JPH11292739A - Hair treatment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hair treatment which shows excellent usability free from liquid drip in the treatment of hair and excellent preservative stability in the viscosity with reduced temporal decrease in the viscosity, gives fine gloss, moistness or pliability to hair and prevents hair from taking an electrical charge to improve combability. SOLUTION: This hair treatment is prepared by including a protein hydrolysate or its derivative, a quaternary ammonium salt of the following general formula (in the formula, R<1> CO shows a nonhydroxylanolin fatty acid acyl group or a lanolin fatty acid acyl group) and a polyethylene glycol stearate. The protein hydrolysate or its derivative, the quaternary ammonium salt of the general formula and the polyethylene glycol stearate are preferably included in amounts of 0.1-40 wt.%, 0.1-10 wt.% and 1-15 wt.%, respectively.

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 conditioner. More particularly, it has excellent usability without dripping during hair treatment, and has a low viscosity with time. The present invention relates to a hair treatment agent that has excellent storage stability of viscosity, imparts good gloss, moisture, and flexibility to hair, and prevents combing of hair to improve combability.

[0002]

2. Description of the Related Art Conventionally, hair treatment agents such as hair rinses, hair treatments, and hair conditioners have been used in the fourth place.
Grade ammonium salt type cationic surfactant as the main component, combined with silicone oil and polymer substance, softens hair with cationic surfactant, improves combability of hair, prevents electrification, The combined use of silicone oil smoothes the surface of the hair, imparts luster to the hair, prevents the generation of split ends due to combing, and forms a coating on the hair surface with a polymeric substance to impart luster to the hair. The hair was prevented from being generated.

[0003]

However, the above-described measures only improve the surface properties of the hair, but are not limited to chemical treatments such as permanent wave treatment, hair dyeing treatment, and the like. There has been a problem that the elution of the components causes damage to the hair, thereby reducing the moisturizing property of the hair and incapable of repairing the hair when the hair becomes puffy.

[0004] Therefore, a protein hydrolyzate (hydrolyzed peptide) or a derivative thereof is blended with a hair treatment agent so as to exert effects such as repairing damaged portions of hair, imparting gloss, moisture, and moisturizing properties to hair. Have been tried.

[0005] However, when a protein hydrolyzate or a derivative thereof is incorporated into a hair treatment agent, the viscosity of the hair treatment agent is reduced, and there is a problem that it becomes difficult to handle such as dripping when treating hair. In order to maintain the viscosity of the agent, there is a restriction that the amount of the protein hydrolyzate or its derivative must be kept at a certain level or less.

[0006] Hair treatment agents generally include thickening agents such as natural polymers such as carrageenan and alginic acid, semi-synthetic polymers such as carboxymethylcellulose and cationized cellulose, and synthetic polymers such as polyvinyl alcohol and acrylic acid polymers. Although blended, these high-molecular substances, if blended in large amounts, cause hair to stick, cause flaking on the hair after drying, and cause turbidity or precipitation due to association depending on the blending agent, The amount of the compounding agent in the hair treatment agent was limited, and their effects could not be sufficiently exerted.

Therefore, it has been desired to develop a hair treatment agent that does not drip when used and has no change in viscosity with time.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a hair treatment agent containing a protein hydrolyzate or a derivative thereof has been added to a non-hydroxylanolin fatty acid amino acid ethyl sulfate. Certain quaternary compounds such as propylethyldimethylammonium and lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate
When a hair treatment agent was prepared by blending a quaternary ammonium salt and polyethylene glycol stearate, it was found that the above-mentioned problems could be solved, and the present invention was completed.

That is, the present invention relates to a protein hydrolyzate or a derivative thereof and a compound represented by the following general formula (I):

[0010]

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Wherein R ¹ CO represents a non-hydroxylanolin fatty acid acyl group or a lanolin fatty acid acyl group.
A hair treating agent comprising a quaternary ammonium salt represented by the formula: and polyethylene glycol stearate.

The hair treatment composition of the present invention has a reduced viscosity even when a protein hydrolyzate or a derivative thereof, which has been limited in amount to reduce the viscosity in the conventional hair treatment composition, is added more than before. There is almost no, therefore, there is no dripping at the time of hair treatment, excellent usability, little decrease in viscosity over time, excellent storage stability of viscosity, and imparts good gloss, moisture, flexibility, etc. to hair To prevent split ends and prevent electrification of hair to improve combability. Hereinafter, this will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, protein hydrolysates or derivatives thereof contained in a hair treatment agent include, for example, collagen (including gelatin as a denatured product thereof), keratin, silk Animal and plant-derived proteins such as fibroin (silk), sericin, casein, conchiolin, elastin, chicken, duck and other egg yolk proteins, egg white proteins, soy proteins, wheat proteins, corn proteins, rice (rice bran) proteins, potato proteins, Alternatively, yeasts of the genera Saccharomyces, Candida and Endomycopsis, yeast proteins isolated from so-called beer yeasts, sake yeasts, proteins extracted from mushrooms (basidiomycetes), proteins isolated from chlorella, and the like. Acid from the microorganism-derived protein, Alkali, and hydrolysis peptides obtained by partial hydrolysis with an enzyme or a combination thereof.

This protein hydrolyzate has a number average molecular weight of 150 in consideration of the sorption property to hair and the action of forming a film.
5,000 are preferable, and 200-3000 are particularly preferable. That is, when the number-average molecular weight of the protein hydrolyzate is smaller than 150, the penetrating effect on hair is excellent, but the film-forming action on hair is not sufficient,
On the other hand, when the number average molecular weight is more than 5,000, although the film-forming effect is strong, the penetrating effect on the hair is weakened, and the protective effect on the hair and the repairing effect on the damaged hair may not be sufficiently exhibited.

The protein hydrolyzate derivative contained in the hair treatment composition of the present invention includes, for example, quaternary ammonium derivatives, silylated derivatives, and ester derivatives of the above protein hydrolysates.

The quaternary ammonium derivative of the above protein hydrolyzate includes, for example, the following general formula (II):

[0017]

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Wherein R ² , R ³ and R ⁴ have 1 to 3 carbon atoms.
An alkyl group or a hydroxyalkyl group of
One or ^{two of} R ^{2 to} R ⁴ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the rest are 1 to 3 carbon atoms.
An alkyl group, a hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, R ⁵ represents an amino acid side chain;
A represents a hydrogen atom or a hydroxyl group, and n represents an integer of 1 to 50].

The quaternary ammonium derivative of the protein hydrolyzate can be obtained, for example, by adding the following general formula (III) to the amino group of the protein hydrolyzate:

[0020]

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Wherein R ² , R ³ and R ⁴ have 1 to 3 carbon atoms.
An alkyl group or a hydroxyalkyl group of
One or ^{two of} R ^{2 to} R ⁴ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the rest are 1 to 3 carbon atoms.
X is a hydroxyalkyl group or a benzyl group having 1 to 3 carbon atoms, and X is Cl, Br, F, I, N
O ₃ , ＳＯSO ₄ , R ⁶ OSO ₃ or R ⁶ SO
₃ (R ⁶ represents a lower alkyl group)] or a glycidyl ammonium salt represented by the following general formula (IV)

[0022]

Embedded image

Wherein R ² , R ³ and R ⁴ have 1 to 3 carbon atoms.
An alkyl group or a hydroxyalkyl group of
One or ^{two of} R ^{2 to} R ⁴ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the rest are 1 to 3 carbon atoms.
X is a hydroxyalkyl group or a benzyl group having 1 to 3 carbon atoms, and X is Cl, Br, F, I, N
O ₃ , ＳＯSO ₄ , R ⁶ OSO ₃ or R ⁶ SO
₃ (R ⁶ represents a lower alkyl group), Y is Cl,
Represents a halogen atom such as Br, F, I, etc.]
-Halogen-2-hydroxypropyl ammonium salt,
Or the following general formula (V)

[0024]

Embedded image

Wherein R ² , R ³ and R ⁴ have 1 to 3 carbon atoms.
An alkyl group or a hydroxyalkyl group of
One or ^{two of} R ^{2 to} R ⁴ are an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the rest are 1 to 3 carbon atoms.
X is a hydroxyalkyl group or a benzyl group having 1 to 3 carbon atoms, and X is Cl, Br, F, I, N
O ₃ , ＳＯSO ₄ , R ⁶ OSO ₃ or R ⁶ SO
₃ (R ⁶ represents a lower alkyl group), Y is Cl,
Represents a halogen atom such as Br, F, I, etc.]
-Halogen-propylammonium salt.

As the silylated derivative of the protein hydrolyzate, for example, the following general formula (VI)

[0027]

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[Wherein at least one of R ⁷ , R ⁸ and R ⁹ represents a hydroxyl group, and the rest represents an alkyl group having 1 to 3 carbon atoms. R ¹⁰ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the terminal of the side chain, and R ¹¹ represents R ¹⁰
Other amino acid side chains are shown. B is a bond, methylene group, propylene group, —CH ₃ OCH ₂ CH (OH) CH
₂ - or _{- (CH 2) 3 OCH 2} CH (OH) CH 2
Wherein p is 0 to 50 and q is 1 to 50
Wherein p + q is an integer of 1 to 50 (however, p and q only indicate the number of amino acids, and do not indicate the order of amino acid sequences).

Such a silylated peptide can be obtained, for example, by adding the following general formula (VII) to an amino group containing an amino group on the amino acid side chain of the protein hydrolyzate:

[0030]

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[Wherein at least one of R ¹² , R ¹³ and R ¹⁴ represents an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom, and the rest is an alkyl group having 1 to 3 carbon atoms;
Represents an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom, a represents an integer of 1 or 3, Z represents Cl, B
a halogen atom such as r, F, I, etc.], or a compound represented by the following general formula (VIII):

[0032]

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[Wherein at least one of R ¹² , R ¹³ and R ¹⁴ represents an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom, and the rest is an alkyl group having 1 to 3 carbon atoms;
Represents an alkoxy group, a hydroxyl group or a halogen atom having 1 to 3 carbon atoms, and b represents an integer of 1 or 3].

Examples of the ester derivative of the protein hydrolyzate include esters of a carboxyl group of the protein hydrolyzate with a hydrocarbon alcohol having 1 to 20 carbon atoms, such as methyl ester, ethyl ester, propyl ester, isopropyl ester, and the like. Lauryl ester, cetyl ester, 2-ethylhexyl ester, 2-hexyldecyl ester, stearyl ester and the like can be mentioned.

The above-mentioned protein hydrolyzate or a derivative thereof sorbs to the hair, protects the hair, repairs the damaged part of the hair, and gives the hair good luster, moisture, moisture retention and the like. When incorporated into a hair treatment agent, the above-mentioned protein hydrolysates or derivatives thereof may be used alone or in combination of two or more.

The content of the above-mentioned protein hydrolyzate or its derivative in the hair treatment agent (blending amount in the hair treatment agent) is preferably 0.1 to 40% by weight, and particularly preferably 1 to 40% by weight.
20% by weight is preferred. That is, when the content of the protein hydrolyzate or its derivative in the hair treatment agent is less than the above range, impart gloss and moisture to the hair, protect the hair, improve combability, The effect of preventing excessive adsorption of the cationic surfactant may not be sufficiently exhibited, and even if the content of the protein hydrolyzate or a derivative thereof in the hair treatment agent is larger than the above range, the content may be reduced. There is almost no increase in the effect with an increase in the amount, and the hair may become sticky.

The quaternary ammonium salt represented by the general formula (I), which is the second essential component in the present invention, includes, for example, non-lanolin fatty acid aminopropylethyldimethylammonium ethylsulfate and hydroxypropyl lanolin fatty acid aminopropyl ethyl sulfate. Ethyl dimethyl ammonium and the like. Commercial products of such ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium include, for example, “Cation NH” (trade name) manufactured by Nippon Seika Co., Ltd. Examples of commercially available products of propylethyldimethylammonium include "Lanostar DP-50" (trade name) manufactured by Nippon Seika Co., Ltd.

The details of the quaternary ammonium salt represented by the above general formula (I) are as described in JP-A-9-143135, and the quaternary ammonium salt of the ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium "Non-hydroxylanolin fatty acid" refers to the following iso-type fatty acid I: 30 to 45% by weight, ante-iso-type fatty acid II: 3
0 to 50% by weight and normal fatty acid III: 10 to 3
0% by weight, the total amount of the iso-fatty acid I and the anteiso-fatty acid II is at least 60% by weight, and
The content of hydroxy fatty acid is less than 10% by weight.

* Iso type fatty acid I CH ₃ —CH (CH ₃ ) — (CH ₂ ) _m —COOH (m
= 6 to 26); * Anteiso fatty acid II CH ₃ CH ₂ —CH (CH ₃ ) — (CH ₂ ) _m —COO
H (m = 6 to 26); * Normal fatty acid III CH ₃ — (CH ₂ ) _m —COOH (m = 8 to 28) _o

The quaternary ammonium salt represented by the above general formula (I) sorbs to the hair to make the hair soft and smooth, and further prevents the charge of the hair to improve the combability. It exerts a conditioning effect on hair.

The fourth compound represented by the above general formula (I)
The content of the quaternary ammonium salt in the hair treatment agent (the amount added to the hair treatment agent) is 0.1 to 10% by weight, particularly 0.1 to 10% by weight.
5 to 5% by weight is preferred. That is, the above general formula (I)
When the content of the quaternary ammonium salt in the hair treatment agent is less than the above range, it imparts flexibility to the hair, prevents split ends, and improves the combability of the hair. May not be able to be fully exhibited.
When the content of the quaternary ammonium salt represented by the general formula (I) in the hair treatment agent is more than the above range, the amount of the quaternary ammonium salt adsorbed on the hair becomes too large, and the hair becomes extremely soft. In addition, the oily feeling may be increased and the hair may feel heavy.

The polyethylene glycol stearate, which is the third essential component in the present invention, is also a solubilizer, but exhibits a thickening effect when used in combination with the quaternary ammonium salt represented by the above general formula (I). This polyethylene glycol stearate may be polyethylene glycol monostearate or polyethylene glycol distearate. The addition mole number of ethylene oxide of polyethylene glycol stearate is 100
To 400, particularly preferably 120 to 200. That is,
If the number of moles of ethylene oxide is smaller than the above range, the thickening effect may not be sufficiently exhibited, and even if the number of moles of ethylene oxide is larger than the above range, there is no great difference in the thickening effect.

Commercially available products of such polyethylene glycol stearate include, for example, “Emanone 3199” and “Emanone 3299” manufactured by Kao Corporation.
(All are trade names), “EMALEX 6300M-ST”, “EMALEX” manufactured by Nippon Emulsion Co., Ltd.
6300di-ST ”(all are trade names), SEP
"Simulsol M59" (trade name) manufactured by PIC
And the like.

The content of the polyethylene glycol stearate in the hair treatment agent (the amount added to the hair treatment agent) is 1 to 15% by weight, particularly 1.5 to 10% by weight.
Is preferred. That is, when the content of the polyethylene glycol stearate in the hair treatment agent is less than the above range, the thickening effect may not be sufficiently exhibited, and the content of the polyethylene glycol stearate in the hair treatment agent may be reduced. Even if the amount is more than the above range, the improvement of the thickening effect with the increase of the content is hardly observed.

The hair treatment composition of the present invention comprises, as essential components, a protein hydrolyzate or a derivative thereof, a quaternary ammonium salt represented by the above general formula (I), and polyethylene glycol stearate. It is prepared by dissolving in a liquid to which a suitable solvent or the like has been added. In addition to these essential components, other components such as an oil component and an activator can be added as long as the effects of the present invention are not impaired.

As such a component, for example, 2-
Alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, undecyl-N-hydroxyethylimidazolinium betaine sodium, undecyl-N-hydroxyethyl-N-carboxymethylimidazolinium betaine, stearyldihydroxyethylbetaine, stearyl Betaine dimethylaminoacetate, coconut oil alkylbetaine, coconut oil fatty acid amidopropyl betaine, coconut oil alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine sodium, coconut oil alkyl-N-carboxyethoxyethyl-N-carboxyethyl Imidazolinium disodium hydroxide, coconut oil alkyl-N-carboxymethoxyethyl-N-carboxymethyl imidazolinium disodium lauryl Acid, N- coconut oil fatty acid acyl -L
-An amphoteric surfactant such as arginine ethyl-DL-pyrrolidone carboxylate, polyoxyethylene alkyl (C12-14) ether (7EO) (EO is ethylene oxide, and the numerical value before EO is ethylene oxide) The number of moles added is shown), 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, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetrade Nonionic surfactants such as butyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxypropylene stearyl ether, alkyl glycoside, alkyl polyglycoside, waxes, paraffins, fatty acid esters, glycerides, oils and fats such as animal and vegetable oils, animals and plants Extract, polysaccharide or derivative thereof, propylene glycol,
Wetting agents such as 1,3-butylene glycol, ethylene glycol, glycerin, and polyethylene glycol; lower alcohols such as ethanol, methanol, propanol, and isopropanol; higher alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol; Or silicones such as cyclic methyl polysiloxane, methyl phenyl polysiloxane, dimethyl polysiloxane polyethylene glycol copolymer, dimethyl polysiloxane polypropylene copolymer, amino-modified silicone oil, and quaternary ammonium-modified silicone oil. it can.

[0047]

The hair treatment composition of the present invention comprises a protein hydrolyzate or a derivative thereof and the fourth compound represented by the above general formula (I).
By containing a quaternary ammonium salt and polyethylene glycol stearate, problems such as dripping due to viscosity reduction as seen in conventional hair treatment agents are eliminated, and excellent usability and viscosity over time Less decrease, excellent storage stability of viscosity, and good gloss, moisturizing hair,
It imparts flexibility, prevents split ends, and prevents charging of hair to improve combability.

Therefore, the hair treatment composition of the present invention can be used in place of conventional hair treatment compositions such as hair rinses, hair treatments and hair conditioners, which have a conditioning effect on hair. Further, the hair treatment agent of the present invention can be used in combination with the above-mentioned hair treatment agent having a conditioning action, and can also be used in combination with other hair cosmetics.

[0049]

Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples. In the following Examples and Comparative Examples, the amounts of the respective components are not expressed in terms of the content in the prepared hair treatment agent but in terms of the blending amount because of the preparation of the hair treatment agent. The amount of each component in the examples and comparative examples is based on parts by weight, and for those whose amount is not a solid content, the solid content concentration is indicated in parentheses after the component name. Show. In addition, the method for measuring the viscosity carried out in the examples is as follows.

[Method of Measuring Viscosity] The viscosity was measured using a B-type rotary viscometer at a sample volume of 200 ml, at a liquid temperature of 25 ° C., and the rotor and the number of revolutions were selected according to the viscosity of the sample. . The measurement was performed three times for each sample, and the average value of the three measurements was defined as the viscosity of the sample. The unit of the viscosity is mPa · s (millipascal second).

Examples 1A to 1C and Comparative Examples 1A to 1C Hair treatment compositions having the compositions shown in Table 1 were prepared, and the reduction in the viscosity of the hair treatment composition due to the incorporation of a protein hydrolyzate or a derivative thereof was investigated. Was applied to the hair, and the hair was evaluated for flexibility, luster, moisture and combability. In Examples 1A to 1C, as the quaternary ammonium salt represented by the general formula (I), ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium was used. Propylethyldimethylammonium is “Cation NH” manufactured by Nippon Seika Co., Ltd.
(Trade name), and in the following examples, the term “cation NH” (trade name) also applies when aminopropylethyldimethylammonium non-hydroxylanolin fatty acid ethyl sulfate is used.

In Examples 1A to 1C and Comparative Examples 1A to 1C, the compounded protein hydrolysates or derivatives thereof were the following three types. Since the compounding amounts of the components are the same, the protein hydrolysates or their derivatives used in Examples and Comparative Examples in Table 1 are not individually described, but are collectively referred to as only the protein hydrolysates or their derivatives. ing. The protein hydrolysates or derivatives thereof used in Examples and Comparative Examples are as follows, and the number average molecular weight of the hydrolyzed peptide portion (in the simplification, described as “MW”) is shown in parentheses. Show. In addition, the blending amount is 1.0% as solid content.

Protein hydrolyzate or derivative thereof 1A: Hydrolyzed silk (MW 1000) 1B: Hydrolyzed wheat protein (MW 700) 1C: N- [2-hydroxy-3- (coconut fatty acid alkyldimonium) propyl chloride ] Hydrolyzed collagen (MW 700)

[0054]

[Table 1]

A hair treatment agent having the same composition as that of each of the above Examples and Comparative Examples was prepared, except that the protein hydrolyzate or its derivative was not added and the amount of sterilized ion-exchanged water was increased. Was used as a blank for each of Examples 1A to 1C and Comparative Examples 1A to 1C, and the viscosity was compared with that of a hair treating agent containing a protein hydrolyzate or a derivative thereof. Table 2 shows the results.

[0056]

[Table 2]

As is evident from the results shown in Table 2, a system containing a non-hydroxylanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate and polyethylene glycol monostearate was made to contain 1% of a protein hydrolyzate or a derivative thereof, respectively. In the hair treatment agents of Examples 1A to 1C, the decrease in viscosity was within 5%, whereas the system containing cetyltrimethylammonium chloride and polyethylene glycol monostearate was added with 1 part of each of the protein hydrolyzate and its derivative. % Of the hair treating agents of Comparative Examples 1A to 1C, the viscosity was reduced by 10% or more, and the hair treating agents mainly containing a quaternary ammonium salt such as cetyltrimethylammonium chloride used as a main component showed an increase in protein content. By containing a hydrolyzate or a derivative thereof, It can be seen that the viscosity of the management agent is greatly reduced.

In general, a hair treatment agent such as a hair rinse or a hair treatment which is applied directly to the head hair and is applied to the hair has a viscosity of 800 mPa · s or more, and sometimes 1 mPa · s or more.
If it is not more than 000 mPa · s, there is a risk of causing dripping and inconvenience in use, but the hair treatment agents of Examples 1A to 1C all have a viscosity of 1200 mPa · s or more, and such a problem may not occur at all. Did not. However, the hair treatment agent of Comparative Example 1C had a viscosity of 709.
Since there was only mPa · s, there was a high possibility that liquid dripping would occur, and there was a possibility of causing a problem in use.

The treatment of the hair with the above-mentioned hair treatment agent was performed as follows. That is, prior to the treatment with the hair treatment agent, a hair bundle having a length of 15 cm and a weight of 1 g was washed with a commercially available shampoo.
Each of the hair treatment agents of A to 1C and Comparative Examples 1A to 1C was applied in an amount of 2 g and rinsed with hot water. After repeating the shampoo washing and the treatment with the hair treatment agent five times, the flexibility, gloss, moisture, and combability of the hair were evaluated on a 5-point scale according to the following evaluation criteria by 10 female panelists. The results are shown in Tables 3 and 4 as average values of 10 persons.

Evaluation Criteria 5: Very Good 4: Good 3: Normal 2: Bad 1: Very Bad

[0061]

[Table 3]

[0062]

[Table 4]

As shown in Tables 3 and 4, Examples 1A to 1
The hair treated with the hair treating agent of Comparative Example 1A has a higher flexibility than the hair treated with the hair treating agent of Comparative Examples 1A to 1C.
The evaluation value was high in any of gloss, moisture, and combability, and the ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium contained in the hair treatment composition of Examples 1A to 1C was compared with Comparative Examples 1A to 1C. It has been clarified that cetyltrimethylammonium chloride contained in a hair treating agent is superior in the action of imparting flexibility, luster and moisture to hair and the action of improving combability of hair.

Example 2 and Comparative Examples 2A to 2E Hair treatment compositions having the compositions shown in Table 5 were prepared, and the appearance immediately after each preparation was visually observed, and the viscosity was measured.
In addition, each hair treatment agent was applied to the hair, and the flexibility, gloss, moisture, and combability of the hair were evaluated. However,
Since Comparative Example 2A was a comparative one containing no quaternary ammonium salt, the sensory evaluation test was not performed. In Example 2, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate was used as the quaternary ammonium salt represented by the general formula (I). "Lanostar DP-50" (trade name) manufactured by KK Co., Ltd., and in the following examples, when lanolin fatty acid aminopropylethyl dimethylammonium ethyl sulfate is used. Name).

Example 2 and Comparative Examples 2B to 2E
The purpose of the present invention is to confirm how the appearance and viscosity of the hair treatment agent are changed by changing the type of the quaternary ammonium salt, and what difference occurs in the sensory evaluation when applied to hair. In Comparative Examples, Comparative Examples 2B to
As shown in FIG. 2E, four quaternary ammonium salts were used.
In B to 2E, the quaternary ammonium salts to be used are not individually described but are collectively described only as quaternary ammonium salts. The quaternary ammonium salts used in Comparative Examples 2B to 2E are as follows, and the blending amount of the quaternary ammonium salts is 2.0% as solid content.

Quaternary ammonium salt 2B: cetyltrimethylammonium chloride 2C: distearyldimethylammonium chloride 2D: stearyltrimethylammonium chloride 2E: alkyltrimethylammonium chloride

[0067]

[Table 5] * 1: N- [2-hydroxy-3- (trimethylammonio) propyl chloride] hydrolyzed collagen

Table 6 shows the appearance and viscosity of each hair treatment agent immediately after preparation.

[0069]

[Table 6]

As shown in Table 6, the hair treatment composition of Example 2 containing lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate as a quaternary ammonium salt is transparent and has a high viscosity of 2012 mPa · s. Comparative Example 2 containing no quaternary ammonium salt
In the hair treatment agent of A, the components were not sufficiently dissolved and the viscosity was very low, and it was revealed that the hair treatment agent of the above-mentioned formulation required a quaternary ammonium salt.

On the other hand, Comparative Examples 2B to 2E containing a quaternary ammonium salt generally used in hair treatment agents
In Comparative Example 2B, only the comparative example 2B containing cetyltrimethylammonium chloride had a transparent appearance, but the viscosity was only about 1/4 of that of Example 2, and the comparative example containing distearyldimethylammonium chloride contained In Example 2C, the appearance was cloudy and the viscosity was low. When the hair treatment agent of Comparative Example 2B or Comparative Example 2C was applied to the hair as it was, there was a sufficient risk of dripping. Comparative Example 2D containing stearyltrimethylammonium chloride and Comparative Example 2 containing alkyltrimethylammonium chloride
In E, the appearance was not transparent, and the viscosity was slightly higher than that of the other comparative examples, but about 3/4 of that of Example 2,
It was clear that the aminopropylethyldimethylammonium ethyl lanolin fatty acid aminopropylethyldimethylammonium was excellent in the viscosity maintaining effect of the hair treatment agent containing the derivative of the protein hydrolyzate.

The treatment of the hair with the above-mentioned hair treating agent was carried out in the same manner as in Example 1 as follows. That is, a hair bundle having a length of 15 cm and a weight of 1 g was washed with a commercially available shampoo, and the hair treatment agent of Example 2 and Comparative Examples 2B to 2E was applied to the washed hair bundle by 2 g each, Rinse with hot water. After repeating the shampoo washing and the treatment with the hair treatment agent five times, the flexibility, gloss, moisture, and combability of the hair were evaluated by a female panelist of five persons in five steps according to the same evaluation criteria as in Example 1. The results are shown in Table 7 as an average value of 10 persons.

[0073]

[Table 7]

As shown in Table 7, the hair treated with the hair treating agent of Example 2 was more flexible, glossy, moisturized and combed than the hair treated with the hair treating agents of Comparative Examples 2B to 2E. The evaluation value was high in any of the items of passability, and the quaternary ammonium salt ethylpropyl lanolin fatty acid aminopropylethyldimethylammonium was replaced with the conventionally used cetyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride and chloride. It has been clarified that alkyltrimethylammonium is more effective in imparting flexibility, luster and moisture to hair and improving hair combability.

Example 3 and Comparative Examples 3A to 3D Hair treatment compositions having the compositions shown in Table 8 were prepared, and the appearance immediately after each preparation was visually observed, and the viscosity was measured.

Example 3 and Comparative Examples 3B to 3D
By changing the type of the thickener (Comparative Example 3A is a comparative example without a thickener), it is intended to confirm how the appearance and viscosity of the hair treatment agent change. In the examples, three types of thickeners were used as shown in Comparative Examples 3B to 3D, but since the compounding amounts thereof were the same, the thickeners to be used are individually described in Comparative Examples 3B to 3D in Table 8. Not collectively, only the thickener is described. The thickeners used in Comparative Examples 3B to 3E are as follows, and the compounding amount of the thickener is 4.0%.

Thickener 3B: polyethylene glycol dioleate 1000 3C: polyoxyethylene methyl dioleate methyl glucoside (120EO) 3D: cationized cellulose

[0078]

[Table 8]

Table 9 shows the appearance and viscosity of each hair treatment composition.

[0080]

[Table 9]

As is clear from Table 9, the hair treatment composition of Example 3 containing polyethylene glycol distearate (140EO) as a thickener was 10813 mPa · s.
Comparative Example 3A, in which the viscosity was as low as 15 mPa · s or less for the hair treatment agent of Comparative Example 3A which did not contain a thickener, and which contained polyethylene glycol dioleate 1000 as a thickener. In the hair treating agent of Comparative Example 3C containing the hair treating agent of 3B and polyoxyethylene dioleic acid methylglucoside (120EO) as a thickening agent, no increase in viscosity was observed. The hair treatment agent of Comparative Example 3D containing cationized cellulose as a thickener had a viscosity of 289 mPa ·
s, and the viscosity was too low to apply to the hair.

Example 4 and Comparative Examples 4A-4B Hydrolyzed keratin (number average molecular weight 1
000) is prepared, and each hair treatment agent is applied to the hair to give the hair flexibility, luster, moisture,
Combability was evaluated.

[0083]

[Table 10]

The treatment of the hair with the above-mentioned hair treating agent was carried out as follows in the same manner as in Example 1. That is, a hair bundle having a length of 15 cm and a weight of 1 g was washed with a commercially available shampoo, and the hair treatment agent of Example 4 and Comparative Examples 4A to 4B was uniformly applied to the washed hair bundle by 2 g each. Apply and rinse with hot water. After repeating this shampoo washing and treatment with the hair treatment agent five times, the flexibility of the hair,
The gloss, moisture, and combability were evaluated by five female panelists according to the same evaluation criteria as in Example 1 in five steps. The results are shown in Table 11 as an average value of 10 persons.

[0085]

[Table 11]

As shown in Table 11, the hair treated with the hair treating agent of Example 4 was more flexible, glossy, moisturized and combed than the hair treated with the hair treating agents of Comparative Example 4A and Comparative Example 4B. The evaluation value was high in any of the items of the passability.
The quaternary ammonium salt lanolin fatty acid aminopropylethyldimethylammonium quaternary ammonium salt contained in the hair treating agent of Comparative Example 4A was contained in the cetyltrimethyl ammonium chloride contained in the hair treating agent of Comparative Example 4A and the hair treating agent of Comparative Example 4B. It has been clarified that the stearyltrimethylammonium chloride is more effective in imparting softness, luster, and moisture to hair, and improving combability of hair.

Example 5 and Comparative Examples 5A-5B Hydrolyzed silk (number average molecular weight 10
00) was prepared, and each hair treatment agent was applied to hair, and the flexibility, gloss, moisture, and combability of the hair were evaluated.

[0088]

[Table 12]

The treatment of the hair with the above-mentioned hair treating agent was carried out as described below in the same manner as in Example 1. That is,
A hair bundle having a length of 15 cm and a weight of 1 g was washed with a commercially available shampoo, and the washed hair bundle was treated with 2 g of each of the hair treatment agents of Example 5 and Comparative Examples 5A to 5B. Rinsed with hot water. After repeating this shampoo washing and treatment with the hair treatment agent five times, the flexibility of the hair,
The gloss, moisture, and combability were evaluated by five female panelists according to the same evaluation criteria as in Example 1 in five steps. The results are shown in Table 13 as an average value of 10 persons.

[0090]

[Table 13]

As shown in Table 13, the hair treated with the hair treating agent of Example 5 was more flexible, glossy, moisturized and combed than the hair treated with the hair treating agents of Comparative Example 5A and Comparative Example 5B. The evaluation value was high in each of the items of the passability.
The quaternary ammonium salt ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium of the quaternary ammonium salt contained in the hair treating agent of Comparative Example 5A was used for the cetyltrimethyl ammonium chloride and the hair treating agent of Comparative Example 5B. It has been found that the stearyltrimethylammonium chloride contained in E. coli is superior in the effect of imparting flexibility, luster and moisture to hair and the effect of improving combability.

Examples 6A to 6G and Comparative Examples 6A to 6G Hair treatment compositions having the compositions shown in Table 14 were prepared, their appearance was visually observed, and the viscosity was measured. Examples 6A to 6G and Comparative Examples 6A to 6G are for confirming how the appearance and viscosity of the hair treatment agent change by changing the type of the protein hydrolyzate to be added, In the examples, seven types of protein hydrolysates (Examples 6A to 6G) were used. However, since the amounts of these components were the same, in Examples 6A to 6G of Table 14, the protein hydrolysates used were individually , And are collectively described only as protein hydrolysates. Comparative Examples 6A to 6G
Is a comparative example in which cetyltrimethylammonium chloride was used as a quaternary ammonium salt, and the same protein hydrolyzate as in Examples 6A to 6G was blended. In Table 14, protein hydrolyzate was used in the same manner as in Example. It is described only as decomposition products. In addition, the compounding amount of the protein hydrolyzate is 9.0% as solid content in each of the examples and the comparative examples.

In Table 14, the protein hydrolysates used in Examples and Comparative Examples are as follows, and the number average molecular weights of the respective protein hydrolysates (abbreviated to “MW”) are shown in parentheses. Write.

Protein hydrolyzate 6A: hydrolyzed collagen (MW 2000) 6B: hydrolyzed keratin (MW 400) 6C: hydrolyzed wheat protein (MW 700) 6D: hydrolyzed silk (MW 1000) 6E: hydrolyzed casein ( MW 600) 6F: Hydrolyzed soybean protein (MW 700) 6G: Hydrolyzed conchiolin (MW 600)

[0095]

[Table 14]

Table 15 shows the appearance and viscosity of each hair treating agent.

[0097]

[Table 15]

As is evident from the results shown in Table 15, the appearance of the hair treatment agent was not significantly different between Examples 6A to 6G and the corresponding Comparative Examples 6A to 6G. Examples 6A-6G were about 7 times higher than the corresponding Comparative Examples 6A-6G, respectively. Further, looking at the viscosities of Examples 6A to 6G, almost no difference in the viscosity of the hair treatment agent due to the difference in the contained protein hydrolyzate was observed.

Examples 7A to 7D and Comparative Examples 7A to 7D Hair treatment agents having the compositions shown in Table 16 were prepared, their appearance was visually observed, and the viscosity was measured. Examples 7A to 7D and Comparative Examples 7A to 7D are for confirming how the viscosity of the hair treatment agent changes by changing the type of the protein hydrolyzate derivative to be added, In Examples, derivatives of four kinds of protein hydrolysates were used as shown in Examples 7A to 7D. However, since their blending amounts are the same, Examples 7A to 7D in Table 16 are used.
Does not separately describe the protein hydrolyzate derivative used, but collectively describes only the protein hydrolyzate derivative. Comparative Examples 7A to 7D are comparative ones in which cetyltrimethylammonium chloride was used as a quaternary ammonium salt, and the same protein hydrolyzate derivatives as in Examples 7A to 7D were blended. As in the case of the above, only the derivative of the protein hydrolyzate is described.
In addition, the compounding amount of the protein hydrolyzate derivative is 6.0% as a solid content in both Examples and Comparative Examples.

In Table 16, the derivatives of the protein hydrolyzate used in Examples and Comparative Examples are as follows, and the number average molecular weight of the protein hydrolyzate portion in each protein hydrolyzate derivative (simplified) , "MW") in parentheses.

Protein hydrolyzate derivative 7A: N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed keratin (MW 100
0) 7B: N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein (MW 7
00C) 7C: N- [2-hydroxy-3- (coco oil fatty acid alkyldiammonium) propyl] hydrolyzed silk (MW 700) 7D: N- [2-hydroxy-3- [3- (dihydroxymethylsilyl) Propoxy] propyl] hydrolyzed collagen (MW 2000)

[0102]

[Table 16]

Table 17 shows the appearance and viscosity of each hair treating agent.

[0104]

[Table 17]

As is evident from the results shown in Table 17, the appearance of the hair treatment agent was not changed in the case of 7A containing N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed keratin. Is transparent and the comparative example is cloudy, and 7B containing N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein or N- [2-hydroxy-3- (coconut oil) Fatty acid alkyldiammonium) propyl] hydrolyzed silk and 7C or N- [2-hydroxy-3-
7D containing [3- (dihydroxymethylsilyl) propoxy] propyl] hydrolyzed collagen was almost the same in both the examples and comparative examples.

However, with respect to the viscosity, the derivatives of the proteolytic substances were 10 times or more more viscous in the hair treatment agent of the example than in the hair treatment agent of the comparative example, and ethyl sulfate was used as a quaternary ammonium salt. The effect of blending the non-hydroxylanolin fatty acid aminopropylethyldimethylammonium was apparent. In Comparative Examples 7A to 7D, the viscosity was 200 mPa · s or less, and the viscosity was insufficient as a hair treatment agent.

[Temporal Stability of Viscosity of Hair Treatment Agent] The hair treatment agents prepared in Examples 1 to 7 were stored at room temperature (25 ° C.) for 30 days, and the viscosities after 1 week and 30 days were measured. Was examined for changes. The results are shown in Tables 18 to 19.

[0108]

[Table 18]

[0109]

[Table 19]

As shown in Tables 18 and 19, the hair treatment agents of Examples 1A to 1C, Examples 2 to 5, 6A to 6B, and 7B to 7D all had a viscosity after one week. Was slightly higher than immediately after preparation, the viscosity after storage for 30 days was almost the same as that after 1 week, the viscosity decreased little with time, and the storage stability of the viscosity was excellent. Example 6C
~ 6G and the hair treating agent of Example 7A, the viscosity of which is one week later than that immediately after preparation (Example 6F) of about 11
%, But there is no decrease in the viscosity thereafter, and all the hair treatment agents have almost the same value after 30 days as after one week, and the decrease in viscosity with time is small, and the storage stability of the viscosity is excellent. Was.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 30, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0037

[Correction method] Change

[Correction contents]

[0037] The quaternary ammonium salt represented by the second formula is an essential component in the present invention (I), for example, ethyl sulfate nonhydroxyl lanolin fatty acid aminopropyl ethyl dimethyl ammonium and ethyl sulfate Sanra Bruno < Aminopropylethyldimethylammonium phosphorus fatty acid and the like. Commercial products of such ethyl sulfate non-hydroxylanolin fatty acid aminopropylethyldimethylammonium include, for example, “Cation NH” (trade name) manufactured by Nippon Seika Co., Ltd. Examples of commercially available products of propylethyldimethylammonium include "Lanostar DP-50" (trade name) manufactured by Nippon Seika Co., Ltd.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0101

[Correction method] Change

[Correction contents]

Protein hydrolyzate derivative 7A: N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed keratin (MW 100
0) 7B: N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein (MW 7
00) 7C: N-chloride [2-hydroxy-3- (coconut oil fatty acid alkyl dimonium) propyl] hydrolyzed silk (MW
700) 7D: N- [2-hydroxy-3- [3- (dihydroxymethylsilyl) propoxy] propyl] hydrolyzed collagen (MW 2000)

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0105

[Correction method] Change

[Correction contents]

As is evident from the results shown in Table 17, the appearance of the hair treatment agent was not changed in the case of 7A containing N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed keratin. Is transparent and the comparative example is cloudy, and 7B containing N- [2-hydroxy-3- (trimethylammonio) propyl] hydrolyzed wheat protein or N- [2-hydroxy-3- (coconut oil) 7C and which contains a fatty acid alkyl dimonium) propyl] hydrolyzed silk, N-[2-hydroxy-3- [3
7D containing-(dihydroxymethylsilyl) propoxy] propyl] hydrolyzed collagen was almost the same in both Examples and Comparative Examples.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0106

[Correction method] Change

[Correction contents]

[0106] However, with respect to viscosity, any derivative of protein <br/> hydrolysates also 10 times or more the viscosity is higher than hair treatment of Comparative Example is more hair treatment agents of Examples, quaternary The effect of blending the aminosulfuric acid non-hydroxylanolin fatty acid aminopropylethyldimethylammonium as the ammonium salt is apparent. In Comparative Examples 7A to 7D, the viscosity was 200 mPa · s or less, and the viscosity was insufficient as a hair treatment agent. there were.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Nobuaki Hattori 5-1-1 Umei, Takasago City, Hyogo Prefecture Inside Nippon Seika Co., Ltd. (72) Inventor Chiaki Mori 5-1-1 Umei, Takasago City, Hyogo Prefecture Nippon Seika Co., Ltd.

Claims (3)

[Claims] 1. A protein hydrolyzate or a derivative thereof,
The following general formula (I): [Wherein R ¹ CO represents a non-hydroxylanolin fatty acid acyl group or a lanolin fatty acid acyl group], and a polyethylene glycol stearate. 2. The content of the protein hydrolyzate or its derivative is 0.1 to 40% by weight, and the content of the quaternary ammonium salt represented by the general formula (I) is 0.1 to 10% by weight.
And the content of polyethylene glycol stearate is 1
The hair treatment composition according to claim 1, which is in an amount of from 15 to 15% by weight. 3. The quaternary ammonium salt represented by the general formula (I) is aminopropylethyldimethylammonium non-hydroxylanolin fatty acid ethyl sulfate or lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate. Hair treatment agent.