JPH0245409A - Cosmetic for hair - Google Patents

Abstract

PURPOSE:To obtain a hair cosmetic effective in preventing the damage of hair and imparting the hair with softness, combing property, bulkiness, luster, etc., by compounding a cationic polymer and a keratin peptide derived from an N-quaternary ammonium. CONSTITUTION:The objective cosmetic can be prepared by compounding (A) 0.05-10wt.% of a compound of formula I (R1-R3 are 1-20C alkyl or one or two of R1-R3 are 1-20C alkyl and the others are 1-3C hydroxyalkyl or benzyl; R4 is H or OH; R5 is amino acid side chain constituting a peptide derived from keratin; n is 2-30) and (B) 0.05-5wt.% of a cationic polymer such as diallyl- quaternary ammonium salt polymer, cationic cellulose or cationic vinyl polymer. The compound of formula I can be produced by reacting a keratin peptide with a glycidyl ammonium salt of formula II, a 3-halogeno-2-hydroxypropyl ammonium salt of formula III or a 3-halogenopropyl ammonium salt of formula IV.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a hair cosmetic containing an N-quaternary ammonium-derived keratin peptide and a cationic polymer.

[Conventional technology]

Various hair cosmetics are used for hair, such as shampoo, hair rinse, aerosol foam, JPJ for permanent wafers, hair cream, hair conditioner, set lotion, hair treatment lotion, hair color, and hair color.

However, by using these hair cosmetics,
The hair may be damaged instead.

For example, if you use a permanent wave agent,
Due to reduction and alkali swelling by the first agent and excessive oxidation by the second agent, a part of the keratin protein that makes up the hair is eluted, and the remaining part of the hair also undergoes physical and chemical changes, causing the hair to look strange. A feeling of dryness or dryness may occur.

In addition, since the surfactants contained in shampoos have a strong surfactant ability, even the sebum and constituent proteins of the hair are eluted, damaging the hair and making it feel dry or coarse after drying. Become.

A hair rinse is used after shampooing to give the hair flexibility and natural shine.
The main ingredients used are alkyltrimethylammonium chloride, dialkyltrimethylammonium chloride, and long-chain alkyl having 16 to 18 carbon atoms.
Cationic surfactants such as alkyldimethylbenzyl ammonium chloride [for example, Tetsusaku Ikeda,
Cosmetic Science J, (1979, 5, 20), ■ Nanzando,
P305-306], these have a strong surfactant ability, so if they are used in large amounts, the sebum and constituent proteins of the hair will be eluted, just like in the case of shampoo, making the hair feel dry or coarse. .

As mentioned above, although the ingredients used as the main ingredients in hair cosmetics have one aspect that is useful in achieving their original purpose, there is a risk of damaging the hair on the other side. The reality is that sufficient consideration has not been given to hair cosmetics.

[Problem to be solved by the invention]

The present invention solves the problem that conventional hair cosmetics cause damage to the hair as a result of their use, and prevents hair damage without interfering with the original function of hair cosmetics. To provide hair cosmetics capable of imparting flexibility, good combability, plumpness, luster, etc. to hair.

[Means to solve the problem]

The present invention provides hair cosmetics with the general formula
R3 is an alkyl group having 1 to 20 carbon atoms, or one or two of R1-R1 is an alkyl group having 1 to 20 carbon atoms,
The remainder is a hydroxyalkyl group or benzyl group having 1 to 3 carbon atoms. R1 is a hydrogen atom or a hydroxyl group, R2 is a side chain of an amino acid constituting a peptide derived from keratin, and n is 2 to 30).
By blending grade ammonium-derived keratin peptides and cationic polymers, hair damage is prevented,
To provide a hair cosmetic that can better exhibit its original functions and impart flexibility, good combability, plumpness, luster, etc. to the hair.

The N-quaternary ammonium-derived keratin peptide represented by the above general formula (1) is composed of a keratin peptide and the following general formula (II) [wherein R1, R8, and R2 are the same as those in the above general formula (1)]. are the same, and X is CI, Br, l5NO,, S04/2
or R & OS Os (Rh is a lower alkyl group)] or the following general formula (III) R Rz N' CHz CH--CHz
Y' XθR,OH (R1, R2, R1 and X in the formula (II
), where Y represents a halogen atom such as CI, Br, 1, etc.) or a 3-halogen-2-hydroxypropylammonium salt represented by the following general formula (rt/)R1 Rs (in the formula R9, Rz, Rs, X and Y are represented by the general formula (
It is the same as in case ①)) It can be obtained by reacting any of the 3-halogenpropylammonium salts shown below.

The above keratin peptides include animal hair, hair, feathers, nails, horns,
Obtained by hydrolyzing hooves, scales, etc. with acids, alkalis, or enzymes.

The above keratin peptides have a chemical structure similar to keratin, which is a constituent protein of hair, and they adsorb to hair through their amino groups, carboxyl groups, or side chains of various amino acids, protect hair, and repair damaged hair. It has a restorative effect. Furthermore, since it is derived from natural protein, it is safe and less irritating to hair.

The N-quaternary ammonium-derived keratin peptide represented by the above-mentioned -Tsuriyoshi (1) is prepared by reacting the above-mentioned keratin peptide with any of the ammonium salts shown by the above-mentioned -Tsuzuriyoshi (11) to (IV). By making it quaternary,
It is a product that has even higher adsorption properties and softening effects on the hair, and it helps condition the hair by adsorbing it to the hair, softening it, and adding moisture and luster to the hair. It has a protective effect. Furthermore, the N-quaternary ammonium-derived keratin peptide indicated by -Tsuzuriyo (I) has a strong surfactant ability like the cationic surfactant mentioned above, and therefore can be used for degreasing and degreasing based on the surfactant ability. No harmful effects such as protein denaturation occur.

On the other hand, as will be explained in detail later, cationic polymers include polymers of diallyl quaternary ammonium salts, cationic cellulose, cationic starch, cationic vinyl polymers, etc. Similar to surfactants, it adsorbs well to hair, and the above-mentioned -
It makes the hair more flexible than the N-quaternary ammonium-derived keratin peptide indicated by Tsuzuriyo ([), improves combability, gives luster and luster to the hair, and makes it easier to condition the hair, but it has a long-term effect. Depending on the usage, the accumulated excessive adsorption and degreasing/cleaning action may cause
It may give an unpleasant feeling such as hair becoming crunchy. Particularly in damaged hair, the adsorption is significant, which may make the hair feel even worse.

Therefore, in the present invention, by using this cationic polymer together with the N-quaternary ammonium-derived keratin peptide represented by the above-mentioned general formula (+), the drawbacks of the cationic polymer can be avoided and the long-term Even when used regularly, it exerts excellent conditioning effects without damaging the hair or deteriorating its texture.

Next, the N-quaternary ammonium-derived keratin peptide and the cationic polymer will be explained in detail in this order.

In the above-mentioned Tsuzuriyo (1), the amino acids whose side chain of the keratin peptide moiety is represented by R1 include alanine, glycine, valine, leucine, isoleucine, proline, phenylalanine, tyrosine, serine, threonine, methionine, arginine, histidine, Examples include lysine, aspartic acid, asparagine, glutamic acid, glutamine, cystine, and tryptophan. Table 1 shows an example of the analysis results of the composition ratios of these amino acids. Although asparagine and glutamine are not shown in Table 1, they are converted into aspartic acid and glutamic acid, respectively, during hydrolysis (completely hydrolyzed with 6N hydrochloric acid in the conventional method) prior to analysis. This is because it has become. In other words, aspartic acid and glutamic acid in Table 1 include those that existed as asparagine and glutamine in keratin. Furthermore, since cystine has two amino groups and two carboxyl groups, Table 1 shows the mole % as half cystine. Also, tryptophan is lost during complete hydrolysis with 6N hydrochloric acid prior to analysis, so although it is not shown in Table 1, about 1% tryptophan is present in keratin.
Contains about mol%.

Table 1 The hydrolysis of keratin to obtain the above keratin peptides is carried out with acids, alkalis or enzymes, as disclosed, for example, in JP-A-59-84898.

For acid hydrolysis, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrobromic acid, and organic acids such as acetic acid and formic acid are used.

For alkaline hydrolysis, sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, lithium carbonate, etc. are used.

For hydrolysis by enzymes, acidic proteolytic enzymes such as pepsin, protase A and protase B, and neutral proteolytic enzymes such as papain, bromelain, thermolysin, trypsin, pronase and chymotrypsin are used. Additionally, domestically produced neutral proteolytic enzymes such as subtilisin and staphylococcal protease can also be used. When using the enzyme, it can be used in the form of microbial cells containing these domestically produced proteolytic enzymes, or in the form of membranes, granules, etc. in which enzymes or microbial cells containing enzymes are immobilized.

The keratin peptide obtained by hydrolysis with an acid, alkali or an enzyme as described above has a formula (1) in which n is 2 to 30 (however, the value of n is an average value,
'n is 2 to 30, which corresponds to an average molecular weight of about 150 to about s, ooo), which is n
If n is less than 2, the adsorption of the keratin peptide itself to hair will be low, and if n exceeds 30, the water solubility will decrease, making it difficult to handle, and the adsorption to hair will decrease.

The N-quaternary ammonium-derived keratin peptide represented by the general formula (1) is obtained by the reaction of the keratin peptide with the ammonium salt represented by the general formulas (II) to (IV), as described above. The reaction formula is as follows. In addition, in showing the reaction formula, the keratin peptide is shown by the following general formula (V).

HEN H-CH-G OH ■ Reaction between keratin peptide and glycidylammonium salt represented by general formula (II) ■ Reaction between keratin peptide and glycidylammonium salt represented by general formula (III) ■
Reaction H with halogen-2-hydroxypropylammonium salt Reaction R3 between keratin peptide and 3-halogenpropylammonium salt represented by general formula (IV) The above keratin peptide represented by ■ or ■ and -8 formula (IT ), a 3-halogen-2-hydroxypropylammonium salt represented by the -m formula (III), or a 3-halogen-2-hydroxypropylammonium salt represented by the general formula (■)
-The reaction with a halogen propylammonium salt is usually
A glycidylammonium salt represented by general formula (II), a 3-halogen-2-hydroxypropylammonium salt represented by m formula (III), or a 3-halogenpropylammonium salt represented by general formula (IV) in an aqueous solution of keratin peptide. During the zero reaction, which is carried out by dropping a solution of
It is preferable to keep the value between 8 and 12, particularly between 9 and 11, and for this purpose, an alkaline solution such as sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. is added dropwise into the reaction solution as necessary. The pH within the reaction system is maintained within the above range by using a glycidylammonium salt, -m, in which the amino group of the keratin peptide is represented by the general formula (n).
In order to react with the 3-halogen-2-hydroxypropylammonium salt represented by the formula (III) or the 3-halogenpropylammonium salt represented by the general formula (N>), the pH is preferably 8 or more on the alkaline side, In addition, when the pH exceeds 12, keratin peptides and general formula (n
), a glycidylammonium salt of formula -m (If
This is because the 3-halogen-2-hydroxypropylammonium salt represented by f), the 3-halogenpropylammonium salt represented by -m formula (IV), etc. cause hydrolysis. The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, when the pH is high and the temperature is high (-m formula (U) glycidylammonium salt, -m formula (Iff) 3-halogen-2-hydroxypropylammonium salt, -m formula (Iff), Since the hydrolysis of 3-halogenpropylammolum salt represented by rt/) is also promoted, it is preferable to keep the temperature at most 80'C or less.

-8 glycidylammonium salt represented by formula (II),
The 3-halogen-2-hydroxypropylammonium salt represented by the -m formula (III), the 3-halogenpropylammonium salt represented by the -m formula (IV), etc. may be used in the form of crystals; A glycidylammonium salt represented by the general formula (n), which is preferably added dropwise as a solution, to a keratin peptide solution, -
Dropwise addition of 3-halogen-2-hydroxypropylammonium salt represented by formula (III), 3-halogenpropylammonium salt represented by formula (IV), etc.
It is preferable to finish in 5 minutes to 6 hours.

In these reactions, hydrogen halides are generated and the pH of the reaction solution decreases, so it is necessary to drop an alkali at the same time as the reaction starts and stir to maintain the pH in the solution within a range suitable for the reaction. is necessary.

The progress and completion of the reaction can be confirmed by measuring the 7-minor nitrogen of the keratin peptide in the reaction solution using the Van Slater method for the reaction to the amino group. Thereafter, the reaction solution is appropriately concentrated or purified by using an ion exchange resin, gel filtration, electrodialysis, etc., and then appropriately concentrated to obtain a reaction product in the form of a solid or a concentrated liquid.

As mentioned above, a glycidylammonium salt represented by the general formula (It) used for the reaction with a keratin peptide,
Specific examples of the 3-halogen-2-hydroxypropylammonium salt represented by the -m formula (I[[) and the 3-halogenpropylammonium salt represented by the -m formula (R/) are as follows. be.

Examples of the glycidyl ammonium salt represented by the general formula (II) include glycidyl trimethyl ammonium chloride, glycidyl triethylammonium chloride, glycidyl triethanol ammonium chloride, glycidyl tripropylammonium chloride, glycidyl triisopropylammonium chloride, glycidyl trimethyl ammonium bromide, and glycidyl trimethyl ammonium chloride. Iodide, glycidyl lauryl dimethyl ammonium chloride, glycidyl myristyl dimethyl ammonium chloride, glycidyl cetyl dimethyl ammonium chloride, glycidyl stefyl dimethyl ammonium chloride, glycidyl lauryl dimethyl ammonium bromide, glycidyl myristyl dimethyl ammonium bromide, glycidyl cetyl dimethyl ammonium bromide, glycidyl stearyl dimethyl ammonium Bromide, glycidyl capryl dimethyl ammonium chloride, glycidyl eicosyl dimethyl ammonium chloride, glycidyl capryl dimethyl ammonium bromide, glycidyl eicosyl dimethyl ammonium bromide, glycidyl lauryl dibenzylammonium chloride, glycidyl cetyl dibenzylammonium chloride, glycidyl stearyl dibenzylammonium chloride, glycidyl lauryl jetanol ammonium chloride, glycidyl cetyl jetanol ammonium chloride,
Glycidylstearylditanol ammonium chloride, glycidyl dilauryl methyl ammonium chloride, glycidyl cetyl dityl ammonium chloride, glycidyl distearyl methyl ammonium chloride, glycidyl dilauryl ethanol ammonium chloride, glycidyl cetyl ditanol ammonium chloride, glycidyl distearyl ethanol ammonium chloride, etc. are used. It will be done.

- As the 3-halogen-2-hydroxypropylammonium salt represented by Tsukuriyo (III), 3-chloro-2
-Hydroxypropyltrimethylammonium chloride, 3-chloro-2-human, roxybrovirtriethylammonium chloride, 3-chloro-2-hydroxypropyltriethanolammonium chloride, 3-
Chloro-2-hydroxypropyltripropylammonium chloride, 3-chloro-2-hydroxypropyltriisopropylammonium chloride, 3-chloro-2-hydroxypropyltrimethylammonium bromide, 3-chloro-2-hydroxypropyltrimethylammonium iodide, 3 -promo 2-hydroxypropyltrimethylammonium chloride, 3-
Promo 2-hydroxypropyltrimethylammonium bromide, lauryl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, myristyl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, cetyl (3-chloro-2-hydroxypropyl) Dimethylammonium chloride, stearyl (3-chloro-2-hydroxypropyl) dimethylammonium chloride, capryl (3-chloro-2-hydroxypropyl)
2-hydroxypropyl)dimethylammonium chloride, eicosyl(3-chloro-2-hydroxypropyl)dimethylammonium chloride, lauryl(3-
Chloro-2-hydroxypropyl) dimethylammonium bromide, myristyl (3-chloro-2-hydroxypropyl) dimethylammonium bromide, cetyl (3-chloro-2-hydroxypropyl) dimethylammonium bromide, stearyl (3-chloro-2-hydroxy propyl) dimethylammonium bromide,
Lauryl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, myristyl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, cetyl (3-chloro-2-hydroxypropyl) dibenzylammonium chloride, stearyl ( 3-chloro-2-hydroxypropyl) dibenzylammonium chloride, lauryl (3-chloro-2-hydroxypropyl) jetanol ammonium chloride, myristyl (3-chloro-2-hydroxypropyl) jetanol ammonium chloride, cetyl (3-
chloro-2-hydroxypropyl) jetanol ammonium chloride, stearyl (3-chloro-2-hydroxypropyl) jetanol ammonium chloride, dilauryl (3-chloro-2-hydroxypropyl)
Methyl ammonium chloride, simiristyl (3-chloro-2-hydroxypropyl) methyl ammonium chloride, dicetyl (3-chloro-2-hydroxypropyl) methyl ammonium chloride, distearyl (
3-chloro-2-hydroxypropyl) methylammonium chloride, lauryl (3-bromo 2-hydroxypropyl) dimethylammonium chloride, myristyl (3-bromo-2-hydroxypropyl) dimethylammonium chloride, cetyl (3-bromo 2-hydroxypropyl) dimethylammonium chloride, propyl) dimethylammonium chloride,
Stearyl (3-bromo-2-hydroxypropyl) dimethylammonium chloride and the like are used.

In addition, the 3-halogenpropylammonium salts represented by the - binding margin (IV) include 3-chloropropyltrimethylammonium chloride, 3-chloropropyltriethylammonium chloride, 3-chloropropyltripropylammonium chloride, 3-chloropropyltrimethylammonium chloride, and 3-chloropropyltrimethylammonium chloride. Isoprobyl ammonium chloride, 3-chloropropyltrimethylammonium bromide, 3-bromopropyltrimethylammonium bromide, lauryl (3-chloropropyl) dimethylammonium chloride, myristyl (3-chloropropyl) dimethylammonium chloride, cetyl (3-chloropropyl) Dimethylammonium chloride, stearyl (3-chloropropyl) dimethylammonium chloride, capryl (3-chloropropyl) dimethylammonium chloride, eicosyl (3-chloropropyl) dimethylammonium chloride, lauryl (3-chloropropyl) dimethylammonium bromide, myristyl (3) -chloropropyl)dimethylammonium bromide, cetyl(3-chloropropyl)dimethylammonium bromide, stearyl(3-chloropropyl)dimethylammonium bromide, lauryl(3-chloropropyl)dibenzylammonium chloride, myristyl(3-chloropropyl)dimethylammonium bromide, Benzyl ammonium chloride, cetyl (3-chloropropyl) dibenzylammonium chloride, stearyl (3-chloropropyl) dibenzylammonium chloride, lauryl (3-chloropropyl) jetanol ammonium chloride, myristyl (3-chloropropyl) jetanol ammonium Chloride, cetyl (3-chloropropyl) jetanol ammonium chloride, stearyl (3-chloropropyl) jetanol ammonium chloride, dilauryl (3-chloropropyl) methyl ammonium chloride, simiristyl (3-chloropropyl) methyl ammonium chloride, dicetyl ( 3-chloropropyl) methylammonium chloride, distearyl (3-chloropropyl) methylammonium chloride, lauryl (3-bromopropyl) dimethylammonium chloride, myristyl (3-bromopropyl) dimethylammonium chloride, cetyl (3-bromopropyl) Dimethylammonium chloride, stearyl (3-promopropyl) dimethylammonium chloride, etc. are used.

R+ SRz and R3 in general formula (1) are the above-mentioned −
Glycidylammonium salt represented by Tsukuriyo (II),
- It is derived from the 3-halogen-2-hydroxypropylammonium salt represented by the binding margin (II) or the 3-halogenpropylammonium salt represented by the general formula (IV), and these R5, R2, and R3 are derived from the above-mentioned - Tsuzuriyo (1
) may be the same or different from each other under the conditions shown in ().

On the other hand, examples of the cationic polymer include polymers of diallyl quaternary ammonium salts, cationic cellulose, cationic starch, and cationic vinyl polymers, as detailed below.

(1) Polymers of diallyl quaternary ammonium salts Examples of polymers of diallyl quaternary ammonium salts include polymers shown in (1) to (4) below.

In (-spelling allowance 0) to (4), R1 and Re are the same or different and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms, and R9 and R1° are the same. Additionally or differently, it represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, and Z represents an anion;
Indicates halogen ions such as chlorine and bromine, inorganic acid residues such as sulfuric acid and nitric acid, and organic acid residues such as methyl sulfuric acid and hydroxycarboxylic acid, and nl, -1 and R8, lI richness indicates a molecular weight of 10,000 to 1 million. (2) Cationic morulose or cationic starch Examples of cationic cellulose or cationic starch include compounds represented by the following general formula (5).

[In the formula, A is a cellulose residue or a starch residue, B is polyoxyethylene or polyoxypropylene with an addition number θ to 10, C is an alkylene group or a hydroxyalkylene group, R11, RI! , R+s are the same or different,
A heterocycle may be formed by including an alkyl group, an aryl group, or a nitrogen atom in the formula.

2 is an anion (halogen ion such as chlorine, bromine, iodine, acid residue such as sulfuric acid, sulfonic acid, nitric acid), l is a positive integer] (3) Cationic vinyl polymer As a cationic vinyl polymer, The following general formulas (6) to (
Examples include polymers shown in 8).

Ze　　R,.

(In the formula, R14 and RI% are the same or different, a hydrogen atom,
Represents an alkyl group or phenyl group having 1 to 6 carbon atoms, and n
, and Z are the same as above) RI& (wherein, R16 is a hydrogen atom or a methyl group, R1?, R
18, R19 are the same or different, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group, T is an oxygen atom or an NH group in an amide bond, Z is an anion, l1
3 is an integer from 1 to lO, nl is the same as above) \ n (wherein, Rto, R□, Ro are the same or different,
hydrogen atom, an alkyl group or substituted alkyl group having 1 or 2 carbon atoms, 2 is an anion, and n is the same as above) Among these cationic polymers, diallyldimethylammonium homopolymer, cationic cellulose, etc. are particularly suitable. preferable.

As mentioned above, the above cationic polymer is
Similar to cationic surfactants, it adsorbs on the hair, makes the hair more flexible than the N-quaternary ammonium-derived keratin peptide shown in the above-mentioned - Tsuduriyo N, and improves the hair's combability. It gives shine to the hair and makes it easier to condition the hair, but depending on long-term use, it can accumulate excessive adsorption and strong degreasing and cleaning effects.
It may give an unpleasant feeling such as hair becoming crunchy. Particularly in damaged hair, the adsorption is significant, which may make the hair feel even worse.

Therefore, this cationic polymer and the general formula (1
) By using it in combination with the N-quaternary ammonium-derived keratin peptide, the drawbacks of cationic polymers are avoided, and even when used for a long time, it does not cause hair damage or deterioration of hair feel, and provides an excellent product. to exert a conditioning effect.

The blending amount of the N-quaternary ammonium-derived keratin peptide and cationic polymer shown in -Tsuriyoshi (1) above in the hair cosmetics is as follows: Keratin peptides 0.05-10%
(wt%, same below), cationic polymer is 0.05
A range of 5% is preferred. This is because - if the amount of the N-quaternary ammonium-derived keratin peptide or cationic polymer, which is indicated by the margin (1), is less than the above range, their effects will not be fully exhibited; N
- If the amount of quaternary ammonium-derived keratin peptide exceeds the above range, it will remain in the hair and make it sticky, and if the amount of cationic polymer exceeds the above range, the hair will be damaged.

Examples of hair cosmetics include shampoos, hair rinses, aerosol foams, hair creams, permanent waving agents, hair conditioners, setting lotions, hair treatment lotions, hair colors, and hair colorants. It will be done.

And, the N-quaternary ammonium-derived keratin peptide and cationic polymer shown in the above-mentioned -Tsuriyo (1),
Basically, it is sufficient to combine the above-mentioned compositions conventionally used in hair cosmetics at the above-mentioned ratio. However, products that originally contain cationic polymers, such as hair rinses and foams , a part of the cationic polymer may be replaced with the N-quaternary ammonium-derived keratin peptide represented by the general formula (1).

In addition to these N-quaternary ammonium-derived keratin peptides and cationic polymers represented by Tsuzuriyo (1), examples of ingredients that may be added to the hair cosmetics include anionic surfactants, nonionic surfactants, etc. surfactants such as cationic surfactants, anionic polymers, nonionic polymers, amphoteric polymers, naturally extracted oils, higher fatty acids, hydrocarbons, fatty acid esters, glycerides, waxes, alkyl alcohols, Alkylamides, oils such as silicone oils (e.g. dimethylpolysiloxane, methylphenylpolysiloxane, and various other modified silicone oils), protein hydrolysates such as collagen peptides, keratin peptides, and silk peptides or their derivatives, moisturizers, alcohols , thickeners, plant extracts, animal extracts, ultraviolet absorbers,
These include pH adjusters, chelating agents, preservatives, pigments, and fragrances.

〔Example〕

Next, the present invention will be explained in more detail with reference to reference examples (manufacturing examples of N-quaternary ammonium-derived keratin peptides) and examples. However, the present invention is not limited only to the examples.

Reference example 1 450 g of 35% hydrochloric acid to 500 g of wool in a Mitsuro flask
was added, and hydrolysis was carried out at 80°C for 16 hours with stirring. After hydrolysis, the reaction mixture was filtered, and the iIt solution was mixed with a weakly basic anion exchange resin Diaion WA-20 (trade name,
After neutralizing with 1,400 ml of Mitsubishi Chemical Industries ■), it was concentrated and filtered to remove the ion exchange resin to a concentration of 4.
A 0% aqueous solution of keratin peptides was obtained. The molecular weight of the keratin peptide thus obtained was measured by gel filtration, and the average molecular weight was 800.

900g of the obtained keratin peptide aqueous solution with a concentration of 40%
(The average molecule of keratin peptide is 1800 (this is expressed as n of -suji (V), the average value is about 8), the total amount of amino nitrogen is 430 mmol] is placed in a reaction container,
While heating to 0°C and stirring, add 87g of an aqueous solution of glycidyltrimethylammonium chloride with a concentration of 75% (
09g equivalent of amino nitrogen in keratin peptide)
The reaction solution was added dropwise over a period of 0 minutes, and during that time, a 20% aqueous sodium hydroxide solution was appropriately added dropwise to maintain the pH of the reaction solution at 10.0. After the completion of the dropwise addition of glycidyltrimethylammonium chloride, stirring was continued for 2 hours while maintaining the pH at 1000, and then after being left for 24 hours, the amino nitrogen was measured, and the total amount of amino nitrogen was 33 mmol. 92% of the amino nitrogen was reacted.

Next, 220 mffi of a weakly acidic cation exchange resin Amberlite RC-50 (trade name, Organo ■) was added to the reaction solution to neutralize it to pH 6.5, and the sodium ions in the reaction solution and the slight remaining unreacted of glycidyltrimethylammonium is adsorbed onto an ion exchange resin, and then the ion exchange resin is removed to obtain N-quaternary ammonium-derived keratin peptide (N-(3-trimethylammonio-2-hydroxypropyl) at a concentration of 30%). An aqueous solution of [keratin peptide] was obtained.

When the resulting aqueous solution was subjected to a quaternary ammonium salt quality reaction, a white precipitate was formed with sodium tetraphenylboronate, and a red precipitate was formed with the Dollagendorff reagent, indicating a positive result.

Furthermore, in order to confirm that the keratin peptide and glycidyltrimethylammonium chloride had reacted, the obtained aqueous solution was subjected to gel filtration (G-25, manufactured by Pharmacia), and each molecular weight fraction was analyzed as described above. When a quality reaction was performed, each fraction was positive for quaternary ammonium salt, confirming that keratin peptide and glycidyltrimethylammonium chloride had reacted.

Reference example 2 100g of sodium hydroxide and 3.0g of water in soog of pig hair
00g was added and left to stand at 40°C for 24 hours to perform hydrolysis, the reaction mixture was filtered, and the filtrate was mixed with weakly acidic cation exchange resin Amberlite IRC-50 (mentioned above) 600ml.
Neutralized with l. After concentrating this, the ion exchange resin was removed by filtration to obtain an aqueous solution of keratin peptide with a concentration of 40%. The molecular weight of the keratin peptide thus obtained was measured by gel filtration, and the average molecular weight was l 1
,200.

900 g of the keratin peptide aqueous solution with a concentration of 40% obtained as described above (the average molecular weight of the keratin peptide is 1,
200 (when expressed as n of - binding margin (V), the average value is about 9), total N272 mmol of amino nitrogen]
was placed in a reaction vessel, and 88.7 g of an aqueous solution of 3-chloro-2-hydroxypropyltrimethylammonium at a concentration of 49% (0.85 equivalent of amino nitrogen in keratin peptide) was added dropwise over 30 minutes while stirring, and During that time, a 20% aqueous sodium hydroxide solution was appropriately added dropwise to maintain the pH of the reaction solution at 10.5. After completing the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium,
Stirring was continued for 2 hours while maintaining the pH at 10.5, and then the amino nitrogen was measured after being left for 24 hours. The total amount of amino nitrogen was 61 mmol, which was 78% of the amino nitrogen. was reacting. Next, the reaction solution was passed through a 320 ml resin column containing a strongly acidic cation exchange resin Diaion 5K-IB (trade name, Mitsubishi Chemical Corporation ■).
Neutralize to pH 6.9, adsorb sodium ions in the reaction solution and a small amount of unreacted 3-chloro-2-hydroxypropyltrimethylammonium onto an ion exchange resin, and then remove the ion exchange resin. and concentration 3
0% N-quaternary ammonium derived keratin peptide (
An aqueous solution of keratin peptide] was obtained.

The obtained aqueous solution was subjected to a quaternary ammonium salt quality reaction in the same manner as in Reference Example 1, and all tests were positive.

In addition, using the obtained aqueous solution, gel filtration was performed in the same manner as in Reference Example 1, and each molecular weight fraction was subjected to a quaternary ammonium salt quality reaction. It was confirmed that 2-hydroxypropyltrimethylammonium chloride had reacted.

Reference example 3 500g of feathers was placed in a high pressure container at 10kg/cd, 200'
After being treated with superheated steam of C for 30 minutes, it was discharged into the atmosphere to obtain a porous puffed feather product. Add water 32 to this,
30 g of papain was added and hydrolysis was carried out at 40°C for 24 hours. After hydrolysis, the reaction mixture was filtered, and the d solution was concentrated under reduced pressure to obtain a keratin peptide with a concentration of 40%. The molecular weight of the keratin peptide thus obtained was measured by gel filtration and found to be an average molecular weight of 600.

700g of the resulting keratin peptide aqueous solution with a concentration of 40%
[Average molecule of keratin peptide 1600 (this is -In
(expressed as n in formula (V), the average value is about 5), a total amount of amino nitrogen of 431 mmol] was placed in a reaction vessel,
3-chloro-2- at a concentration of 49% while stirring at 30″C.
Hydroxypropyltrimethylammonium aqueous solution 16
5g (1.0 amino nitrogen of keratin peptide
equivalent amount) was added dropwise over 1 hour, and during that time, a 20% aqueous sodium hydroxide solution was appropriately added dropwise to adjust the pH of the reaction solution to 11.
．． It was maintained at 0. After dropping 3-chloro-2-hydroxypropyltrimethylammonium, the pH was adjusted to 11.0.
Stirring was continued for 2 hours while maintaining the temperature, and then after being left for 24 hours, the amino nitrogen was measured. The total amount of amino nitrogen was 40 mmol, and 93% of the amino nitrogen had reacted. . Next, add 100 m of weakly acidic cation exchange resin Amberlite JRC-50 (mentioned above) to the reaction solution.
2 was added to adsorb the sodium ions in the reaction solution and the slight remaining unreacted 3-chloro-2-hydroxypropyltrimethylammonium onto the ion exchange resin, and then the ion exchange resin was removed to give a concentration of 30%. N-quaternary ammonium-derived keratin peptide [N-(3-)
An aqueous solution of dimethylammonio-2-hydroxypropyl) keratin peptide was obtained.

The resulting aqueous solution was subjected to a quaternary ammonium salt reaction in the same manner as in Reference Example 1, and all results were positive.

In addition, using the obtained aqueous solution, gel i was prepared in the same manner as in Reference Example 1.
However, when a quaternary ammonium salt reaction was performed on each molecular weight fraction, each fraction was positive, confirming that the keratin peptide and 3-chloro-2-hydroxypropyltrimethylammonium had reacted. It was done.

The N-quaternary ammonium-derived keratin peptides obtained in Reference Examples 1 to 3 as described above and commercially available cationic polymers were blended to prepare hair cosmetics shown in the following examples, and their performance was compared with a hair cosmetic containing no N-quaternary ammonium-derived keratin peptide or cationic polymer.

Example 1 (About Shampoo) A shampoo with the formulation shown in Table 2 was prepared, and the shampoo was used to wash the hair of 10 female panelists. Evaluation was made on the basis of ``feeling of softness'' and ``feeling of plumpness.''Evaluation was done on a 5-point scale from 1 to 5.
The evaluation results are shown in Table 2 as the average value of the evaluation values of 10 people (the higher the evaluation value, the better the characteristics). Note that the number of parts of each component in Table 2 is based on parts by weight. Also,
The same applies to Tables 3 to 7 below. In addition, the second ~
In Table 7, the types of N-quaternary ammonium-derived keratin peptides are indicated by reference numbers.

As shown in Table 2, the shampoo of Example 1 which contained a cationic polymer and N quaternary ammonium-derived keratin peptide, the shampoo of Comparative Example 1-1 which did not contain both, and the shampoo which contained only a cationic polymer. Comparative example 1
Compared to the shampoo of Comparative Example 1-3, which contained only the N quaternary ammonium-derived keratin peptide, the shampoo of Comparative Example 1-2 was superior in the suppleness, combability, and plumpness of the hair after washing. Further, in the case of the shampoo of Example 1, no hair damage was observed.

Example 2 (Hair Rinse) A hair rinse with the formulation shown in Table 3 was prepared, and the hair rinse was applied to 10 female panelists after washing their hair with the shampoo of Comparative Example 1-3. "Flexibility"
The same evaluations as in Example 1 were made for , "<stickability", and "gloss". The evaluation results are shown in Table 3.

As shown in Table 3, the hair rinse of Example 2 containing a cationic polymer and N-quaternary ammonium-derived keratin peptide is different from that of Comparative Example 2, which does not contain both.
1, the hair rinse of Comparative Example 2-2 containing only a cationic polymer, and the hair rinse of Comparative Example 2-3 containing only N-[quaternary ammonium-derived keratin peptide]. It had excellent suppleness, combability, and shine. Further, in the case of the hair rinse of Example 2, no hair damage was observed.

Example 3 [About aerosol type foam] An aerosol type foam having the formulation shown in Table 4 was prepared, and the foam 8
To 0 parts by weight, add 10 parts by weight of Freon 12 (trade name) and parts by weight of propane/butane mixed LPGIO,
sealed in an aerosol type container.

Table 1: Using the above aerosol foam, compared to the range of use of a conventional aerosol foam that does not contain N-quaternary ammonium-derived keratin peptide and contains only a cationic polymer, it was found that the hair was less damaged. The skin has become more supple, and a plumper, natural-looking set has been created.

ui example 4 [About hair cream] A hair cream having the formulation shown in Table 5 was prepared.

When compared with the usage range shown in Table 1, the hair became more supple and flexible, the hair could be set more easily, and the durability of the cent was also excellent. Naturally, no hair damage was observed.

Example 5 [About permanent wave 1st agent] 6th
A permanent wave first agent having the formulation shown in the table was prepared.

Table 6 Using the hair cream described above, using the conventional hair cream that does not contain N-quaternary ammonium-derived keratin peptide and cationic polymer, and using the above permanent wave first agent, 6% bromic acid prepared separately. When a permanent wave treatment was performed on the hair bundle using a sodium aqueous solution as the second permanent wave agent, it was found that the conventional permanent wave agent 1, which does not contain N-quaternary ammonium-derived keratin peptide and cationic polymer, was used as a permanent wave agent.
Compared to the hair dye, the hair was less damaged, fluffy, shiny, and had an excellent feel. Further, no hair damage was observed.

Example 6 [Hair conditioner] A hair conditioner having the formulation shown in Table 7 was prepared.

Table 7 When the above hair conditioner was used and compared with a conventional hair conditioner that does not contain N-quaternary ammonium-derived keratin peptide and cationic polymer, it was found that the hair was made supple and had good combability. The result was a plump, natural-looking finish with a glossy finish, and no damage to the hair was observed.

[Effects of the Invention] As explained above, in the present invention, an N-quaternary ammonium-derived keratin peptide represented by the -C formula (1),
By blending with a cationic polymer, hair cosmetics can prevent damage to the hair and impart flexibility, good combability, fullness, shine, etc. to the hair without interfering with the original functions of hair cosmetics. was completed.

Director General of the Patent Office Yoshi 1) Takeshi Moon 1, Indication of the case, Patent Application No. 196451 of 1988 2, Name of the invention, hair cosmetics 3, Relationship with the amended person case Address of patent applicant: Higashiosaka City, Osaka Prefecture 1-2-14 Nuichi-cho Name Acid Phase Chemicals Co., Ltd. Representative Yoshioka-Sei 4, Agent 550 Phone: 06 (531) 82
77 Address: 1-23 Kitahorie-chome, Nishi-ku, Osaka Yota Building Yotsubashikan Column “Detailed explanation of the invention” in the specification (1) Page 13, line 9 of the specification to page 15, line 11 from the bottom [N-quaternary ammonium indicated by - binding margin (1), keratin peptide indicated by ■, ■ or ■ above, and J are corrected as follows.

As mentioned above, the N-quaternary ammonium-derived keratin peptides represented by - Tsuzuriyo (I) can be obtained by the reaction of keratin peptides with ammonium salts represented by general formulas (n) to (TV). , and their reaction formulas are as follows. In showing the reaction formulas, the keratin peptide is represented by the following general formula (V).

R3 HEN H-CH-CO翰OH ■ Reaction R, Rs between keratin peptide and glycidylammonium salt represented by general formula (II) ■ Keratin peptide and 3-halogen-2-hydroxypropyl represented by mm formula ([[) Reaction R3 with ammonium salt ■ Keratin peptide and 3- represented by general formula (IV)
Reaction with halogen propylammonium salt (2) Page 28 of the specification, lines 11 to last line, “(2) Kaotinic cellulose or cationic 8 powder...”
``Are R1□, R1□, and R13 the same as the roxyalkylene group?'' is corrected as follows.

(2) Cationic Morulose or Cationic Starch Examples of cationic cellulose or cationic starch include compounds represented by the following general formula (5).

The keratin peptide indicated by ■, ■ or ■ above and R1+ A COB CN"R+z・Z"El (5
) [In the formula, A is a cellulose residue or a starch residue, B is a polyoxyethylene or polyoxypropylene with an addition number of 0 to 10, C is an alkylene group or a hydrobovine dialkylene group, and RI I, R62, and R13 are the same (3) "About 8" on the last line of page 34 of the specification is amended to "about 7."

(4) Page 37 of the specification, line 9 (7) 'Approx. 9'' to 'Approx. 10''
J (!-correct.

that's all

Claims (3)

[Claims] (1) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc.
~20 alkyl groups, the remainder being hydroxyalkyl groups having 1 to 3 carbon atoms or benzyl groups. R_4 is a hydrogen atom or a hydroxyl group, R_5 is a side chain of an amino acid constituting a peptide derived from keratin, and n is 2 to 30. A hair cosmetic characterized by being formulated with a polymer. (2) The hair cosmetic according to claim 1, wherein the cationic polymer is a polymer of diallyl quaternary ammonium salt, cationic cellulose, cationic starch, or cationic vinyl polymer. (3) A claim in which the amount of the N-quaternary ammonium-derived keratin peptide represented by the general formula (I) is 0.05 to 10% by weight, and the amount of the cationic polymer is 0.05 to 5% by weight. The hair cosmetic according to item 1 or 2.