JP2001039838A - Hair processing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject hair processing agent imparting gloss, moisture and firmness to hair, smoothing hair and improving running property of hair through a comb, capable of finishing satisfactory texture of hair by including a specific quaternary ammonium derivative. SOLUTION: This hair processing agent comprises, preferably 0.05-20 wt.% of a N-quaternary ammonium derivative of a partial decomposition product of oxidized keratin expressed by formula (R1-R3 are each a 1-20C alkyl or alkenyl; A is a 2-3C alkylene or hydroxyalkylene, R4 is an amino acid side chain of a peptide originating from keratin; b is 0 or 1; m is 2-20; n is 20-200; M is an alkali metal, alkali-earth metal, a lower alkanol-amine, etc.). The derivative is preferably obtained, for example, by hydrolyzing wool in an alkaline aqueous solution such as sodium hydroxide, etc., at 80 deg.C for 1-6 hours, and then oxidizing with an oxidant, adding an acid to the filtrate after filtration, precipitating insoluble part and then separating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hair treatment agent such as a hair rinse, a hair treatment, and a hair cream.
The present invention also relates to a hair treatment agent capable of improving the combability of hair by smoothing the hair and finishing the hair with a good feel.

[0002]

2. Description of the Related Art Conventionally, collagen, keratin, silk,
A hair cosmetic may contain an N-quaternary ammonium derivative of a protein hydrolyzate obtained by introducing a quaternary ammonium group into a hydrolyzed peptide obtained by hydrolyzing a protein derived from a natural product such as soybean or wheat. Is being done. This is because the N-quaternary ammonium derivatives of these hydrolyzed peptides have good sorption to hair, prevent hair damage, recover damaged hair, and smooth hair to improve combability. It has an improving effect, and furthermore, the peptide portion of the N-quaternary ammonium derivative of the hydrolyzed peptide is derived from a natural protein, has little irritation to hair and skin, and has high safety. is there.

[0003] Among the above-mentioned protein sources, keratin, in particular, has a high cystine content, and hydrolyzed keratin easily binds to cystine in hair keratin, and therefore has excellent sorption properties to hair, and has an effect of preventing hair damage. Due to the large effect of recovering damaged hair, N-quaternary ammonium derivatives of hydrolyzed keratin have already been used in various hair cosmetics including hair treatment agents.

However, hydrolyzed keratin and its N-quaternary ammonium derivative, which are generally used in hair cosmetics, have a peptide moiety having a number average molecular weight of 200-2.
Most of them have a good sorption property to the hair, but have a problem that they are inferior to N-quaternary ammonium derivatives of hydrolyzed collagen and hydrolyzed silk with respect to the ability to form a film and impart gloss. there were. The reason for limiting the molecular weight of the hydrolyzed keratin used in hair cosmetics to the above range is that if the molecular weight is too small, the ability to form a film is reduced, and the hair protecting effect is reduced. This is because when applied, the hair becomes stiff, the solubility in water is reduced, and the hair is apt to precipitate, or it becomes turbid or precipitates during storage in association with other components in the cosmetic formulation. .

[0005] The N-quaternary ammonium derivative of the hydrolyzed peptide has the effect of smoothing the hair and improving the combability of the hair, but has the same molecular weight as the effect of imparting the hair to the beam. Therefore, a high-molecular weight hydrolyzed peptide or a synthetic polymer is used in combination in order to maintain the hair beam and exhibit hair styling properties.

However, when these high-molecular-weight hydrolyzable peptides and synthetic polymers are used in combination, the feeling of the hair becomes stiff and the feel becomes poor. There was a problem that flaking (a phenomenon in which the formed film was cracked and peeled off like scales) was likely to occur.

[0007]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems in the prior art, and provides gloss and moisture to hair.
An object of the present invention is to provide a hair treatment agent that imparts a beam, smoothes hair, improves combability of hair, and can finish hair with a good feel.

[0008]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have found that the oxidized partially decomposed product of keratin represented by the following general formula (I) has the N-
The present inventors have found that a high-grade ammonium derivative can impart gloss, moisture, and beam to hair, and can improve the combability of hair by smoothing the hair and finish the hair with a good feel. It was just.

That is, the present invention provides a compound represented by the general formula (I)

[0010]

Embedded image[Wherein, R¹, R^Two, R^ThreeIs alkyl having 1 to 20 carbon atoms
Or an alkenyl group having 1 to 20 carbon atoms, or R¹
~ R^ThreeOne or two of which have 1 to 20 carbon atoms
Or an alkenyl group having 1 to 20 carbon atoms,
Alkyl group having 1 to 3 carbon atoms, hydroxy group having 1 to 3 carbon atoms
It is a alkyl group or a benzyl group. A has 2 to 3 carbon atoms
Alkylene group or hydroxyalkyl having 2 to 3 carbon atoms
Group, R ^FourIs the amino acid side chain of the keratin-derived peptide
And b is 0 or 1, m is 2 to 20, n is 20 to 2.
M is an alkali metal, an alkaline earth metal,
Ammonia, lower alkanolamine or lower alkyl
Amine (where m and n indicate the number of amino acids)
And does not indicate the order of the amino acid sequences.)]
N-quaternary anion of oxidized partial decomposition product of keratin represented by
Hair treatment agent characterized by containing a monium derivative
About.

The oxidized partial decomposition product of keratin is N-
In the general formula (I) representing a quaternary ammonium derivative, m
Are set to 2 to 20 and n is set to 20 to 200, as described later in detail, because the oxidized partial decomposition product of keratin N-
The peptide moiety of the quaternary ammonium derivative (ie,
The number-average molecular weight of the keratin partially decomposed product of keratin to about 2,000 to about 20,000, and the like. The number average molecular weight of the peptide moiety is the average number of peptides obtained from the total nitrogen content and the amino nitrogen content of the oxidized partial decomposition product of keratin, and the amino acid It is a value calculated based on the average molecular weight.

That is, the number average molecular weight is calculated by the following equation.

In the above formula, the reason why “18” is subtracted from the average amino acid molecular weight is that one molecule of water (H ₂ O) is dehydrated for one amino acid when a peptide bond is formed. , “18”, and finally “18” is added to the “OH” of the terminal COOH.
And the molecular weight “17 and 1” of “H” of terminal NH ₂ .

The average amino acid molecular weight of keratin is determined by determining the ratio of amino acids present by amino acid analysis, multiplying the ratio by the molecular weight of each amino acid, and summing the results. In the present specification, the average amino acid molecular weight is 1%.
24.

Oxidized degradation product of keratin (α-keratose)
So far, Japanese Patent Publication No. 61-60807 and Japanese Patent Publication No. 61-60
808, Japanese Patent Publication No. 2-38563,
JP-A-7-144213 and the like have proposed hair treatment agents and hair rinse agents in which an oxidized decomposition product of keratin is used in combination with a cationic surfactant, a cationic polymer, a polyphenol compound, and the like. The oxidized decomposed product of keratin used in is obtained by oxidizing keratin in an aqueous ammonia solution and then adjusting the pH to 4 with hydrochloric acid and precipitating it, so that the molecular weight distribution is wide,
Because it contains high molecular weight oxidatively decomposed products, it gives the hair a stiff feel due to the effect of high molecular weight oxidatively decomposed products when applied to hair, and tends to cause turbidity and sedimentation when blended in cosmetics, resulting in storage stability There was a problem of chipping.

On the other hand, the oxidized partially decomposed product of keratin represented by the general formula (I) used in the present invention,
Since the number-average molecular weight of the peptide moiety of the quaternary ammonium derivative is adjusted to about 2,000 to about 20,000, it does not give a stiff feeling when applied to hair, and has a narrow molecular weight distribution so that it can be contained in cosmetics. There is no danger of turbidity or sedimentation during storage, and storage stability is excellent.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The keratin used as the starting material for the N-quaternary ammonium derivative of the oxidized partially decomposed product of keratin represented by the general formula (I) used in the present invention includes, for example, wool, feathers, and hair. Keratin constituting horns, claws, hooves and the like can be used, but wool is particularly preferred from the viewpoint of easy availability.

The peptide moiety in the N-quaternary ammonium derivative of the oxidized partially decomposed product of keratin represented by the above general formula (I) has a number average molecular weight of about 2,000 to about 200.
The method for producing the peptide portion is, for example, hydrolyzing keratin with an alkali agent, oxidizing the decomposed solution with an oxidizing agent, and then adjusting the oxidized solution to pH 3
A method of generating by adjusting to に 4 is adopted. To explain this concretely, for example, wool is treated at 80 ° C. for 1 to 6 in an aqueous solution of an alkaline agent such as sodium hydroxide.
After hydrolyzing for a period of time, oxidize with an oxidizing agent such as aqueous hydrogen peroxide or formic acid. After filtration, add an acid such as hydrochloric acid or sulfuric acid to the filtrate to adjust the pH to 3-4 to precipitate insolubles. To separate. This insoluble material is washed with a saline solution or the like, and then neutralized and dissolved to a pH of 6 to 8 with a basic substance such as sodium hydroxide, ammonia water, or an alkanolamine to thereby dissolve the oxidized partially decomposed product of keratin. The peptide portion of the quaternary ammonium derivative is obtained as an aqueous solution in the form of an alkali salt, and is used as it is or after desalting and purification by ion exchange resin or electrodialysis, etc., and used as a raw material for the production of the N-quaternary ammonium derivative. . Further, the peptide portion can also be obtained by powdering the solution by spray-drying and freeze-drying a solution neutralized and dissolved with a basic substance.

Next, the oxidized partially decomposed product (peptide) of keratin obtained as described above is converted to an N-quaternary ammonium derivative. A known method for producing a quaternary ammonium derivative can be employed. That is, an aqueous solution of an alkali salt of an oxidized partial decomposition product of keratin obtained as described above is, for example, represented by the following general formula (II):

[0020]

Embedded image

Wherein R ¹ , R ² and R ^{3 each} have 1 to 2 carbon atoms.
An alkyl group of 0 or an alkenyl group having 1 to 20 carbon atoms,
Alternatively, one or two of R ^{1 to} R ³ have 1 to 1 carbon atoms.
20 alkyl groups or alkenyl groups having 1 to 20 carbon atoms, the rest being alkyl groups having 1 to 3 carbon atoms, hydroxyalkyl groups or benzyl groups having 1 to 3 carbon atoms, X is Cl,
Br, I, NO ₃ , ＳＯSO ₄ , R ⁵ OSO ₃ (R ⁵
Represents a lower alkyl group) or glycidyl ammonium salt represented by R ⁵ SO ₃ (R ⁵ is the same as described above)], or the following general formula (III)

[0022]

Embedded image

Wherein R ¹ , R ² , R ³ and X are the same as those in the above formula (II), and Y is Cl, Br, I
Represents a halogen atom, etc.]
Hydroxypropyl ammonium salt or the following general formula (VI)

[0024]

Embedded image

Wherein R ¹ , R ² , R ³ , X and Y are the same as those in the formula (III).
-Halogen propyl ammonium salt, or the following general formula (V)

[0026]

Embedded image

Wherein R ¹ , R ² , R ³ , X and Y are the same as those in the formula (III).
-N-quaternary ammonium derivative of oxidized partial decomposition product of keratin represented by the general formula (I) is obtained by reacting any one of -halogenethylammonium salt.

The N-quaternary ammonium derivative of the partially decomposed oxidized product of keratin represented by the above general formula (I) can be converted to a basic substance such as sodium hydroxide, aqueous ammonia or alkanolamine or an acid such as hydrochloric acid or sulfuric acid. It is obtained as an aqueous solution in the form of an alkali salt by adjusting the pH to 6 to 8, and used as it is or after desalting and purification by ion exchange resin or electrodialysis, etc., for use in the hair treatment agent of the present invention. The N-quaternary ammonium derivative of the partially decomposed product of keratin can be obtained as a powder by spray-drying and freeze-drying the solution.

In the peptide part of the general formula (I) representing the N-quaternary ammonium derivative of the partially decomposed product of keratin to be contained in the hair treatment composition of the present invention, m is 2 to 2
The reason why 0 and n are 20 to 200 is that the number average molecular weight of the peptide portion of the N-quaternary ammonium derivative of the oxidized partial decomposition product of keratin is about 2000 to about 20,000, and that This is based on the fact that about one cysteine is contained, and the cysteine moiety is oxidized to form a moiety indicated by m.

The hair treatment composition of the present invention includes, for example, hair rinses, hair treatments, PPT (polypeptide) treatments, hair creams, hair styling gels, hair styling foams and the like.

The content of the N-quaternary ammonium derivative of the oxidized partially decomposed product of keratin represented by the general formula (I) in the hair treatment composition of the present invention (the amount incorporated into the hair treatment composition) is Depending on the method of use of the hair treatment agent, such as a type that is washed away after application and a type that is not washed away, 0.05 to 20% by weight of the hair treatment agent is preferable, and particularly 0.5% by weight.
-15% by weight is preferred. This is because when the content of the N-quaternary ammonium derivative of the oxidized partially decomposed product of keratin represented by the general formula (I) in the hair treatment agent is smaller than the above range, the effect of giving hair a sufficient effect is obtained. In addition to being unable to exert its effect, there is a possibility that the effect of imparting gloss and moisture to the hair may be reduced, and conversely, in a hair treatment agent of an N-quaternary ammonium derivative of an oxidized partially decomposed product of keratin represented by the general formula (I) When the content in is more than the above range,
This is because the hair may have a stiff or sticky feeling.

The hair treatment composition of the present invention is prepared by using an N-quaternary ammonium derivative of an oxidized partially decomposed product of keratin represented by the general formula (I) as an essential component. Of the oxidized partial decomposition product of keratin
Other components can be appropriately added as long as the properties of the quaternary ammonium derivative are not impaired.

As such a component, for example, polyoxyethylene alkyl (C 14-14) ether (7EO) (EO is ethylene oxide, EO
Indicates the number of moles of ethylene oxide added), polyoxyethylene octyl phenyl ether,
Polyoxyethylene oleyl ether, polyoxyethylene glyceryl oleate, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene cetyl stearyl diether, polyoxyethylene sorbitol lanolin (40EO), polyoxyethylene nonyl phenyl ether, poly Nonionic surfactants such as oxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxypropylene stearyl ether, alkyl glycoside, and alkyl polyglycoside; Stearyltrimethylammonium chloride, Cetyltrimethylammonium chloride, Cetos chloride Allyltrimethylammonium, stearylbis (diethylene glycol) hydroxyethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium bromide, tri [polyoxyethylene (5EO)] stearylammonium, stearyldimethylbenzylammonium chloride, behenyltrimethylammonium bromide Cetyltrimethylammonium iodide, oleylbenzyldimethylammonium chloride, oleylbis [polyoxyethylene (15EO)] methylammonium chloride, polyoxypropylenemethyldiethylammonium chloride, mink oil alkylamidopropyldimethylhydroxyethylammonium chloride, γ-gluconamide chloride Propyldimethylhydroxyammonium, alkylpyri Synthesis of cationic surfactants such as dinium salts, cationic polymers such as cationized cellulose, cationized hydroxyethylcellulose, cationized guar gum, polydiallyldimethylammonium chloride, polyvinylpyrrolidone and polyethyleneimine; amphoteric polymers and anionic polymers Polymer, diethanolamide isostearate, monoethanolamide undecylenate, diethanolamide oleate, tallow fatty acid monoethanolamide, hardened tallow fatty acid diethanolamide, stearic acid diethanolamide, stearic acid monoethanolamide, myristate diethanolamide, coconut oil alkyl ethanol Amide, coconut oil alkyl diethanolamide, lauric acid isopropanolamide, lauric acid ethanolamide Thickeners such as lauric acid diethanolamide, lanolin fatty acid diethanolamide, waxes, paraffins, fatty acid esters, glycerides, oils and fats such as animal and vegetable oils, animal and plant extracts, collagen, keratin, fibroin, sericin, casein, soybean, wheat, Hydrolyzed peptides and derivatives of proteins derived from animals, plants, and microorganisms such as corn, potatoes, rice (rice bran), yeast, and mushrooms, derivatives thereof, polysaccharides and derivatives thereof, propylene glycol, 1,3-butylene glycol, ethylene glycol, and glycerin , Wetting agents such as polyglycerin and polyethylene glycol, lower alcohols such as ethanol, methanol, propanol and isopropanol, cetanol, stearyl alcohol, isostearyl alcohol, iso- Higher alcohols such as tyl alcohol, oleyl alcohol, and behenyl alcohol; and tertiary alcohols such as dimethylaminoethylamide laurate, diethylaminoethylamide myristate, dimethylaminopropylamide stearate, dimethylaminopropylamide isostearate, and dimethylaminopropylamide behenate. Primary amidoamine compound, L-aspartic acid, sodium L-aspartate, DL-alanine, L-arginine, glycine, L-glutamic acid,
Examples include amino acids such as L-cysteine and L-threonine, and silicone derivatives such as linear or cyclic methylpolysiloxane, methylphenylpolysiloxane, and amino-modified silicone.

[0034]

The hair treatment composition of the present invention contains an N-quaternary ammonium derivative of a partially decomposed product of oxidized keratin represented by the general formula (I).
The N-quaternary ammonium derivative of the oxidized partially decomposed product of keratin represented by the formula (1) has a better sorption property to hair than the conventional N-quaternary ammonium salt of hydrolyzed keratin, and gives gloss and moisture to hair. By imparting a beam, the hair is smoothed, the combability of the hair is improved, and the hair can be finished with a good feel.

[0035]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. Prior to the examples, the oxidized partially decomposed product of keratin represented by the general formula (I) was N-
A method for producing a quaternary ammonium derivative will be described as a reference example.
In the following Reference Examples, Examples, Comparative Examples, and the like, all percentages indicating the concentration of a solution, a dispersion, and the like are% by weight.

REFERENCE EXAMPLE 1 1000 g of water and 25 g of sodium hydroxide were placed in a beaker having an internal volume of 5 liters, and 250 g of crushed wool was stirred.
Was added and stirring was continued at 80 ° C. for 5 hours to hydrolyze the wool. After the hydrolysis, the mixture was cooled to room temperature, 150 g of 35% hydrogen peroxide solution was added, stirring was continued for 1 hour, and the mixture was left standing for 24 hours to oxidize the decomposition solution. After completion of the oxidation, the solution was filtered to remove insolubles, and 40 g of 36% hydrochloric acid was added to the filtrate to adjust the pH of the solution to 3.5, and the insolubles were separated as floating precipitates. The lower aqueous layer was removed, and the insolubles were removed with 0.5% saline 30.
After washing twice with 0 g, the insolubles were dissolved in an aqueous sodium hydroxide solution after the washing, the pH was adjusted to 7, and the solid concentration was 20%.
Thus, 600 g of an aqueous solution of sodium salt of oxidized partial decomposition product of keratin was obtained. The sodium salt of the oxidized partial decomposition product of keratin thus obtained had a number average molecular weight of 3562.

Next, 500 g of an aqueous sodium salt solution of the oxidized partially decomposed product of keratin was placed in a beaker having an internal volume of 2 liters, and a 20% aqueous sodium hydroxide solution was added thereto.
H was adjusted to 9.5. This solution was heated with stirring to obtain 40
, And 22 g of a 75% aqueous solution of glycidyltrimethylammonium chloride (3 equivalents to the amount of amino nitrogen of the sodium salt of the oxidized partially decomposed product of keratin) was added dropwise thereto over 1 hour. For 4 hours to complete the reaction. The reaction solution is diluted with diluted hydrochloric acid to pH
7, which was desalted by electrodialysis, and then concentrated under reduced pressure to obtain an N-oxidized partially decomposed product of keratin having a solid concentration of 20%.
480 g of an aqueous solution of a sodium salt of a (3-trimethylammonio) -2-hydroxypropyl derivative was obtained.

REFERENCE EXAMPLE 2 1000 g of water and 20 g of sodium hydroxide were placed in a beaker having an inner volume of 5 liters, and 250 g of crushed wool was stirred.
Was added and stirring was continued at 80 ° C. for 5 hours to hydrolyze the wool. After the hydrolysis, the mixture was cooled to room temperature, 150 g of 35% hydrogen peroxide solution was added, stirring was continued for 1 hour, and the mixture was left standing for 24 hours to oxidize the decomposition solution. After completion of the oxidation, the solution was filtered to remove insolubles, and 35 g of 36% hydrochloric acid was added to the filtrate to adjust the pH of the solution to 3.5, and the insolubles were separated as floating precipitates. The lower aqueous layer was removed, and the insolubles were removed with 0.5% saline 30.
After washing twice with 0 g, the insolubles were dissolved in an aqueous sodium hydroxide solution after the washing, the pH was adjusted to 7, and the solid concentration was 20%.
Thus, 625 g of an aqueous solution of sodium salt of a partially decomposed product of oxidized keratin was obtained. The sodium salt of the oxidized partially decomposed product of keratin thus obtained had a number average molecular weight of 4,219.

Next, 500 g of an aqueous sodium salt solution of the oxidized partially decomposed product of keratin was put into a beaker having an internal volume of 2 liters, and a 20% aqueous sodium hydroxide solution was added thereto.
H was adjusted to 9.5. This solution was heated with stirring to obtain 40
C., and 71 g of a 35% aqueous solution of 3-chloro-2-hydroxydimethyl coconut oil alkylammonium chloride (2 equivalents based on the amount of amino nitrogen of the sodium salt of the partially decomposed product of keratin) was added thereto over 2 hours. And dropped. During this time, a 20% aqueous sodium hydroxide solution was added to maintain the pH of the reaction solution at 9.5. After completion of the dropwise addition, stirring was further continued at 45 ° C. for 3 hours to complete the reaction. The reaction solution was adjusted to pH 7 with dilute hydrochloric acid, the concentration was adjusted, and a sodium salt aqueous solution of an N- (3-coconut alkyldimethylammonio) -2-hydroxypropyl derivative of an oxidized partially decomposed product of keratin having a solid concentration of 20% was used. Was obtained 598 g.

REFERENCE EXAMPLE 3 1000 g of water and 22 g of sodium hydroxide were placed in a beaker having an internal volume of 5 liters, and 250 g of crushed wool was stirred.
Was added and stirring was continued at 80 ° C. for 3 hours to hydrolyze the wool. After the hydrolysis, the mixture was cooled to room temperature, 150 g of 35% hydrogen peroxide solution was added, stirring was continued for 1 hour, and the mixture was left standing for 24 hours to oxidize the decomposition solution. After completion of the oxidation, the solution was filtered to remove insolubles, and 36 g of 36% hydrochloric acid was added to the filtrate to adjust the pH of the solution to 3.5, and the insolubles were separated as floating precipitates. The lower aqueous layer was removed, and the insolubles were reduced to 0.5% saline 35.
Washed twice with 0 g. After washing, the insolubles were dissolved in a 20% aqueous sodium hydroxide solution, the pH was adjusted to 7, and 660 g of an aqueous solution of a sodium salt of an oxidized partially decomposed product of keratin having a solid content of 20% was obtained. The sodium salt of the oxidized partial decomposition product of keratin thus obtained has a number average molecular weight of 4
040.

Next, 500 g of an aqueous solution of the sodium salt of the oxidized partially decomposed product of keratin was placed in a beaker having an internal volume of 2 liters, and the pH was adjusted to 9.5 by adding a 20% aqueous sodium hydroxide solution. This solution was heated with stirring to obtain 4
0 ° C., in which a 35% aqueous solution of 3-chloro-2-hydroxydimethyllauryl ammonium chloride 5
1 g (2 equivalents to the amount of amino nitrogen of the sodium salt of the oxidized partially decomposed product of keratin) was added dropwise over 2 hours.
During this time, a 20% aqueous sodium hydroxide solution was added to keep the pH of the reaction solution at 9.5. After completion of the dropwise addition, stirring was further continued at 45 ° C. for 4 hours to complete the reaction. The pH of the reaction solution was adjusted to 3.5 by adding 36% hydrochloric acid to the reaction solution, and the insoluble matter was separated as a floating precipitate. The lower aqueous layer was removed, and the insolubles were washed twice with 350 g of 1% saline. After washing, the insolubles were adjusted to pH 7 with triethanolamine,
By adjusting the concentration, N- (3-lauryldimethylammonio)-of the partially decomposed product of oxidized keratin having a solid concentration of 20%
450 g of an aqueous solution of a triethanolamine salt of a 2-hydroxypropyl derivative was obtained.

Example 1 and Comparative Examples 1 and 2 Three types of hair rinses having the compositions shown in Table 1 were prepared, and each of the hair rinses was used for shampoo-washed hair. , Moisture, smoothness, combability and less stiffness were evaluated. In addition, the compounding amount of each component in Table 1 is based on parts by weight, and when the compounding amount is not the solid content, the solid content concentration is shown in parentheses after the component name. These are the same in Table 3, Table 5, Table 7, Table 9, and the like showing the following compositions. In addition, although the expression is referred to as a blending amount here, this is an amount at the time of preparation, and is quantitatively the same as the content after preparation.

In Example 1, the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin produced in Reference Example 1 was used. Comparative Example 2 uses a N- (3-trimethylammonio) -2-hydroxypropyl derivative of hydrolyzed keratin having a molecular weight of 1,000.
Of hydrolyzed keratin having a number average molecular weight of 1000 used in
-(3-trimethylammonio) -2-hydroxypropyl derivative and hydrolyzed collagen having a number average molecular weight of 4000 are used in combination.

[0044]

[Table 1] * 1: Promois WK-HQ (trade name) manufactured by Seiwa Kasei Co., Ltd.

Prior to the hair rinse treatment, three hair bundles each having a length of 15 cm and a weight of 1 g were prepared, washed with a commercially available shampoo containing no hydrolyzed peptide or a derivative thereof, and rinsed with hot water. The hair rinses of Example 1 and Comparative Examples 1-2 were respectively applied to the washed hair bundles for 2 times.
Treat with each g and rinse with hot water. After repeating this shampoo washing and hair rinsing treatment 5 times,
Moistness, smoothness, combability and low stiffness were given to 10 female panelists, the best was [2 points], the second best was [1 point], and the bad was [0].
Point].

Next, 14 hairs were extracted from each of the hair bundles after the sensory evaluation, and an evaluation test of the hair beam was performed in the following manner. That is, a knot (knot) is made lightly at a substantially central portion of the hair extracted from each of the hair bundles as shown in FIG. 1, and a 10 g weight is attached to the tip of the hair (the lower side in FIG. 1). The hair was suspended in a humidity chamber at a humidity of 58% for 1 minute, and then the weight on the hair tip side was removed. The knots formed on the hair were photographed with a scanning electron microscope, and the size (major axis) of the hair knots was measured with an image processing device based on the photographed image. JSM-5800LV, and SemaFore (trade name) made by the company for image processing]. The size of the knots of 14 hairs was measured for each sample, the results of the four samples, two of the largest measurement results and two of the smallest measurement results, were averaged, and the average of the ten results was obtained. Was taken as the average value of the knot size of each sample. Table 2 shows the average value of the knot size of each sample as the evaluation result of the hair beam.

[0047]

[Table 2]

As shown in Table 2, the hair treated with the hair rinse of Example 1 had a gloss, moisture, smoothness, combability, and stiffness that was higher than the hair treated with the hair rinse of Comparative Examples 1-2. The evaluation value was high in any of the evaluation items having a small feeling. As is clear from the results, the hair rinse of Example 1 containing the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin was obtained by using the conventional hydrolyzed keratin. The hair rinse of Comparative Example 1 containing an N- (3-trimethylammonio) -2-hydroxypropyl derivative and the N- (3-trimethylammonio) -2-hydroxypropyl derivative of hydrolyzed keratin in combination with hydrolyzed collagen Compared to the hair rinse of Comparative Example 2, the effect of imparting luster and moisture to the hair and improving the combability of the hair was excellent. In particular, in the evaluation of smoothness, all the panelists evaluated that the hair treated with the hair rinse of Example 1 had a smooth feel despite having a smooth feel.

The size of the knot indicating the evaluation result of the hair beam was determined in the Example containing the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin. The hair treated with the first hair rinse was the largest, and the hydrolyzed keratin N- (3
N- (3-trimethylammonio) -2-hydroxypropyl derivative of hydrolyzed keratin about 1.3 times that of hair treated with the hair rinse of Comparative Example 1 containing -trimethylammonio) -2-hydroxypropyl derivative About 1.17 times that of the hair treated with the hair rinse of Comparative Example 2 in which keratin was used in combination with hydrolyzed collagen, and sodium of an N- (3-trimethylammonio) -2-hydroxypropyl derivative of a partially decomposed product of keratin. It was clear that the salt had an excellent effect of imparting a beam to the hair.

Example 2 and Comparative Examples 3 to 4 Three types of PPT (polypeptide) treatments having the compositions shown in Table 3 were prepared, and each of the PPT treatments was used for washed hair to compare hair beams. The hair was examined for luster, moisture, smoothness, combability, and ease of cohesion (hair styling).

In Example 2, the sodium salt of the N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin prepared in Reference Example 2 was used. Then number average molecular weight 100
In Comparative Example 4, a hydrolyzed collagen having a number average molecular weight of 2,000 was used as the N- (3-coconut alkyl dimethyl ammonium). E) A 2-hydroxypropyl derivative is used.

[0052]

[Table 3] * 2: Seiko Chemical Co., Ltd., Promois WK-HCAQ (trade name) * 3: Seiwa Chemical Co., Ltd., Promois W-52CAQ (trade name) * 4: Fuji Chemical Co., Ltd., Fuji Chemical HEC CF-Y (product name)

Prior to the treatment by the PPT treatment, three hair bundles each having a length of 15 cm and a weight of 1 g were prepared, washed with sodium polyoxyethylene (3) lauryl ether sulfate, and rinsed with hot water. This hair bundle was treated with 2 g of each of the PPT treatments of Example 2 and Comparative Examples 3 and 4, rinsed with hot water and dried with a hair dryer. Gloss, moisture, smoothness, beam, combability and unity (hair styling) of the hair of this hair bundle
Was evaluated by the same evaluation criteria as in Example 1 by 10 female panelists. Next, each hair bundle after the sensory evaluation was 1
Four hairs were extracted and subjected to a hair beam evaluation test in the same manner as in Example 1. The results are shown in Table 4 as average values.

[0054]

[Table 4]

As is evident from the results shown in Table 4, in all of the evaluation items such as gloss, moisture, smoothness, combability and cohesion of the hair, the majority of the panelists P of Comparative Examples 3 and 4
He said that it was better than PT treatment,
The PPT treatment of Example 2 containing the sodium salt of an N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative of oxidized partial decomposition product of keratin was conventionally used generally as a PPT treatment agent. Containing hydrolyzed keratin N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative and hydrolyzed collagen N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative Compared to the PPT treatments of Comparative Examples 3 and 4, the effect of imparting gloss, moisture, and smoothness to the hair is excellent, and the effect of facilitating hair cohesion and facilitating hair styling is excellent. It was clear. In particular, most of the panelists who answered that the PPT treatment of Example 2 was excellent showed that the hair treated with the PPT treatment of Example 2 had no stickiness and was supple despite the presence of a beam. Was.

The size of the knot, which indicates the evaluation result of the hair beam, is determined by including the sodium salt of the N- (3-coconut alkyldimethylammonio) -2-hydroxypropyl derivative of oxidized partial decomposition product of keratin. P of Example 2
The hair treated with the PT treatment was the largest, and the hair treated with the PPT treatment of Comparative Example 3 containing the N- (3-cocoalkyldimethylammonio) -2-hydroxypropyl derivative of hydrolyzed keratin was about 1. About 1.7 times that of the hair treated with the PPT treatment of Comparative Example 4 containing the N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative of hydrolyzed collagen, which is keratin N- (3-coconut oil alkyl dityl ammonium) of partially oxidized decomposition product of
It was clear that the sodium salt of the -2-hydroxypropyl derivative had an excellent effect of imparting hair to the hair.

Example 3 and Comparative Examples 5 to 6 Three types of hair styling gels having the compositions shown in Table 5 were prepared, and the washed hair tresses were treated with each of the hair styling gels. Gloss, moisture, beam,
Combability, stiffness, and wave feel were evaluated.

In Example 3, N- (3-trimethylammonio) of the oxidized partially decomposed product of keratin produced in Reference Example 1 was used.
In Comparative Example 5, N-methacryloyloxyethyl N, N
-Dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer liquid [manufactured by Mitsubishi Chemical Corporation, Yuka Former SM (trade name)] was used. In Comparative Example 6, hydrolyzed collagen having a number average molecular weight of 1,000 was used. An N- (3-trimethylammonio) -2-hydroxypropyl derivative is used.

[0059]

[Table 5] * 5: Mitsubishi Chemical Corporation, Yuka Former SM (trade name) * 6: Seiwa Chemical Co., Ltd., Promois W-42Q (trade name) * 7: Rohm and Haas Co., Ltd., Aculin 22 (trade name) * 8: Secept H (trade name) manufactured by Seiwa Kasei Co., Ltd.

Prior to the treatment with the above hair styling gel, a hair bundle having a length of 30 cm and a weight of 2.5 g was previously washed with a 2% aqueous solution of sodium polyoxyethylene (3) lauryl ether sulfate and rinsed in running tap water to room temperature. And air-dried. This hair bundle was wound around a hair curling rod having a diameter of 25 mm, and the hair bundle wound around the rod was wound into Example 3
2 g of each of the hair styling gels of Comparative Examples 5 and 6 was separately applied, and dried with a hair dryer.
After drying, the hair bundle was removed from the rod, and the gloss, moistness, beam, smoothness, combability, low stiffness and wave feeling of the hair were evaluated by 10 female panelists according to the same evaluation criteria as in Example 1. It was evaluated. Table 6 shows the results as an average value of 10 persons.

[0061]

[Table 6]

As shown in Table 6, the hair styling gel of Example 3 containing the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin was obtained from N- Compared with the hair styling gel of Comparative Example 5 containing a methacryloyloxyethyl N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate copolymer solution, in the evaluation items other than the hair beam, All of the evaluation values were high, and N- (3-
Sodium salt of trimethylammonio) -2-hydroxypropyl derivative sorbs to hair, shines and moisturizes hair,
It was found to give smoothness, combability and good wave feel. In addition, the hair styling gel of Example 3 was obtained by hydrolyzing collagen N- (3-
Compared to the hair styling gel of Comparative Example 6 containing the (trimethylammonio) -2-hydroxypropyl derivative, the hair shine, moistness, stiffness, suppleness, combability, and wave feel were all reduced. The evaluation value is high, and the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin contained in the hair styling gel of Example 3 is said to have a high film-forming effect. Sorbs better to the hair than the N- (3-trimethylammonio) -2-hydroxypropyl derivative of hydrolyzed collagen,
It was found to impart moisture, beam, smoothness and good combability.

As for the feeling of stiffness and the feeling of wave, the hair treated with the hair styling gel of Example 3 was soft by all the panelists, while the hair bundle treated with the hair styling gel of Comparative Example 6 was soft. Has a very hard feel and has a tough feeling,
It was clear that the sodium salt of the N- (3-trimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin contained in the hair styling gel of Example 3 gave a more natural feel. .

Example 4 and Comparative Example 7 Two kinds of hair creams having the compositions shown in Table 7 were prepared, and each of the hair creams was used for washed hair to obtain gloss, moisture, paste, combability and the like of the hair. The feeling of touch was examined.

In Example 4, the sodium salt of an N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative of the oxidized partially decomposed product of keratin produced in Reference Example 2 was used. An N- (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative of hydrolyzed keratin having a molecular weight of 1,000 and hydrolyzed collagen having a number average molecular weight of 2,000 are used in combination.

[0066]

[Table 7] * 9: Promois WK-HCAQ (trade name) manufactured by Seiwa Kasei Co., Ltd. * 10: Promois W-52 (trade name) manufactured by Seiwa Kasei Co., Ltd. * 11: Ayakol manufactured by Seiwa Kasei Co., Ltd. HC-1209 (trade name) * 12: KF96 350CS (trade name) manufactured by Shin-Etsu Silicone Co., Ltd.

Prior to the treatment with the hair cream, a hair bundle having a length of 30 cm and a weight of 2.5 g was previously washed with a 2% aqueous solution of sodium polyoxyethylene (3) lauryl ether sulfate, rinsed in running tap water, and then washed at room temperature. Air dried. Example 4 and Comparative Example 7 each containing 2 g of this hair bundle
Was applied uniformly and the hair bundle was dried with a hair dryer. Ten female panelists were asked to evaluate which of Example 4 and Comparative Example 7 was better in terms of gloss, moistness, stiffness, smoothness, combability and feel of the dried hair. Table 8 shows the results.

[0068]

[Table 8]

As shown in Table 8, the hair was treated with the hair cream of Example 4 for the majority of the panelists in any of the evaluation items of gloss, moisture, beam, smoothness, combability, and hand feeling of the hair. Evaluated that it was better than the hair treated with the hair cream of Comparative Example 7, and found that N-
The sodium salt of the (3-coconut oil alkyldimethylammonio) -2-hydroxypropyl derivative was N- (3-hydrogenated keratin contained in the hair cream of Comparative Example 7).
Than coconut oil alkyl dimethyl ammonium) -2-hydroxypropyl derivative in combination with hydrolyzed collagen,
It was clear that the effect of imparting gloss, moistness, beam, smoothness and combability to hair was excellent.

Regarding the feeling of touch, the majority of the panelists showed that the hair treated with the hair cream of Example 4 had a supple hair while the hair treated with the hair cream of Comparative Example 7 had a slightly hard feel. Had to be evaluated.

Example 5 and Comparative Example 8 Two types of foam bases for mousse hair styling foams having the compositions shown in Table 9 were prepared, and the foam base and the propellant were each filled in a spray container [foam base: Propellant = 89:11 (weight ratio)], and the hair was treated with each of the mousse-shaped hair styling foams to evaluate gloss, moisture, beam, suppleness, and combability.

In Example 5, a triethanolamine salt of an N- (3-lauryldimethylammonio) -2-hydroxypropyl derivative of an oxidized partially decomposed product of keratin produced in Reference Example 3 was used. In Comparative Example 8, an acrylic resin was used. An alkanolamine solution is used.

[0073]

[Table 9] * 13: Plus size L-6740B (trade name) manufactured by Yoyo Kagaku Kogyo Co., Ltd. * 14: SH3749 (trade name) manufactured by Toray Dow Corning Co., Ltd. * 15: Seiwa Chemical Co., Ltd., Secept H (product name)

With respect to the above mousse hair styling foam, 10 female panelists were treated once a day with the mousse hair styling foam of Comparative Example 8 for the first 5 days, and for the next 5 days Moist hair was treated with a styling foam.

The treatment was carried out by taking 2 to 5 g of a mousse hair styling foam on the palm (the amount varies depending on the amount of hair), applying it to the hair by hand rubbing, and drying it with a hair dryer.

After a period of use of 10 days (ie after 5 days of use of the mousse hair styling foam of Example 5), the ease of cohesion of the hair, the gloss, the moisture, the beam, the combability and the feel of the hair are: A question was asked whether the mousse hair styling foam of Comparative Example 8 was better, worse, or unchanged than when it was used. Table 10 shows the results.

[0077]

[Table 10]

As shown in Table 10, the oxidized partially decomposed product of keratin was N- (3-lauryldimethylammonio) -2.
-After using the mousse-shaped hair styling foam of Example 5 containing the triethanolamine salt of a hydroxypropyl derivative, the hair was easier to unite, shiny, moisturized, glued, combed, and squeezed than before use. Many people answered that the feel was improved, and the triethanolamine salt of N- (3-lauryldimethylammonio) -2-hydroxypropyl derivative of oxidized partial decomposition product of keratin was absorbed on the hair, It was apparent that the compound had an effect of imparting easiness of cohesion, luster, moisture, and a beam, improving combability, and improving the feeling of touch.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing knots (knots) of hair at the time of evaluating a beam of hair.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Sakiko Uchida 1-2-1 Fukuichi-cho, Higashi-Osaka-shi, Osaka F-term (reference) 4C083 AC012 AC102 AC122 AC152 AC182 AC242 AC302 AC352 AC422 AC442 AC482 AC542 AD092 AD162 AD282 AD441 AD442 AD512 CC32 CC33 CC39 DD08 DD23 DD31 DD41 EE06 EE07 EE21 EE28

Claims (2)

[Claims] 1. A compound of the general formula (I)[Wherein, R¹, R^Two, R^ThreeIs alkyl having 1 to 20 carbon atoms
Or an alkenyl group having 1 to 20 carbon atoms, or R¹
~ R^ThreeOne or two of which have 1 to 20 carbon atoms
Or an alkenyl group having 1 to 20 carbon atoms,
Alkyl group having 1 to 3 carbon atoms, hydroxy group having 1 to 3 carbon atoms
It is a alkyl group or a benzyl group. A has 2 to 3 carbon atoms
Alkylene group or hydroxyalkyl having 2 to 3 carbon atoms
Group, R ^FourIs the amino acid side chain of the keratin-derived peptide
And b is 0 or 1, m is 2 to 20, n is 20 to 2.
M is an alkali metal, an alkaline earth metal,
Ammonia, lower alkanolamine or lower alkyl
Amine (where m and n indicate the number of amino acids)
And does not indicate the order of the amino acid sequences.)]
N-quaternary anion of oxidized partial decomposition product of keratin represented by
Hair treatment characterized by containing a monium derivative
Agent. 2. The hair treatment composition according to claim 1, wherein the content of the N-quaternary ammonium derivative of the partially decomposed product of keratin represented by the general formula (I) is 0.05 to 20% by weight.