moisture feeling, smoothness and combability when applied to hair.

In Example 6, the hydrolyzed cuticle protein ethyl ester having a number average molecular weight of 1254 in the hydrolyzed protein portion and 1,3-butylene glycol were blended, and Comparative Example 11 was blended with the hydrolyzed cuticle protein ethyl ester, Comparative product 12 does not contain 3-butylene glycol, and Comparative Example 12 is a blank product containing only 1,3-butylene glycol and no ester derivative of hydrolyzed cuticle protein.

* 5 is Plus Size L-53P (trade name) manufactured by Kyoyo Chemical Industry Co., Ltd.

Prior to the treatment with the hair styling agent, three hair bundles having a length of 15 cm and a weight of 1 g were prepared, washed with 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate, rinsed with hot water, and dried with a hair dryer. . The dried hair bundle was treated with 2 g of each of the hair styling materials of Example 6 and Comparative Examples 11 to 12, sufficiently dried with a hair dryer, and allowed to stand at room temperature for 1 hour. After standing for 1 hour, each hair bundle was washed with a 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate, rinsed with hot water, and dried with a hair dryer. After repeating this shampoo washing and hair styling treatment five times, 10 female panelists were allowed to evaluate the gloss, moistness, smoothness and combability of the hair according to the same evaluation criteria as in Example 2, and the average value thereof. It was written as follows. The results are shown in Table 13.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 13, hair treated with the hair styling agent of Example 6 containing hydrolyzed cuticle protein ethyl ester and 1,3-butylene glycol was blended with the ester derivative of hydrolyzed cuticle protein, and 1,3 -Compared with the hair treated with the hair styling agent of Comparative Example 11 containing no butylene glycol, the evaluation value is high in any of gloss, moisture, smoothness and combability of the hair, and the hydrolyzed cuticle protein It was clear that when the ester derivative and 1,3-butylene glycol were blended, the above effects were imparted to the hair when no 1,3-butylene glycol was blended.

Example 7 and Comparative Examples 13-14
Three types of first permanent wave agents having the compositions shown in Table 14 were prepared, and each permanent wave was added to the hair bundle using the first permanent wave agent and the second permanent wave agent consisting of a 6% sodium bromate aqueous solution. The hair was treated, and the gloss, moisture feeling and smoothness of the hair were evaluated.

In Example 7, a hydrolyzed cuticle protein having a number average molecular weight of 1254 and 1,3-butylene glycol were blended, and in Comparative Example 13, the hydrolyzed cuticle protein was blended and 1,3-butylene glycol was not blended. Comparative Example 14 is a blank product containing only 1,3-butylene glycol and no hydrolyzed cuticle protein.

The treatment of the hair with the first permanent wave agent was performed as follows. That is, hair with a length of 20 cm is washed with a 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether in advance, rinsed in running tap water, and air-dried at room temperature to obtain a hair bundle consisting of 40 hairs. They were made and wound around rods each having a length of 10 cm and a diameter of 1 cm. Apply 2 ml each of the permanent wave first agent of Example 7 and Comparative Examples 13 to 14 to the hair bundle wound around the rod, cover these hair bundles with wraps, leave them for 15 minutes, and then gently with running water After washing for 10 seconds, 2 ml of the second permanent wave agent was applied, covered with wrap, allowed to stand for 15 minutes, and then gently washed in running water for 30 seconds. Each rod is dried in a hot air dryer at 60 ° C., and after drying, the hair bundle is removed from the rod, and 10 panelists are allowed to evaluate the gloss, moisture and smoothness of the hair according to the same evaluation criteria as in Example 2. The average value was expressed as follows. The results are shown in Table 15.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 15, hair treated with the first agent for permanent wave of Example 7 containing hydrolyzed cuticle protein and 1,3-butylene glycol was formulated with the hydrolyzed cuticle protein, Compared with the hair treated with the first permanent wave agent of Comparative Example 13 containing no butylene glycol, the evaluation value is the same or higher in any of gloss, moisture and smoothness of the hair, and the hydrolyzed cuticle protein and It was clear that when 1,3-butylene glycol was blended with the first agent for permanent wave, a superior effect was imparted to the hair than when 1,3-butylene glycol was not blended.

Example 8 and Comparative Examples 15-16
Three types of oxidized hair dye first agent having the composition shown in Table 16 were prepared, and each oxidized hair dye first agent and the oxidized hair dye second agent shown in Table 17 below were mixed, After the hair was dyed, the gloss, moisture, smoothness and combability of the hair were evaluated.

In Example 8, a hydrolyzed cuticle protein having a number average molecular weight of 448 and 1,3-butylene glycol are blended, and Comparative Example 15 is a comparative product in which the hydrolyzed cuticle protein is blended but not 1,3-butylene glycol. Comparative Example 16 is a blank product containing only 1,3-butylene glycol and no hydrolyzed cuticle protein.

The oxidation hair dye second agent is common to Example 8 and Comparative Examples 15 to 16, as shown in Table 17.

The treatment of hair with the above oxidation hair dye was performed as follows. That is, three hair bundles having a length of 15 cm and a weight of 1 g were prepared, and these hair bundles were washed with 2% aqueous solution of polyoxyethylene (3) sodium lauryl ether sulfate, rinsed in running tap water, Air dried. To these hair bundles, an oxidized hair dye obtained by mixing the same amount of the oxidized hair dye first agent of Example 8 and the second agent, and an oxidized hair dye first agent of Comparative Examples 15 to 16 and Apply 2g each of the oxidized hair dye mixed with the same amount of the above second agent, then leave it for 30 minutes, rinse with hot water, then wash with 2% polyoxyethylene (3) sodium lauryl ether sulfate solution Further, it was rinsed in running tap water and dried with a hair dryer. Ten panelists evaluated the gloss, moisture feeling, smoothness and combability of the hair bundle after drying according to the same evaluation criteria as in Example 2, and the average values were expressed as follows. The results are shown in Table 18.
1.1-1.5: Δ
1.6-2.0: ○
2.1-2.5: ◎

As shown in Table 18, the hair dyed with the oxidized hair dye of Example 8 in which the hydrolyzed cuticle protein and 1,3-butylene glycol were blended was blended with the hydrolyzed cuticle protein and 1,3 -The evaluation value is the same or higher in terms of gloss, moisture, smoothness, and combability compared to the hair dyed with the oxidized hair dye of Comparative Example 15 containing no butylene glycol. When decomposing cuticle protein and 1,3-butylene glycol are blended in an oxidized hair dye, it is clear that the hair has superior effects to those obtained when 1,3-butylene glycol is not blended. there were.

Claims (4)

(A) at least one selected from the group consisting of hydrolyzed cuticle protein and derivatives thereof, 0.05 to 20% by mass, and (B) 1,3-butylene glycol 3.5 to 10% by mass Hair cosmetics. The hydrolyzed cuticle protein of component (A) is obtained by hydrolyzing wool-derived cuticle protein with hydrochloric acid or hydrochloric acid and thioglycolic acid, and the total amount of cystine and cysteine as constituent amino acids in amino acid analysis is 12 mol as half cystine. %, And the number average molecular weight of the peptide moiety is 100 to 3,000. The derivative of the hydrolyzed cuticle protein of component (A) is selected from the group consisting of acylated derivatives, quaternary ammonium derivatives, silylated derivatives, alkyl glycerylated derivatives, 2-hydroxyalkylated derivatives, ester derivatives of hydrolyzed cuticle proteins. The hair cosmetic according to claim 1 or 2, wherein the hair cosmetic is at least one selected. The hair cosmetic composition according to claim 1, wherein the content of 1,3-butylene glycol as the component (B) is 3.5 to 7% by mass.