JPH0713005B2 - Cosmetics for hair - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a cosmetic composition for hair.

[Prior Art] For hair, shampoo, hair rinse, aerosol type foam, permanent wave agent, hair cream,
Various hair cosmetics such as hair conditioner, set lotion, hair treatment lotion, hair color, and hair bleach are used.

However, by using these hair cosmetics,
On the contrary, the hair may be damaged.

For example, when using a permanent waving agent,
Part of the keratin protein that composes hair elutes due to reduction with the first agent, alkali swelling, and over-oxidation with the second agent, and the remaining portion of the hair also undergoes physical and scientific changes, which makes the hair unnatural. Feeling or dryness occurs.
Also, in shampoo, since the surfactant contained in the shampoo has a strong surfactant activity, even the sebum and constituent proteins of the hair are eluted, the hair is damaged, and the hair feels dry or dry after drying. Become. Hair rinse is used after shampooing to give the hair softness and natural luster, but the main ingredient is a long-chain alkylalkyltrimethylammonium with 16 to 18 carbon atoms. Chlorides, dialkyltrimethylammonium chlorides, alkyldimethylbenzylammonium chlorides, etc., have strong surface-active properties, so when the amount used is large, even the sebum and constituent proteins of hair are eluted, as in shampoos. The hair will begin to feel dry or dry.

As described above, the components used as the main ingredient of the cosmetic for hair have a useful function in achieving the original purpose on one side, but may damage the hair on the other side. The fact is that the above-mentioned hair cosmetics have not been fully considered.

[Problems to be solved by the invention]

The present invention solves the problem that the conventional cosmetic for hair, as a result of its use, damages the hair in return, and prevents damage to the hair without inhibiting the original function of the cosmetic for hair. However, it is an object of the present invention to provide a cosmetic for hair that can impart suppleness, good combability, plumpness, luster and the like to the hair.

[Means for solving problems]

The present invention provides a cosmetic for hair according to general formula (I) (In the formula, R is a side chain of an amino acid constituting a polypeptide derived from collagen, and n is 3 to 20)
By containing a quaternary trimethylammonium-derived collagen polypeptide represented by and a cationic polymer, damage to the hair is prevented, the original function of the hair cosmetic composition is better exhibited, and the hair is supple, It is intended to provide a hair cosmetic composition capable of imparting good combability, plumpness, and color luster.

Examples of the amino acid whose side chain is represented by R in the general formula (I) include alanine, glycine, valine, leucine, isoleucine, proline, phenylalanine, tyrosine, serine, threonine, methionine, arginine,
Histidine, lysine, aspartic acid, asparagine,
Examples thereof include glutamic acid, glutamine, hydroxyproline and hydroxylysine. Table 1 shows an example of the analysis results of the composition ratio of these amino acids. It should be noted that, although asparagine and glutamine are not shown in Table 1, they are aspartic acid and glutamic acid, respectively, when they are hydrolyzed before the analysis (in the usual method, they are completely hydrolyzed by 6N hydrochloric acid). Is. That is, aspartic acid and glutamic acid in Table 1 also include those existing as asparagine and glutamine in the polypeptide.

The quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I) is 3-chloro-2.
-Obtained by reaction of hydroxypropyltrimethylammonium chloride with collagen-derived polypeptide.

3-Chloro-2-hydroxypropyltrimethylammonium chloride (hereinafter referred to as CTA) used in the above reaction is known as existing chemical substance (2) -181, and has a concentration of 50% (wt%, the same applies hereinafter). The aqueous solution before and after is commercially available and is easily available.On the other hand, the collagen-derived polypeptide is obtained by hydrolyzing a protein constituting collagen or gelatin which is a modified product thereof with an acid, an alkali, or a protease. Obtained by In the hydrolysis, by appropriately selecting the amount of acid, alkali, or enzyme to be added, reaction temperature, and reaction time, the value of n of the collagen-derived polypeptide obtained is 3 to 20, that is, the molecular weight is about 300 to about 2 , 0
00 can be preferred. The details of hydrolysis for obtaining collagen-derived polypeptide and the reaction between CTA and collagen-derived polypeptide for obtaining quaternary trimethylammonium-derived collagen polypeptide represented by general formula (I) are described in This is as shown in JP-A-60-243010 filed by the applicant.

The quaternary trimethylammonium-derived collagen polypeptide as described above is one in which a hydrolyzate of collagen having a peptide structure similar to that of keratin of hair is cationized to enhance its adsorptivity to hair. It has a peptide structure similar to that of keratin, and has the action of adhering to hair and imparting moisturizing and flexibility to hair, thereby helping to condition hair and protecting hair. This quaternary trimethylammonium-derived collagen polypeptide does not have a surface-active ability like a cationic polymer described later, and therefore does not cause harmful effects such as degreasing and protein denaturation based on the surface-active ability.

On the other hand, examples of the cationic polymer include a polymer of diallyl quaternary ammonium salt, cationic cellulose, cationic starch, and cationic vinyl polymer, which are described in detail below.

(1) Polymer of diallyl quaternary ammonium salt Examples of the polymer of diallyl quaternary ammonium salt include polymers represented by the following general formulas (1) to (4).

(In the general formulas (1) to (4), R₁, R₂Is the same or again
Are different from each other, a hydrogen atom or a carbon number of 1 to 18, preferably
Represents an alkyl group having 1 to 4 carbon atoms, R₃, R_FourIs the same or again
Are different from each other, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or
Represents a phenyl group, X Is an anion residue, salt
Hagen ions such as elemental and bromine, inorganics such as sulfuric acid and nitric acid
Organic such as acid residue, methylsulfuric acid and hydroxycarboxylic acid
Acid residue, n₁, M₁And m₂Has a molecular weight of 10,000 to 1,000,000
(2 indicates the number given) (2) Cationic cellulose or cationic starch cuticle
One of the following is used as on-type cellulose or cationic starch.
Examples thereof include compounds represented by general formula (5).

(In the formula, A is a cellulose residue or starch residue, B is an alkyl group or a hydroxyalkyl group, R ₅ , R ₆ and R ₇ are the same or different, and an alkyl group, an aryl group or a nitrogen atom in the formula X may be an anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, nitric acid, etc.) and l is a positive integer) (3) Cationic vinyl polymer Cationic vinyl polymer The following general formula (6)-
Examples thereof include the polymers represented by (8).

(In the formula, R₈, R₉Are the same or different, hydrogen atom, carbon number 1
~ 6 alkyl group or phenyl group, n₁And X
Is the same as above)(In the formula, R_TenIs a hydrogen atom or a methyl group, R₁₁, R₁₂, R₁₃
Are the same or different and each is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Alkyl group or substituted alkyl group, Y is an oxygen atom or an alkyl group.
NH group in amide bond, X is anion, m₃Is an integer from 1 to 10,
n₁Is the same as above)(In the formula, R₁₄, R₁₅, R₁₆Are the same or different, hydrogen
Atoms, alkyl groups having 1 or 2 carbon atoms or substituted alkyl groups
Kill group, X is anion, n₁Is the same as above) Among these cationic polymers, diallyldimethyl
Ammonium homopolymer, cationic cellulose, etc.
Particularly preferred.

The cationic polymer as described above, like the cationic surfactant, is well adsorbed on the hair and makes the hair softer than the quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I), and , Improves combability, gives gloss to hair, and makes it easier to condition hair, but depending on long-term use, due to excessive accumulation of this and strong degreasing and cleaning action,
May give unpleasant sensations such as crunchy hair. In particular, damaged hair may be more unfavorable to the touch due to the remarkable adsorption.

Therefore, by using this cationic polymer in combination with the quaternary trimethylammonium-derived collagen polypeptide represented by the above general formula (I), the drawbacks of the cationic polymer are prevented from appearing, and even if it is used for a long time. It exerts an excellent conditioning action without damaging the hair or reducing the feel.

The amount of the quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I) and the cationic polymer in the hair cosmetic composition is such that the quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I) is used. Peptide 0.05 to 10%, cationic polymer 0.05 to
A range of 5% is preferable. This is because when the amount of the quaternary trimethylammonium-derived collagen polypeptide or the cationic polymer represented by the general formula (I) is less than the above range, those effects are not sufficiently exhibited, and the general formula (I)
When the amount of the quaternary trimethylammonium-derived collagen polypeptide shown by is more than the above range, it remains in the hair and becomes sticky, and when the amount of the cationic polymer is more than the above range, the hair is damaged. is there.

Examples of hair cosmetics include all hair cosmetics such as shampoo, hair rinse, aerosol foam, hair cream, permanent waving agent, hair conditioner, set lotion, hair treatment lotion, hair color and hair bleach. .

Then, the quaternary trimethylammonium-derived collagen polypeptide or the cationic polymer represented by the general formula (I) is basically added to the composition conventionally used for these hair cosmetics in the above proportion. do it. However, in the case where the cationic polymer was originally blended such as hair rinse and foam, a part of the cationic polymer is represented by the fourth formula (I).
It may be replaced with a grade trimethylammonium-derived collagen polypeptide.

As an example of the components blended in the hair cosmetic composition,
For example, anionic surfactant, nonionic surfactant,
Surfactants such as cationic surfactants, anionic polymers, nonionic polymers, polymers such as amphoteric polymers, naturally extracted oils, higher fatty acids, hydrocarbons, fatty acid esters, glycerides, waxes, alkyl alcohols, alkyl amides, Silicone oil (eg, dimethylpolysiloxane, methylphenylpolysiloxane,
Other oils such as modified silicone oil), protein hydrolysates such as collagen polypeptide, keratin polypeptide, silk polypeptide or derivatives thereof, moisturizers, alcohols, thickeners, plant extracts, animal extracts, UV absorbers , PH adjusters, chelating agents, preservatives, dyes, and fragrances.

〔Example〕

Next, the present invention will be described in more detail with reference to Reference Examples (Production Examples of Quaternary Trimethylammonium-Derived Collagen Polypeptide) and Examples. However, the present invention is not limited to the examples.

Reference Example 1 700 g of water was added to 300 g of powdered gelatin, dissolved while heating, 60 g of concentrated hydrochloric acid was added at 70 ° C., hydrolysis was carried out for 1 hour with stirring, and then the reaction mixture was filtered and filtered with water. In 2l
Diluted to a weakly basic anion exchange resin DIAION WA20
(Trade name, Mitsubishi Kasei Co., Ltd.) was passed through a 290 ml resin tower for neutralization. This is concentrated under reduced pressure and then filtered to give a concentration of 40%.
An aqueous solution of collagen-derived polypeptide was obtained. The molecular weight of the collagen-derived polypeptide obtained in this manner was measured by gel filtration to give an average molecular weight of 900.
Met.

The obtained aqueous solution of collagen-derived polypeptide having a concentration of 40% 700 g (average molecular weight of collagen-derived polypeptide was 90
0, the total amount of amino nitrogen (310 mmol) was placed in a reaction vessel, and 103 g of a 51% concentration CTA aqueous solution (0.9 equivalent of amino nitrogen of collagen-derived polypeptide) was added dropwise over 30 minutes while stirring at 35 ° C. The pH of the reaction solution was maintained at 10.0 by appropriately adding 20% aqueous sodium hydroxide solution during that period. After the addition of CTA was completed, stirring was continued for 2 hours while maintaining the pH at 10.0, and then the mixture was allowed to stand for 24 hours. When the amount of amino nitrogen was measured, the total amount of amino nitrogen was 42 mmol. 84% of the element was reacting. Next, a weak acidic cation exchange resin Amberlite IRC was added to the reaction solution.
Add -50 ml (trade name, Organo Co., Ltd.) 170 ml, neutralize to pH 6.5, and adsorb sodium ions in the reaction solution and a small amount of unreacted CTA to the ion exchange resin. The ion exchange resin was removed to obtain an aqueous solution of quaternary trimethylammonium-derived collagen polypeptide having a concentration of 30%.

When the resulting aqueous solution was subjected to a quaternary ammonium salt exhibiting reaction, a white precipitate was produced by sodium tetraphenylboron and a red precipitate was produced by the Dolargendorf's reagent, which was positive.

Furthermore, in order to confirm that the collagen-derived polypeptide and CTA are bound, gel filtration (G-25, Pharmacia) was performed using the obtained aqueous solution, and each molecular weight fraction was subjected to the above-mentioned presentation. When a sexual reaction was performed, it was confirmed that each fraction was positive for a quaternary ammonium salt exhibiting reaction, and that collagen-derived polypeptide and CTA were bound to each other.

Reference Example 2 500 g of plate-like gelatin was dissolved while stirring 700 g of 6% aqueous sodium hydroxide solution, and hydrolysis was carried out for 1 hour while stirring at 80 ° C. Then, the reaction mixture was filtered, and the filtrate was diluted to 2 l with water. Weak acid cation exchange resin Amberlite IRC-5
0 (trade name, Organo Co., Ltd.) was passed through a 500 ml resin tower for neutralization. This was concentrated under reduced pressure and then filtered to obtain an aqueous solution of collagen-derived polypeptide having a concentration of 35%. The molecular weight of the collagen-derived polypeptide thus obtained was measured by gel filtration and found to be 500.

1 kg of an aqueous solution of collagen-derived polypeptide having a concentration of 35% obtained as described above (average molecular weight of collagen-derived polypeptide of 500, total amount of amino nitrogen 697 mmol) was placed in a reaction vessel, and the concentration was 49% while stirring. CTA
228 g of an aqueous solution (0.85 equivalent of amino nitrogen of collagen-derived polypeptide) was added dropwise over 30 minutes, and a 20% aqueous sodium hydroxide solution was appropriately added during that period to prepare a reaction solution.
The pH was maintained at 9.5. After the addition of CTA was completed, stirring was continued for 5 hours while maintaining the pH at 9.5, and then the mixture was allowed to stand for 24 hours, after which the amount of amino nitrogen was measured. The total amount of amino nitrogen was 147 mmol. 79% of the element was reacting. Next, a weakly acidic cation exchange resin Diaion SK-1B (trade name, Mitsubishi Kasei Co., Ltd.) 32 was added to the reaction solution.
The solution was passed through a 0 ml resin tower, neutralized to pH 6.9, sodium ions in the reaction solution and unreacted CTA slightly remaining were adsorbed on the ion exchange resin, and then the ion exchange resin was removed. An aqueous solution of quaternary trimethyl ammonium derivatized collagen polypeptide having a concentration of 30% was obtained.

Reference Example 3 650 g of water was added to 350 g of granular gelatin and the mixture was heated to 50 ° C. to dissolve the gelatin, and then the neutral proteolytic enzyme papain 20 was added.
After adding mg and hydrolyzing for 3 hours with stirring at 50 ° C., the reaction mixture was filtered to obtain an aqueous solution of collagen-derived polypeptide having a concentration of 35%. The molecular weight of the collagen-derived polypeptide thus obtained was measured by gel filtration, and the average molecular weight was 1,700.

800 g of the obtained collagen-derived polypeptide aqueous solution with a concentration of 35% (average molecular weight of collagen-derived polypeptide 1,
700, the total amount of amino nitrogen (140 mmol) was placed in a reaction vessel and stirred at 30 ° C., while stirring, 63.1 g of a 49% concentration CTA aqueous solution.
(Collagen-Derived Polypeptide 1.
(0 equivalent) was added dropwise over 1 hour, and a 20% aqueous sodium hydroxide solution was appropriately added during that time to maintain the pH of the reaction solution at 11.0. After the addition of CTA was completed, stirring was continued for 3 hours while maintaining the pH at 11.0, and then the mixture was allowed to stand for 24 hours, after which the amount of amino nitrogen was measured to be 14
Millimoles, 90% of the amino nitrogen was reacted. Next, 120 ml of weakly acidic cation exchange resin Amberlite IRC-50 (supra) was added to the reaction solution to allow sodium ions in the reaction solution and unreacted CTA slightly remaining to be adsorbed on the ion exchange resin. The exchange resin was removed to obtain an aqueous solution of quaternary trimethylammonium-derived collagen polypeptide with a concentration of 30%.

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

Further, using the obtained aqueous solution, gel filtration was carried out in the same manner as in Reference Example 1, and a quaternary trimethylammonium salt-exposing reaction was carried out for each molecular weight fraction. As a result, each fraction was positive, and collagen-derived polypeptide and CTA
It was confirmed that and were combined.

As described above, the quaternary trimethylammonium-derived collagen polypeptide obtained in Reference Examples 1 to 3 and a commercially available cationic polymer were blended to prepare hair cosmetics shown in the following examples, and those The performance was compared with hair cosmetics containing no quaternary trimethylammonium-derived collagen polypeptide or cationic polymer.

Example 1 [Shampoo] A shampoo having a composition shown in Table 2 was prepared, and 10 female panelists washed the hair with the shampoo, and the feel after washing the hair was "suppleness" and "combability". "," Fluffy feeling "was evaluated. The evaluation was carried out in 5 grades from 1 to 5, and the evaluation results are shown in Table 2 as an average value of the evaluation values of 10 persons (the higher the evaluation value, the better the characteristics). In addition, the compounding parts number of each component in Table 2 is based on parts by weight. The same applies to Tables 3 to 7 described later. In Tables 2 to 7, types of quaternary trimethylammonium-derived collagen polypeptide are shown by reference example numbers.

As shown in Table 2, the shampoo of Example 1 in which the cationic polymer and the quaternary trimethylammonium-derived collagen polypeptide were blended, the shampoo of Comparative Example 1-1 in which neither was blended, only the cationic polymer was used. The shampoo of Comparative Example 1-2 and the shampoo of Comparative Example 1-3 containing only the quaternary trimethylammonium-derived collagen polypeptide are superior in suppleness, combability and plumpness of the hair after washing. It was Further, in the case of the shampoo of Example 1, no hair damage was observed.

Example 2 [Hair conditioner] A hair conditioner having the composition shown in Table 3 was prepared, and the hair conditioner was applied to 10 female panelists after shampooing with the shampoo of Comparative Example 1-3, and then applied to the hair to obtain "suppleness". "
The "combability" and "gloss" were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

As shown in Table 3, the hair rinse of Example 2 in which the cationic polymer and the quaternary trimethylammonium-derived collagen polypeptide were blended, the hair rinse of Comparative Example 2-1 in which both were not blended, the cationic Compared to the hair rinse of Comparative Example 2-2 containing only the polymer and the hair rinse of Comparative Example 2-3 containing only the quaternary trimethylammonium-derived collagen polypeptide, the suppleness and combability of the hair after use were high. The luster was excellent. Moreover, in the case of the hair rinse of Example 2, no damage to the hair was observed.

Example 3 [Aerosol type foam] An aerosol type foam having the composition shown in Table 4 was prepared, and 10 parts by weight of Freon 12 (trade name) and 10 parts by weight of propane / butane mixed LPG were added to 80 parts by weight of the foam. In addition, it was sealed in an aerosol type container.

Compared with the feeling of use of the conventional aerosol type foam in which the quaternary trimethylammonium-derivatized collagen polypeptide was not used but only the cationic polymer was used using the above aerosol type foam, the hair was less damaged and the hair was better. The set is supple and has a more fluffy and natural finish.

Example 4 [Hair cream] A hair cream having the composition shown in Table 5 was prepared.

Using the above hair cream, when compared with the feeling of use of a conventional hair cream that does not contain a quaternary trimethylammonium-derived collagen polypeptide and a cationic polymer, the hair becomes more supple and soft, and the hair becomes easier. It was possible to set it on and the durability of the set was excellent. Of course, no hair damage was observed.

Example 5 [Regarding Permanent Wave First Agent] A permanent wave first agent having the composition shown in Table 6 was prepared.

Using the above permanent wave first agent, a 6% aqueous sodium bromate solution prepared separately was used as a permanent wave second agent, and the hair bundle was subjected to a permanent wave treatment. As a result, a quaternary trimethylammonium-derived collagen polypeptide and a cationic polymer were obtained. Hair damage was less, plump, shiny, and excellent in touch, as compared with the conventional permanent wave first agent, which was not blended. No damage to the hair was observed.

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

When the above hair conditioner was used and compared with a conventional hair conditioner containing no quaternary trimethylammonium-derived collagen polypeptide and a cationic polymer, the hair was supple and gave good combability, and was fluffy and natural. The finish was good and glossy, and no damage to the hair was observed.

〔The invention's effect〕

As described above, in the present invention, by inhibiting the quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I) and the cationic polymer, the original function of the cosmetic for hair is inhibited. Without giving the hair, it was possible to prevent damage to the hair and to impart suppleness, good combability, plumpness, luster and the like to the hair.

Claims (3)

[Claims] 1. A general formula (I) (In the formula, R is a side chain of an amino acid constituting a polypeptide derived from collagen, and n is 3 to 20)
A cosmetic for hair comprising the quaternary trimethylammonium-derived collagen polypeptide represented by and a cationic polymer. 2. The hair cosmetic composition 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. The compounding amount of the quaternary trimethylammonium-derived collagen polypeptide represented by the general formula (I) is
0.05-10% by weight, the amount of cationic polymer is 0.05
The hair cosmetic composition according to claim 1 or 2, wherein the content is 5% by weight.