JP3446976B2 - 1st agent for permanent wave - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a first agent for permanent wave, more specifically, it prevents damage to hair during permanent wave treatment, recovers damaged hair, and imparts excellent wave to hair. You can
Moreover, it has excellent storage stability, and is the first permanent wave type.
Regarding agents.

[0002]

2. Description of the Related Art Permanent wave agents that have been generally used in the past include aqueous solutions containing a reducing agent such as thioglycolic acid and cysteine as a main component, and basic substances such as ammonia, monoethanolamine and triethanolamine. Was added to adjust the pH to 8 to 10 as the first agent, and an aqueous solution of an oxidizing agent such as sodium bromate and hydrogen peroxide was used as the second agent.

The mechanism of waving hair with such a permanent waving agent is such that the first agent is applied to the hair, the hair is wound around a rod and the hair is curled, and the constituent protein of the hair ( (Certain), which is a protein), undergoes reductive cleavage of the disulfide bond of cystine to generate a mercapto group, and then the second agent oxidizes the mercapto group to form a disulfide bond at a new position in the hair, thus fixing the wave. It is what makes me.

[0004]

However, in the case of such a permanent waving agent, the oxidization by the second agent followed by the disulfide bond of cystine cleaved by the reducing agent by the first agent completely restores it to the original state. It does not always regenerate cystine by forming a zirfide bond, and a part of the mercapto group generated from cystine by the treatment with the first agent is over-oxidized by the second agent and thioglycolic acid remaining in the hair. Alternatively, a side reaction such as reaction with the mercapto group of cysteine to form a disulfide bond occurs. As a result, damage such as elution of a part of the keratin protein in the hair and physical and chemical changes in other parts of the hair occur. As a result, not only does the hair feel strange and dry, but also the hair is greatly damaged.

Therefore, it has been attempted to add silicones to a permanent waving agent to reduce the dry feeling of the hair after the permanent waving treatment, improve combability, and restore the strength of damaged hair. ing.

However, since silicones form a film on the hair, the feeling of dryness on the surface is reduced, but there is no fundamental recovery action against damage to the hair due to elution of keratin protein from the hair, Further, there is a problem that the hair cannot be moisturized and that the hair is less likely to be waved due to the silicone film formed on the hair.

[0007] Silicones are generally lipophilic (hydrophobic) substances and are easily sorbed to highly hydrophobic hair with little damage, but damaged hair, that is, hydrophilic groups are exposed on the surface due to damage. It is said that it is difficult to sorb hair that has become hydrophilic, and sorption on hair that has been greatly damaged by the permanent wave treatment cannot be expected. Furthermore, since permanent wave agents are generally water-soluble, it is necessary to mix an emulsifier at the same time when blending silicones, but silicones may separate during storage depending on storage conditions. The compounded permanent waving agent has a problem of lacking storage stability.

Therefore, the present invention is capable of suppressing damage to the hair during permanent wave treatment, recovering damaged hair, and imparting excellent wave, luster and moisturizing to the hair, and also storage stability. It is an object of the present invention to provide a superior first agent for permanent wave.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a functional group containing only one silicon atom in the amino group of a peptide containing the amino group of the amino acid side chain. The following general formula (I) covalently bonded to

[0010]

[Chemical 3]

[In the formula, ^{two of} R ¹ , R ² and R ³ represent a hydroxyl group, and the rest represent a methyl group. R ⁴ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the end of the side chain, R ⁵ represents a side chain of an amino acid other than R ⁴ , a is 1 or 3, and m is 0. Greater than 50 or less, n
Is 1 to 200 and m + n is 2 to 200 (however, m
And n only indicate the number of amino acids, not the order of amino acid sequences)] or a silylated peptide represented by the following general formula (II)

[0012]

[Chemical 4]

[In the formula, ^{two of} R ¹ , R ² and R ³ represent a hydroxyl group, and the rest represent a methyl group. R ⁴ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the end of the side chain, R ⁵ represents a side chain of an amino acid other than R ⁴ , a is 1 or 3, and m is 0. Greater than 50 or less, n
Is 1 to 200 and m + n is 2 to 200 (however, m
And n only indicates the number of amino acids, and does not indicate the order of amino acid sequences.)] When the silylated peptide represented by the following formula is added to the first agent for permanent wave,
The permanent wave for permanent wave that can prevent damage to the hair during permanent wave treatment, recover damaged hair, and impart excellent wave power, luster and moisturizing to the hair, and also have excellent storage stability. The inventors have found that an agent can be obtained and completed the present invention.

That is, the silylated peptide sorbs on the hair by the sorption action of the peptide portion, protects the hair during the permanent wave treatment, prevents the hair from being damaged by the permanent wave treatment, and restores the damaged hair. ,
At the same time, the hair is moisturized, and the silyl functional group portion is also sorbed to the hair through the peptide portion, so that the surface of the hair is made smooth and the hair is provided with gloss and luster. Further, since this silylated peptide sorbs to hair by a normal peptide sorption mechanism, it is possible to impart desired excellent wave to hair without disturbing the permanent wave treatment of hair.

In addition to the above effects, the present inventors have found that when a cationic surfactant is added to the permanent wave first agent in combination with the silylated peptide,
It has also been found that more preferable results are obtained such that flexibility is imparted to the hair, combability of the hair is improved, and the wave efficiency described below is also improved.

The first agent for permanent wave of the present invention contains a reducing agent as a main agent, and contains a silylated peptide,
Further, it is prepared by using a silylated peptide and a cationic surfactant in combination, and their components will be described in detail below.

[Silylated Peptide] The silylated peptide represented by the above general formula (I) is, for example, the following general formula (III)

[0018]

[Chemical 5]

[In the formula, one of R ⁶ , R ⁷ and R ⁸ represents a methyl group, and the remaining two represent an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom. a is 1 or 3, and X is a halogen atom such as Cl, Br, F, or I], and the following general formula (IV)

[0020]

[Chemical 6]

[Wherein R ⁴ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the terminal of the side chain,
R ⁵ represents a side chain of an amino acid other than R ^4, m is greater than 0 and 50 or less, obtained by n is 1 to 200, m + n is a condensation reaction of peptides represented by a 2-200] To be

The silylated peptide represented by the general formula (II) is, for example, the following general formula (V)

[0023]

[Chemical 7]

[In the formula, one of R ⁶ , R ⁷ and R ⁸ represents a methyl group, and the remaining two represent an alkoxy group having 1 to 3 carbon atoms, a hydroxyl group or a halogen atom. a represents 1 or 3] and a silyl compound represented by the general formula (IV) are subjected to a condensation reaction.

[Characteristics of Silylated Peptide] The silylated peptide represented by the general formula (I) and the general formula (I
As is clear from the chemical structural formula, the silylated peptide represented by I) is a silicon atom based on the silyl compound represented by the general formula (III) or the silyl compound represented by the general formula (V). Since it has a silyl functional group moiety containing, and a peptide moiety based on the peptides represented by the general formula (IV), when this is compounded in the first agent for permanent wave, the excellent spreading property of the silyl functional group moiety, Friction reduction, gloss and luster imparting action, water repellency imparting action and sorptive action of peptide part on hair, resulting in volume increase of hair, firmness imparting, protective action by film formation, moisturizing action, etc. Can be demonstrated at the same time. Moreover, since the peptides have good sorption properties on damaged hair, the silylated peptide can sorb a silyl functional group via a peptide moiety on damaged hair that is difficult to sorb with silicones. It can improve the feel of damaged hair and contribute to the recovery of strength.

Therefore, when this silylated peptide is blended with the first agent for permanent wave, damage to the hair during the permanent wave treatment is prevented, damaged hair can be restored, and gloss and moisturization are imparted to the hair. It smoothes the hair, improves combability of the hair, and prevents split ends and cut hair.

For example, when silicone is used to impart elasticity to hair as in the prior art, a high molecular weight one is required, but once a high molecular weight silicone adheres to the hair, it is difficult to remove, and therefore permanent wave treatment is required. In addition to being difficult to do, it reduces the sorption effect of peptides on hair. However, the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II) has a low molecular weight silyl functional group bonded to the peptide portion, Since it sorbs by a normal peptide sorption mechanism, the silylated peptide can be reversibly desorbed from the hair by washing with a peptide-free detergent, and the above-mentioned adverse effects do not occur.

Moreover, since the silylated peptide represented by the general formula (I) and the silylated peptide represented by the general formula (II) have a silyl functional group portion and a peptide portion in one substance, the conventional silicone is used. Unlike the mixture of these and the polypeptide, the silyl functional group portion has high sorption on the hair.

In the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II), ^{two of} R ¹ , R ² and R ³ are hydroxyl groups and the rest are methyl groups. Is a water-soluble first agent for permanent wave, wherein the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II) is water-soluble. This is to maintain good storage stability. Also, a is specified as 1 or 3 because a is 2
In the case of, the storage stability in the state of the silyl compound represented by the general formula (III) or the silyl compound represented by the general formula (V) is poor, and when a is larger than 3, the silyl functional group moiety in the whole molecule is This is because the ratio of the silyl functional group becomes small and the characteristics of the silyl functional group moiety cannot be fully exhibited.

[Peptide Moiety in Silylated Peptide] In the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II), R ⁴ has an amino group at the terminal of the side chain. Examples of the basic amino acid having a terminal amino group at the terminal of the side chain, which is a residue excluding the terminal amino group of the basic amino acid, include lysine, arginine, hydroxylysine, and the like.
R ⁵ represents a side chain of an amino acid other than R ⁴ , and examples of such an amino acid include glutamic acid, aspartic acid, alanine, serine, threonine, valine,
Methionine, leucine, isoleucine, tyrosine, phenylalanine, proline, hydroxyproline and the like can be mentioned.

In the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II), m is more than 0 and 50 or less (0 <m ≦ 50), preferably m Greater than 0 and less than or equal to 10 (0 <m ≦ 10)
And n is 1 to 200, preferably 1 to 10
0, more preferably 2 to 40, and m + n is 2 to 20.
0, preferably 2 to 100, more preferably 3
˜50, which is due to the following reason.

That is, when m is larger than the above range, the number of silyl functional groups bonded to the amino group of the side chain is increased, and the sorption action on the original hair of the peptide is decreased. The ratio of the silyl functional group portion to the silyl functional group portion is reduced, and the effect of the silyl functional group portion cannot be fully exerted. When m + n is larger than the above range, the peptide has poor sorption and penetrability on hair. In addition to the decrease in molecular weight of the peptide, it tends to aggregate during storage, resulting in poor storage stability. The above m, n and m + n are theoretically integers, but when the peptide portion is a hydrolyzed protein as described below, the hydrolyzed protein is obtained as a mixture of those having different molecular weights. The measured value is an average value.

The peptides represented by the above general formula (IV) include peptides or esters of peptides.

The above-mentioned peptide is a natural peptide, a synthetic peptide, a hydrolyzed peptide obtained by partially hydrolyzing a protein with an acid, an alkali or an enzyme.

Examples of natural peptides include glutathione, bacitracin A, insulin, glucagon, oxytocin, vasopressin, and the like, and synthetic peptides include, for example, polyglycine, polylysine, polyglutamic acid, and polyserine.

Examples of the hydrolyzed peptide include collagen (including its modified product gelatin), keratin, silk fibroin, sericin, casein, conchiolin, elastin, chicken, egg yolk protein of eggs, etc.
Proteins derived from plants and animals such as egg white protein, soy protein, wheat protein, corn protein, rice (rice bran) protein, potato protein, or yeasts of the genera Saccharomyces, Candita and Endomycopsis, so-called beer yeast, sake yeast. Peptides obtained by partially hydrolyzing microorganism-derived proteins such as yeast proteins isolated from yeasts, proteins extracted from mushrooms (basidiomycetes), proteins isolated from Chlorella with acid, alkali or enzyme Is mentioned. The hydrolyzed protein also includes a mixture of peptides composed of the various amino acids described above, in which the amount of the amino acids is 2 to 200.

Further, as the ester of the above peptide,
1 to 20 carbon atoms in the carboxyl group of the peptide
With hydrocarbon alcohols such as methyl ester, ethyl ester, propyl ester, isopropyl ester, lauryl ester, cetyl ester, 2
-Ethylhexyl ester, 2-hexyldecyl ester, stearyl ester and the like can be mentioned.

[Synthesis of Silylated Peptide] The silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II) is a silyl compound represented by the general formula (III). Alternatively, the silyl compound represented by the general formula (V) and the peptide represented by the general formula (IV) can be obtained by catalytic reaction. The silyl compound represented by the general formula (III) or As the silyl compound represented by the general formula (V), a commercially available silane coupling agent can be used. Examples of such a silane coupling agent include TSL8390, TSL8219, and TS manufactured by Toshiba Silicone Co., Ltd.
L8395, TSL8326, TSL8325, TSL
8320, TSL8355, TSL8350 (all are trade names), Nippon Unicar Co., Ltd. A-143 (trade name), Toray Dow Corning Silicone Co., Ltd. SH6040, SH6076 (all are trade names), KBM403, KBM402 manufactured by Shin-Etsu Silicone Co., Ltd.
KBM703 (both are trade names) and the like.

The reaction of the silyl compound represented by the general formula (III) or the silyl compound represented by the general formula (V) with the peptides represented by the general formula (IV) is carried out by first reacting the silyl compound with 30 After converting the alkoxy group or the halogen atom bonded to the silicon atom to a hydroxyl group by stirring in water at -50 ° C for 5 to 20 minutes to hydrolyze, the hydroxylated silyl compound is represented by the general formula (IV). It is carried out by dropping it into a solution of the peptides to be brought into contact with each other.

In the above reaction, the peptide was 30-50.
It is preferable to use an aqueous solution of about wt%, and the dropping of the hydroxylated silyl compound is preferably completed in 30 minutes to 5 hours.

When the silyl compound represented by the general formula (III) is used, during the reaction, hydrogen halide is produced by the reaction and the pH after the reaction is lowered. It is preferable to maintain the pH in the reaction system at 8 to 11, particularly 9 to 10, by dropping an alkaline solution such as. Further, when the silyl compound represented by the general formula (V) is used, the pH does not decrease due to the reaction, but the reaction proceeds on the basic side, so the pH of the peptide solution is 8 to 11, particularly 9 to 10. It is preferable to keep it at 10.

The reaction proceeds at room temperature, but the higher the temperature, the faster the reaction rate. However, since the hydrolysis of the silyl compound is promoted when the temperature rises in a high pH state, it is preferably at most 70 ° C. or lower, and particularly preferably 40 to 60 ° C.

The progress and completion of the reaction can be confirmed by measuring the amount of amino nitrogen of the peptides in the reaction by the Van Slyke method.

After the completion of the reaction, the reaction solution is neutralized, then appropriately concentrated, and purified by ion exchange resin, dialysis membrane, electrodialysis, gel filtration, ultrafiltration, etc., and is kept as a liquid or powdered to be a permanent. It is used for the preparation of the first agent for wave.

In the silylated peptide represented by the above general formula (I), the introduction rate of the silyl functional group (that is, the functional group containing only one silicon atom) into the amino group of the peptide is 50% or more and 85% or less. Is preferred. If the introduction rate of the silyl functional group is less than 50%, the characteristics based on the silyl compound may not be sufficiently exhibited, and if it is more than 85%, the hydrophobicity may increase and the hydrophilicity may decrease.

In the silylated peptide represented by the general formula (II), the introduction rate of the silyl functional group into the amino group of the peptide is preferably 50% or more and 75% or less. If the introduction rate of the silyl functional group is less than 50%, the characteristics based on the silyl compound may not be sufficiently exhibited.
If it exceeds 5%, the hydrophobicity may increase and the hydrophilicity may decrease.

[First Agent for Permanent Wave Containing Silylated Peptide] The silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II) may be used alone. However, two or more kinds may be mixed and used. And, the compounding amount of the silylated peptide in the first agent for permanent wave (content in the first agent for permanent wave) is 0.1 to 15% by weight, particularly 1
It is preferably in the range of 5 wt%. That is, when the amount of the silylated peptide compounded in the permanent wave first agent is less than the above range, it protects the hair to prevent damage to the hair, imparts luster and moisturization to the hair, and has a cationic interface. When used in combination with an active agent, the effect of preventing excessive adsorption of the cationic surfactant is not sufficiently exerted, and
Even if the amount of the silylated peptide compounded in the first agent for permanent wave is more than the above range, no increase in the effect due to the increase of the compounded amount is observed, and the excessive adsorption of the silylated peptide causes the hair to be There is a risk of stickiness.

The reducing agent serves as the main agent for reducing and cleaving the disulfide bond of cystine in the keratin, which is a constituent protein of hair, so that the hair is waved. , For example, thioglycolic acid, thioglycolic acid ammonium, thioglycolic acid salts such as thioglycolic acid monoethanolamine, thioglycolic acid esters such as glycerin thioglycolate, cysteine, cysteine hydrochloride, cysteine salts such as acetylcysteine, Thioglycerol,
Organic mercaptan compounds such as thiolactic acid, thiomalic acid, cysteamine, cysteamine salt, sodium sulfite,
Sulfite salts such as sodium hydrogen sulfite, potassium sulfite and ammonium sulfite are used.

These reducing agents may be used alone or in combination of two or more. The content of this reducing agent in the first agent for permanent wave is preferably 1 to 10% by weight, particularly 2 to 8% by weight. That is, when the content of the reducing agent in the first agent for permanent wave is less than the above range, the hair cannot be sufficiently waved, and the content of the reducing agent in the first agent for permanent wave is When it is more than the above range, the disulfide bond of the hair is reduced too much, the elution of protein from the hair becomes violent, and the hair may be greatly damaged.

The first agent for permanent wave of the present invention is prepared by incorporating the above-mentioned reducing agent and the above-mentioned silylated peptide as essential components into water or a liquid containing water as a main component. Of course, the silylated peptide may be added to the prepared first agent for permanent wave containing a reducing agent or being prepared, and the reducing agent and the silylated peptide may be added in any order. The first agent for permanent wave of the present invention may appropriately contain other components besides the above-mentioned essential components as long as the effects of the present invention are not impaired.

The added components will be described in detail later. In particular, in addition to the silylated peptide represented by the general formula (I) or the silylated peptide represented by the general formula (II) and a reducing agent, a cation is added. In addition to the above-mentioned effects, when the first surfactant for permanent wave contains a cationic surfactant, the hair is imparted with flexibility, the combability of the hair is improved, and the wave efficiency is further improved.

That is, the cationic surfactant is adsorbed on the hair to soften the hair, the hair is easily wavy, the combability of the hair is improved, the hair is prevented from being charged, and a coating is formed on the hair. To prevent the silylated peptide that has penetrated into the hair from being lost by washing the hair and the like, thereby retaining the moisturizing property of the silylated peptide.

Examples of the above-mentioned cationic surfactant include stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetostearyltrimethylammonium chloride, stearylbis (diethyleneglycol) hydroxyethylammonium chloride, behenyltrimethylammonium chloride and behenyltrimethylammonium bromide. , Cetyltrimethylammonium iodide, oleylbenzyldimethylammonium chloride, oleylbis [polyoxyethylene (15EO)] methylammonium chloride (where EO is ethylene oxide, and the value before EO indicates the number of moles of ethylene oxide added),
Tri [polyoxyethylene (5EO)] stearyl ammonium chloride, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, polyoxypropylene methyl diethyl ammonium chloride, mink oil fatty acid amide propyl dimethyl hydroxyethyl ammonium chloride, alkyl pyridinium salt, -γ-chloride Gluconamido propyl dimethyl hydroxyethyl ammonium etc. are mentioned. These cationic surfactants may be used alone or in combination of two or more.

The content of these cationic surfactants in the first agent for permanent wave (content in the first agent for permanent wave) is 0.1.
The range of 5 to 5% by weight, particularly 0.2 to 2% by weight is preferable.
That is, when the compounding amount of the cationic surfactant in the first agent for permanent wave is less than the above range,
If the amount of the cationic surfactant in the first agent for permanent wave is more than the above range, the effect cannot be sufficiently exerted, and the amount adsorbed on the hair becomes too large, and In addition to making it extremely soft, it may cause inconvenience to the touch, as well as elution of protein components from the hair, deterioration of the moisturizing ability of the hair, and dryness of the hair.

First permanent wave combination containing this reducing agent, silylated peptide and cationic surfactant
In addition to these essential components, other components can be appropriately added to the agent as long as the effects of the present invention are not impaired.

In the first agent for permanent wave of the present invention, the components which can be added in addition to the essential components include, for example, licorice derivatives such as glycyrrhizinic acid, carbenoxolone disodium, allantoin, guaiazulene, aloe, α-bisabolol and the like. Anti-inflammatory agent, coconut oil fatty acid diethanolamide, 2-ethylenehexyl sodium sulfosuccinate, sorbitan monolaurate, polyoxyethylene nonyl phenyl ether, penetrants such as benzyl alcohol, ammonium lauryl sulfate, ethanolamine lauryl sulfate, sodium lauryl sulfate, lauryl Alkylsulfates such as triethanolamine sulfate, polyoxyethylene (2EO) lauryl ether triethanolamine sulfate, polyoxyethylene (3
EO) alkyl (any of C 11 to C 15 or 2
Mixtures of two or more kinds) Polyoxyethylene alkyl ether sulfate such as sodium ether sulfate, sodium laurylbenzenesulfonate, alkylbenzenesulfonate such as triethanolamine laurylbenzenesulfonate, polyoxyethylene (3EO) tridecyl ether sodium acetate, etc. Polyoxyethylene alkyl ether acetate, coconut oil fatty acid sarcosine sodium, lauroyl sarcosine triethanolamine, sodium lauroylmethyl-β-alanine, sodium lauroyl-L-glutamate, triethanolamine lauroyl-L-glutamic acid, coconut oil fatty acid-L -Sodium glutamate, coconut oil fatty acid-L-glutamic acid triethanolamine, coconut oil fatty acid methyl taurine sodium, lauroylme N- acylamino acid salts, ether alkane sodium sulfonate sulfates such as Le taurine sodium, hydrogenated coconut oil fatty acid glycerin sodium sulfate,
Undecylenoylamide ethyl sulfosuccinate disodium salt, sodium octylphenoxydiethoxyethyl sulfonate, oleic acid amide disodium sulfosuccinate salt, dioctyl sodium sulfosuccinate salt, lauryl disodium sulfosuccinate salt, polyoxyethylene alkyl (C12-15) ether Phosphoric acid (8-10E
O), sodium polyoxyethylene oleyl ether phosphate, sodium polyoxyethylene cetyl ether phosphate, disodium lauryl polyoxyethylene sulfosuccinate, sodium polyoxyethylene lauryl ether phosphate, sodium lauryl sulfoacetate, sodium tetradecene sulfonate, Undecylenoyl hydrolyzed collagen potassium, lauric acid hydrolyzed collagen sodium, coconut oil fatty acid hydrolyzed collagen sodium, potassium, anionic surfactants such as salts of triethanolamine, 2-alkyl-N-carboxymethyl-N-hydroxy Ethylimidazolinium betaine, undecyl hydroxyethyl imidazolium betaine sodium, undecyl-N-hydroxyethyl-
N-carboxymethyl imidazolinium betaine, stearyl dihydroxyethyl betaine, stearyl dimethylamino acetic acid betaine, coconut oil alkyl betaine, coconut oil fatty acid amidopropyl betaine, coconut oil alkyl-N
-Carboxyethyl-N-hydroxyethyl imidazolinium betaine sodium, coconut oil alkyl-N-carboxyethoxyethyl-N-carboxyethyl imidazolinium disodium hydroxide, coconut oil alkyl N
-Carboxymethoxyethyl-N-carboxymethylimidazolinium disodium lauryl sulfate, amphoteric surfactants such as N-coconut oil fatty acid acyl L-arginine ethyl DL-pyrrolidone carboxylate, polyoxyethylene alkyl (having 12 to 12 carbon atoms). 14) ether (7EO),
Polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene glyceryl oleate, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene cetyl stearyl diether, polyoxyethylene sorbitol lanolin (40EO), Nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyl tetradecyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, polyoxypropylene stearyl ether , Cationized cellulose, cationized hydroxyethyl cellulose, poly (diallyl chloride Lumonium), polyvinylpyrrolidone, cationic polymers such as polyethyleneimine, amphoteric polymers, synthetic polymers such as anionic polymers, isostearic acid diethanolamide, undecylenic acid monoethanolamide, oleic acid diethanolamide, tallow fatty acid monoethanolamide, hardened beef tallow Fatty acid diethanolamide, stearic acid diethanolamide, stearic acid diethylaminoethylamide, stearic acid monoethanolamide, myristic acid diethanolamide, coconut oil fatty acid ethanolamide, coconut oil fatty acid diethanolamide, lauric acid isopropanolamide, lauric acid ethanolamide, lauric acid Diethanolamide, lanolin fatty acid diethanolamide,
Thickeners such as sodium carboxymethyl cellulose, hydroxyethyl cellulose, carboxyvinyl polymer, carrageenan, xanthan gum, triglycopolysaccharide, waxes, paraffins, fatty acid esters, glycerides, oils and fats such as animal and vegetable oils such as lecithin, squalane and avocado oil, animal and plant extraction Thing, collagen, keratin, silk, casein, soybean, wheat, corn,
Hydrolyzed peptides of proteins derived from animals and plants or microorganisms such as potatoes, yeasts and mushrooms and peptide ester derivatives thereof, N-quaternary ammonium derivatives of hydrolyzed peptides of proteins derived from animals and plants or microorganisms, and trimethylammonio-2 A quaternary ammonium derivative having an alkyl chain of 1 to 7, a hydroxypropyl derivative, a triethylammonio-2-hydroxypropyl derivative, a diethylmethylammonio-2-hydroxypropyl derivative, a polysaccharide or a derivative thereof, propylene glycol, 1 , Wetting agents such as 3-butylene glycol, ethylene glycol, glycerin and polyethylene glycol, lower alcohols such as ethanol, methanol, propyl alcohol and isopropyl alcohol, behenyl alcohol Higher alcohols Lumpur, cetyl alcohol, stearyl alcohol, oleyl alcohol, L- aspartic acid, sodium L- aspartate, DL-alanine, L- arginine, glycine, L
-Amino acids such as glutamic acid, L-cysteine, and L-threonine.

[0057]

EFFECT OF THE INVENTION According to the first agent for permanent wave of the present invention, good wave can be applied to the hair without damaging the hair and keeping the hair in good condition. That is, the silylated peptide contained in the first agent for permanent wave prevents hair damage due to permanent wave treatment, restores damaged hair, and imparts moisturizing and luster to the hair, and is silylated. Since the peptide does not interfere with the permanent waving, it is possible to impart excellent waves to the hair.

Further, the first agent for permanent wave of the present invention has excellent storage stability because the silylated peptide has water solubility.

When a cationic surfactant is used in combination, the cationic surfactant softens the hair and makes the hair easily wavy, and improves combability of the hair to form a film on the hair. Then, since the outflow of the silylated peptide sorbed on the hair is suppressed, the moisturizing property of the peptide portion of the silylated peptide is maintained for a long time, and the dryness of the hair is prevented.

[0060]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only those examples. Prior to the examples, the tensile strength test of the hair, the wave efficiency, and the method for measuring the cysteic acid content in the hair, which are carried out in the examples, will be described.

[Hair Tensile Strength Test] A site for measuring the hair tensile strength (18c in the examples).
The major axis and the minor axis of the central part of the hair (m) are measured with a micrometer, and the cross-sectional area is calculated. Next, an adhesive tape [Scotch filament tape, manufactured by Sumitomo 3M Ltd.] is fixed to the hair with an interval of 0.5 mm in the front and back around the point. The part to which this tape was fixed was fixed to the clamp of a tensile tester (Rheometer manufactured by Fudo Kogyo Co., Ltd.), the strength at the time of cutting hair was measured, and the tensile force per cross-sectional area was calculated from the previously determined cross-sectional area. Strength (kgf / m
m ² ) is calculated. The tensile strength of 30 hairs per sample was measured, the average value was calculated for each sample, and the result is shown by the average value.

[Wave Efficiency] Ten hairs are bundled, the roots of the hairs are aligned and fixed with a vinyl tape, and the length is aligned to 18 cm. Use a glass tube with a diameter of 10 mm and a length of 80 mm for the rod and mark every 10 mm in advance (5 mm on the opposite side as well)
Shift and mark). Then, the hair bundle is wrapped around the rod so as to pass over the mark, and both ends are fixed with rubber bands.
2 ml of the first agent for permanent wave is applied to the hair bundle, the rod is covered with wrap, and the hair is left for 15 minutes. After gently washing with running water for about 10 seconds, 2 ml of the second agent is applied, covered with wrap, and left for 15 minutes. Then, after gently washing in running water for 30 seconds, it was dried in a dryer at 50 ° C for 20 seconds.
Dry for minutes. Then, the rubber band on the bristle side is removed, and the rod is horizontally suspended in the desiccator and dried for 12 hours. After drying, the hair bundle is removed from the rod, the wavelength and wave number of the wave are measured, a weight of 3 g is attached to the tip of the hair, and the hair is left in a vertical state in a desiccator for 12 hours.
Remove the weight and measure the wave wavelength and wave number. Further, the hair bundle is kept vertical and left for 24 hours or more in a desiccator, and after a certain time, the wavelength and wave number of the wave are measured again.

The wavelength and wave number are measured as shown in FIG.
Except for the waves at both ends, the distance from the apex of the second wave is also measured on the left and right. If the distances from the vertices of the left and right waves are L ₁ and L _2, and the numbers of waves between L ₁ and L ₂ are n ₁ and n ₂ , respectively, the average wavelength (L) is calculated by the following formula. To be

The wavelength (diameter) of the rod itself is 10 mm.
Therefore, the wave efficiency is calculated by the following equation.

In addition, the wave efficiency after the wave processing,
From the ratio of the wave efficiency after the weight is removed and the wave is recovered after being left for a certain period of time, the wave retention rate is obtained as shown in the following equation.

[Amount of Cysteinic Acid in Hair] To 0.01 g of hair, 2 g of 6N hydrochloric acid was added, and the mixture was kept at 105 ° C. for 20 minutes.
After complete hydrolysis, the amount of cysteic acid (mol%) is determined by an amino acid automatic analyzer. The amount of cysteic acid in the hair indicates the degree of damage to the hair, and the smaller the value, the less the damage to the hair.

Examples 1 and 2 and Comparative Examples 1 to 3 Five types of first agents for permanent wave shown in Tables 1 and 2 were prepared and prepared from the respective first agents for permanent wave and a 6% sodium bromate aqueous solution. The hair bundle was subjected to a permanent wave treatment using the second agent for permanent wave, and the wave efficiency, wave retention rate, tensile strength and amount of cysteic acid in the hair were examined.

In Examples 1 and 2, as the silylated peptide, R ¹ ═CH ₃ and R ^{2 in the} general formula (I) were used.
And R ³ = OH, a = 3, the average value of m = 2, the average value of n = 8, the average value of m + n = 10, and the introduction rate of the silyl functional group was 61%. Example 1
In Examples 1 to 2, methylpolysiloxane [SH200C-100cs (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.] was used as the silicone instead of the silylated peptide. In Comparative Examples 1 and 2, since the methyl polysiloxane was separated, it was used after stirring well before use. In Example 2 and Comparative Example 2, a cationic surfactant was added, but in Comparative Example 3, silylated peptide, methyl polysiloxane, cationic surfactant, etc. were not used at all.

The blending amounts of the components in Tables 1 and 2 are based on parts by weight, and when the blending amount is not the solid content, the solid content concentration is shown in parentheses after the component name. These are the same in the following examples.

[0070]

[Table 1]

[0071]

[Table 2]

Four hair bundles each consisting of 10 hairs were prepared for each of the Examples and Comparative Examples, and each hair bundle was subjected to permanent wave treatment by the method described in the section of measuring the wave efficiency, and the wave efficiency and The wave retention rate after 5 days was determined. Next, each hair bundle is subjected to a tensile strength test, and for 40 hairs, the cross-sectional area of a portion 9 cm from the end is measured, and 5 hairs each from the larger and smaller cross-sectional area are tested. It was excluded and the tensile strength of the remaining 30 hairs was measured. Furthermore, a part of the hair after the permanent wave treatment was decomposed to measure the amount of cysteic acid. The results are shown in Table 3.

[0073]

[Table 3]

As is clear from the results shown in Table 3, when treated with the first agent for permanent wave of Examples 1 and 2, the first agent for permanent wave of Comparative Examples 1 to 3 was used.
The wave efficiency and the wave retention rate are larger than those in the case of treating with the agent. Particularly, Example 2 in which the silylated peptide and the cationic surfactant are blended has the highest wave efficiency and is the blank of the permanent wave of Comparative Example 3. The wave efficiency was increased by about 6.9% when treated with the first agent for use. In addition, both the cases of treating with the permanent wave first agent of Comparative Example 1 and Comparative Example 2 had lower wave efficiency than the case of treating with the permanent wave first agent of Comparative Example 3, which was It is considered that this is because methylpolysiloxane made it difficult to perform the permanent wave treatment.

Regarding the tensile strength per cross-sectional area of the hair, when treated with the first agent for permanent wave of Examples 1 and 2, the first step for permanent wave of Comparative Example 3 was used.
It was revealed that the silylated peptide sorbed on the hair to increase the tensile strength, which was increased by 10% or more as compared with the case of treating with the agent. Furthermore, when treated with the first agent for permanent wave of Examples 1 and 2, the amount of cysteic acid in the hair was smaller than that when treated with any of the first agents for permanent wave of Comparative Examples 1 to 3, It has been clarified that the first agent for permanent wave of Examples 1 and 2 containing the modified peptide causes less damage to the hair during the permanent wave treatment.

Example 3 and Comparative Examples 4 to 5 Three types of first permanent wave compositions having the compositions shown in Table 4
The agent was prepared.

In this Example 3, as the silylated peptide, in the general formula (II), R ¹ ═CH ₃ , R ² and R ³ ═OH, a = 1, the average value of m = 1.4, Silylated hydrolyzed collagen having an average value of 18.6, an average value of m + n of 20 and a silyl functional group introduction rate of 67% was used, and benzalkonium chloride was used as a cationic surfactant. In Comparative Example 4, instead of the silylated peptide, methylphenylpolysiloxane [Toray
SH556 (trade name) manufactured by Dow Corning Silicone Co., Ltd. was used, and none of them was used in Comparative Example 5. In Comparative Example 4, since the methyl phenyl polysiloxane of silicone was separated, it was used after being sufficiently stirred before use.

[0078]

[Table 4]

In the tests relating to these Example 3 and Comparative Examples 4 to 5, a hair bundle having a weight of 1 g and a length of 15 cm was used.
Wrap it around a rod with a diameter of 1 cm, 6% for the second agent
Permanent wave treatment was performed using an aqueous sodium bromate solution. The suppleness of the hair after treatment, the luster of the hair,
Moisture was evaluated by 10 panelists (7 females, 3 males). The evaluation criteria are the best (2 points), the next best (1 point), and the worst (0 point), and the results are shown as an average value of 10 persons.

Further, the tensile strength of the hair after the permanent wave treatment and the amount of cysteic acid in the hair were measured.
For the measurement of the tensile strength, 30 hairs from each hair bundle were selected and used in the same manner as in Example 1. The results (average value) are shown in Table 5.

[0081]

[Table 5]

As is clear from the results shown in Table 5, when treated with the first agent for permanent wave of Example 3 containing silylated hydrolyzed collagen, Comparative Examples 4 to 5 were used.
Compared with the case of treatment with the first agent for permanent wave, the evaluation values of hair suppleness, luster and moisture are all high, and the tensile strength of hair is large, the amount of cysteic acid in hair is small, and silylated. It has been shown that hydrolyzed collagen sorbs well on hair, prevents damage to the hair during permanent wave treatment, and increases the tensile strength of the hair.

Examples 4 to 5 and Comparative Examples 6 to 8 Five types of first agents for permanent wave having the compositions shown in Tables 6 to 7 were prepared.

In Examples 4 to 5, as the silylated peptide, R ¹ ═CH ₃ in the general formula (II),
R ² and R ³ = OH, a = 3, the average value of m = 1, the average value of n = 7, the average value of m + n = 8, and the introduction rate of silyl functional group was 62%. Oleyl bis [polyoxyethylene (15EO)] methylammonium chloride is used as the cationic surfactant. In Comparative Example 6, octamethylcyclotetrasiloxane [SH244 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd.] was used as the silicone instead of the silylated peptide, and in Comparative Example 7, none of them was used. In Example 5 and Comparative Example 7, a cationic surfactant was added, but in Comparative Example 8, silylated peptide, silicone, cationic surfactant, etc. were not used at all. In Comparative Example 6 and Comparative Example 7, since octamethylcyclotetrasiloxane of silicone was separated, it was used after being well stirred before use.

[0085]

[Table 6]

[0086]

[Table 7]

Then, in the same manner as in Example 1 described above, the first agent for permanent wave of Examples 4 to 5 and Comparative Examples 6 to 8 and 2% hydrogen peroxide solution as the second agent were used, and rods were used. Permanent wave treatment was carried out on the hair wound around, and the wave efficiency of the hair after the treatment, the wave retention rate after 5 days, the tensile strength of each hair and the amount of cysteic acid in the hair were examined. The results are shown in Table 8.

[0088]

[Table 8]

As is clear from the results shown in Table 8, the treatment with the first agent for permanent wave of Examples 4 to 5 is higher than that of the first agent for permanent wave of Comparative Examples 6 to 8. The wave efficiency and the wave retention rate were also large. In particular, when treated with the first agent for permanent wave of Example 5 in which the silylated peptide and the cationic surfactant were blended, the wave efficiency and the wave retention rate were the highest. However, Comparative Example 6 containing octamethylcyclotetrasiloxane as the silicone
When treated with the first agent for permanent wave of Nos. 7 to 7, both the wave efficiency and the wave retention rate were smaller than those when treated with the first agent for permanent wave of Comparative Example 8 corresponding to the blank. It is considered that this is because the incorporation of silicone made it difficult to perform the permanent wave treatment.

With cysteine perm, the wave efficiency is slightly lower than that of the permanent wave treatment using thioglycolic acid as a reducing agent, but the hair is less damaged, so that the tensile strength and the amount of cysteic acid in the hair are
Although the difference between Examples and Comparative Examples is not so large, the hair treated with the first agent for permanent wave of Examples 4 to 5 is still treated with the first agent for permanent wave of Comparative Examples 6 to 8. It has been found that the tensile strength of the hair is higher than that of the hair and the amount of cysteic acid in the hair is small, and the silylated hydrolyzed wheat protein is sorbed on the hair to prevent the hair from being damaged during the permanent wave treatment. Was there.

[Storage Stability of First Agent for Permanent Wave] The first agent for permanent wave prepared in each example was stored at room temperature (15 to 25 ° C.) for 30 days to determine whether precipitation or layer separation occurred. Was visually observed. The results are shown in Table 9 by "+" when precipitation or layer separation occurred and by "-" when precipitation or layer separation did not occur. In addition, since the first agent for permanent wave prepared by blending silicone in Comparative Example did not use an emulsifier, layer separation occurred from the time of preparation, and thus a storage test was not performed.

[0092]

[Table 9]

As shown in Table 9, each of the first agents for permanent wave of Examples 1 to 5 had excellent storage stability without precipitation or layer separation after storage at room temperature for 30 days.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a state of hair after a permanent wave treatment.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Chika Nakano 1-2-14, Nunoichi-cho, Higashi-Osaka City, Osaka Prefecture Seiwa Kasei Co., Ltd. (56) Reference Japanese Patent Laid-Open No. 3-223207 (JP, A) Kaihei 4-154713 (JP, A) JP-A-5-17323 (JP, A) Takeo Tamura, Cosmetics Science, Japan Hair Science Society, August 20, 1981, 6th edition, pp. 354-379 ( 58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/09

Claims (4)

(57) [Claims] 1. A first agent for permanent wave containing a reducing agent as a main agent, wherein the functional group containing only one silicon atom is covalently bonded to the amino group of the peptide containing the amino group of the amino acid side chain. (I) ^{Wherein, R 1, R 2, R} 3 2 or Chi caries represents a hydroxyl group,
The rest represent methyl groups. R ⁴ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the end of the side chain, R ⁵ represents a side chain of an amino acid other than R ⁴ , a is 1 or 3, and m is 0. Greater than 50 and n is 1 to 20
0, m + n is 2 to 200 (however, m and n only indicate the number of amino acids, and do not indicate the order of amino acid sequences)], or the following general formula ( II) [Chemical 2] ^{Wherein, R 1, R 2, R} 3 2 or Chi caries represents a hydroxyl group,
The rest represent methyl groups. R ⁴ represents a residue excluding the terminal amino group of a basic amino acid having an amino group at the end of the side chain, R ⁵ represents a side chain of an amino acid other than R ⁴ , a is 1 or 3, and m is 0. Greater than 50 and n is 1 to 20
0, m + n is 2 to 200 (however, m and n only indicate the number of amino acids, and do not indicate the order of amino acid sequences)]. The first agent for permanent wave. 2. The amount of the silylated peptide compounded is 0.1 to 10.
The first agent for permanent wave according to claim 1, which is 15% by weight. 3. The first agent for permanent wave according to claim 1, which further comprises a cationic surfactant. 4. The compounding amount of the cationic surfactant is 0.
The first agent for permanent wave according to claim 3, which is 1 to 5% by weight.