JPS6033405B2 - hair setting agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a hair setting agent containing a film-forming substance, water, and alcohol as main components, which is characterized in that a specific water-removalable keratin hydrolyzate is used as a film-forming substance. Regarding setting agents.

Conventionally, film-forming substances for hair setting agents such as setting lotions and hair sprays include plant gums such as gum tragacanth, gum karaya, and quince seed, pectin, sodium alginate, carboxymethyl cellulose, polyvinylpyrrolidone, and sodium polyacrylate. Highly viscous substances and water-resistant polymeric substances such as acrylic acid ester-methacrylic acid ester copolymers have been used, but vegetable rubber has a film strength of 4 and lacks set retention, and water-soluble All of them lose their effectiveness when you wash your hair, and water-insoluble ones give a strange feeling, and they have the disadvantage that they tend to attract dust because they are electrostatically charged, so although they are all preferable, they are figure,
Therefore, there is a demand for a film-forming substance that does not cause discomfort and can maintain the holding power of the set for a long period of time. As a result of various studies in response to such demands, the present inventors reduced keratin with mercaptans or sulfides in an alkaline region, and then hydrolyzed it with an enzyme to create a mercapto group in each molecule. It has been discovered that when a water-soluble keratin hydrolyzate having two or more scales is used as a film-forming substance in a hair setting agent, it does not give a strange feeling and maintains its setting retention power for a long period of time.Based on this, the present invention has been made. I've come to the point where I can complete it.

That is, when keratin is reduced with mercaptans or sulfides in an alkaline environment, the disulfide bonds in keratin are cleaved and mercapto groups are generated, and when it is then hydrolyzed with enzymes, the peptide bonds are cleaved and the molecular weight decreases. , the number of carboxyl groups and amino/groups increases.

At that time, the hydrolyzate obtained by adjusting the degree of hydrolysis appropriately has water solubility and contains two mercapto groups in one molecule.
When the keratin hydrolyzate has a film-forming ability, the keratin hydrolyzate has a film-forming ability and is catalyzed by an enzyme in the air (if desired, a water-soluble metal compound such as iron gluconate may be used as a catalyst, or (Peroxides such as hydrogen oxide may be used as oxidizing agents), the mercapto groups in the hydrolyzate are oxidized and form disulfide bonds between adjacent keratin hydrolyzate molecules, thereby It has the remarkable property that it cross-links with each other one after another and becomes a polymer, eventually becoming water-insoluble. Therefore, this keratin hydrolyzate is dissolved in a diluted mixed solution of water and alcohol, applied or sprayed onto hair wrapped around curlers or hair that has already been set, and then heated with a hair dryer. When dried, the mercapto groups in the keratin hydrolyzate are oxidized and crosslinked with the mercapto groups of other molecules of the keratin hydrolyzate that are in contact with the layer to form disulfide bonds, leaving the hair set. It forms a water-insoluble polymer film on the hair.

Moreover, this keratin hydrolyzate has amino groups and carboxyl groups in its molecules, so these bond with the carboxyl groups and amino groups in the hair to form salts, so the bond with the hair is strong. Even when washed with water, it does not easily separate due to its water insolubility.

In addition, this keratin hydrolyzate has a chemical structure similar to that of hair, so it does not cause any discomfort when applied to hair, and since it has peptide bonds, it is breathable and does not cause hair to become stuffy. There is no static electricity, and there is little dust adhesion.

In obtaining such a keratin hydrolyzate, any keratin constituting wool, feathers, hair, horns, claws, hooves, etc. can be used as the starting material, but from the viewpoint of easy availability, Particularly preferred is wool.

Examples of mercaptans used as reducing agents include thioglycolic acid, cysteine, mercaptoethanol, thioglycerin, and thiosalcylic acid. Examples of sulfides include sodium sulfide, potassium sulfide, ammonium sulfide, and trisulfide. Examples include tanolamine, sulfurized jetanolamine, and sulfurized monoethanolamine.

Examples of enzymes used for hydrolysis include acidic proteolytic enzymes such as pepsin, protase A, and broctase B, and neutral proteolytic enzymes such as bromelain, guine, thermolysin, trypsin, and chymotrypsin. It will be done. The specific steps for obtaining the keratin hydrolyzate are as follows: First, keratin is placed in an aqueous solution of a reducing agent adjusted to an alkaline range, and the air in the system is preferably replaced with an inert gas such as nitrogen under a vacuum cleaner. The disulfide bond of cystine in keratin is reductively cleaved at a temperature of 0 to 40°C to form a mercapto group.

When using an alkaline substance such as sulfide as a reducing agent, it is not necessary to add an alkaline substance to keep the reaction solution alkaline, but if the reducing agent is thioglycolic acid or mecaptoethanol, When the reaction solution is acidic, such as, it is desirable to add an alkaline agent such as caustic soda or caustic potash to maintain the reaction solution in an alkaline range. And the quality of the reaction solution is PH
It is preferable to adjust it so that it is 8-11. It is preferable to add urea to the reaction solution because urea swells keratin and facilitates the action of the reducing agent. After the reduction reaction, the reaction mixture is subjected to reduced pressure to remove unreacted substances, and the solution is roughly passed through ultraviolet filtration to about 1/2 to 1%
Concentrate to this point.

Next, the concentrate obtained as described above is subjected to dialysis,
The remaining reducing agent is removed and the pH is adjusted to a pH suitable for the next enzymatic decomposition.

After dialysis, an enzyme is added to the reaction product to perform hydrolysis.

In the case of acidic enzymes such as pepsin, the pH during enzymatic decomposition is preferably adjusted to a range of pHI to 3.
In the case of neutral enzymes such as bromelain, the pH is 5 to 8.
It is preferable to adjust it within the range of . The reaction temperature is preferably 30 to 45q0, and the reaction time is usually 30 to 45q0.
~2 unique intervals are adopted. The amount of enzyme used as well as the reaction time and temperature have a large effect on the molecular weight of the hydrolyzate.

Therefore, how much enzyme to use, reaction time and reaction temperature should be determined empirically by examining the molecular weight distribution of the obtained hydrolyzate using the gel analysis method. The optimum conditions can be determined by In addition, in this invention, it is preferable to adjust the average molecular weight of the hydrolyzate obtained to the range of 2000-20000. In other words, keratin generally contains one cystine for every one amino acid, and the average molecular weight of the amino acids in keratin is about 100.
Therefore, the average molecular weight of the keratin hydrolyzate is 2
If the average molecular weight exceeds 000, two or more mercapto groups will be contained in one molecule of the hydrolyzate, and if the average molecular weight exceeds 20,000, the hydrolyzate will become immovable and difficult to handle. be. Therefore, in order to prepare the hair setting agent of the present invention using such a keratin hydrolyzate,
For example, the keratin hydrolyzate is added to a mixed solution of water and alcohol at a concentration of 0.5 to 10% (by weight, hereinafter referred to as the same), preferably about 1 to 5%, and if necessary, castor oil, Plasticizers such as liquid paraffin and water-soluble lanolin derivatives, softeners such as glycerin and propylene glycol, chelating agents, preservatives, fragrances, surfactants, and the like may be added as appropriate.

Note that the keratin hydrolyzate is usually obtained in the form of an aqueous solution, but in this specification, all amounts thereof are indicated as the amount of solid content. In the present invention, examples of alcohol used include ethyl alcohol and inpropyl alcohol, with ethyl alcohol being particularly preferred. Also, the amount of alcohol used is 5-15%.
It is preferable to keep it at a certain level. The hair setting agent of the present invention is usually used as a setting lotion, but it is of course also possible to seal it together with compressed gas in a closed container and use it as a hair spray. Next, the hair setting agent of the present invention will be explained with reference to Examples.

Example 1 [Manufacture of keratin hydrolyzate] 1.Pour 480 ml of urea into the beaker, add distilled water to make the total volume about 900 ml, and after lighting to dissolve most of the urea, 21 mercapto Tanol 20' and ED
Added TAI Yu.

Next, add 20% caustic soda aqueous solution to adjust the solution to pH 8.
Distilled water was added and the entire solution was left overnight. After adding 20 g of degreased wool to this solution and stirring to remove the generated bubbles, the container was covered and left at room temperature for 3 days with occasional lighting.

Next, the resulting reaction mixture was passed through a vacuum filter to remove unreacted wool. Approximately 820% of the obtained wasp liquid was passed through an ultrafiltration device (
The concentration of the reaction product is increased by ultrafiltration using Amicon's Model 402 Cell, Diaflow Membrane UM-10 (molecular weight cut off: 10,000), and the solvent containing urea and reducing agent is He passed away.

The concentrate was concentrated to a concentration of 400°C, and the resulting concentrate was packed into a cellophane dialysis tube and dialyzed against 5 sleeves of 0.1N formic acid for 8 hours, and the dialysis was repeated twice with 5 sleeves of 0.1N formic acid for 8 hours each.

The concentrated solution after dialysis was transferred to a 500' beaker, and a solution of 40 parts of pepsin dissolved in 4 parts of 0.1N acetic acid was added thereto.

The keratin was hydrolyzed over a period of 8 hours while the reaction solution was kept at 370° C. with a hot water tank and the reaction solution was thoroughly soaked with an electromagnetic strainer. After the reaction was completed, the reaction solution was adjusted to -7 using a 20% caustic soda aqueous solution using a PH meter while cooling the container with ice to inactivate pepsin. The obtained reaction solution was filtered under reduced pressure, and 2 parts of acetic acid was added to the solution to make the solution acidic again.

The above solution was subjected to ultrafiltration using an ultrafilter (manufactured by Amicon, Model 402 cell, Diaflow Cell UM-2 (molecular weight cut off: 1000)) to desalt and concentrate to 150'. The obtained concentrate was transferred to a 200 mm eggplant type kolben with a stopper and concentrated under reduced pressure using a rotary evaporator to obtain a keratin hydrolyzate with a dry koji content of 20%.

A portion of the obtained hydrolyzate was taken and diluted with 0.1N acetic acid.
After diluting to a 5% solution, gel filtration (agarose gel G-50 manufactured by Pharmacia) was performed, and the peptide concentration in each fraction was determined by measuring the absorbance of blood at wavelength 23 with an ultraviolet partial photometer. Furthermore, using table salt and tribucin as standard substances, the relationship between the effluent fraction in G-50 and the logarithm of the molecular weight was determined, and based on this, the molecular weight of the keratin hydrolyzate was determined to be approximately 2200.
It turned out to be.

In addition, a part of the obtained keratin hydrolyzate was taken and its peptide concentration was measured by the burette method using crystalline albumin as a standard substance, and the peptide concentration was measured by the Ellman method using cysteine hydrochloride as a standard substance. When the concentration of cysteine residues in the sample was determined, it was found that a peptide with a molecular weight of approximately 2,200 contained mercapto groups equivalent to 12.6 cysteine per 100 days; 220
It was found that an average of 2.3 mercapto groups were contained per 0 peptide.

[Preparation of hair setting agent and results of its use] A hair setting agent having the following formulation was prepared using the keratin hydrolyzate obtained as described above.

Keratin hydrolyzate 4% ethyl alcohol 10% chelating agent (EDTA) 0.1% preservative
Appropriate amount of fragrance
Appropriate amount of purified water
This hair setting agent (remaining 100%) was applied to hair wound around curlers and dried with a hair dryer for 15 minutes.

Hair set in this way is non-sticky and
Moreover, there was no adhesion of dust, and the hair remained almost in its original state even after washing and drying the hair five times. Comparative Examples 1-2 A hair setting agent having the following formulation was prepared.

Comparative Example 1 Comparative Example 2 Polyvinylpyrrolidone 3%
-Acrylic resin alkanolamine liquid (50%)-
6% propylene glycol 2% 2% polyoxyethylene (20 moles) 1.5% 1.5
% Stearyl alcohol Ethyl alcohol 10% 10% Preservative Appropriate amount Appropriate amount Fragrance
Appropriate amount Appropriate amount of purified water
Remainder Remainder 100% 100%Next, the hair setting agents of Example 1, Comparative Example 1, and Comparative Example 2 were examined for curl retention, feeling of use, and dust adhesion.

Experimental example 1 Curl retention ◎ Adjustment of test hair One end of 30 female hairs was tied up to form a curl, washed with a 2% sodium lauryl sulfate aqueous solution, thoroughly rinsed with water, air-dried at room temperature, and formed into a test hair. did.

◎Experimental method After the hair adjusted as described above was wrapped and fixed using a plastic rod with a diameter of 2 cm while applying a force of 30 weights, the above-mentioned hair setting agent was applied separately to the hair. and dried with a hair dryer for 18 minutes.

After drying, the curl was removed from the rod, the upper end of the curl was fixed and hung indoors, and the straight meridian of the curl was measured after a predetermined period of time had elapsed. The results are shown in Table 1. Table 1 Experimental Example 2 Feeling of use and dust adhesion The hair setting agents of Example 1 and Comparative Example 1 were each applied to a panel of five experts, and 6 hours after application, the presence or absence of any discomfort and the adhesion of dust were evaluated. The presence or absence of was investigated.

The results are shown in Table 2. Table 2 As shown in Tables 1 and 2, the hair setting agent of the present invention has a curl retention property equal to or better than that of conventional hair setting agents, and has a particularly good feeling of use and prevention of dust adhesion. In this respect, the hair setting agent of the present invention is superior to conventional hair setting agents.

Example 2 [Production of keratin hydrolyzate] Wool 35% was adjusted to 10.5% with caustic soda.
After adding sodium M thioglycolate to the container for one night and removing the generated bubbles, the air in the container was replaced with nitrogen, and the container was allowed to stand at room temperature for one hour while being shaken occasionally.

Next, the obtained reaction mixture was passed through a vacuum filter to remove unreacted substances, and the obtained solution was concentrated in the same manner as in Example 1 until the reaction solution reached 1'.

The obtained concentrate was packed into a cellophane dialysis tube, and the concentration was 0.
Dialysis was repeated three times for 6 hours each with 1N formic acid.

Transfer the concentrated solution after dialysis to a 500ml beaker, add a solution of 20 parts of pepsin dissolved in 2 parts of 0.1N acetic acid, and stir while keeping the reaction solution at 370 °C. Hydrolyzed for hours.

Furthermore, the reaction solution was concentrated under reduced pressure on a 45° C. wound bath using a rotary evaporator to almost evaporate to dryness. Next, 50% of distilled water was added to dissolve the reaction product, and then filtered under reduced pressure. To the resulting monkey fluid, an aqueous solution of caustic soda was added to adjust the pH to 5 to inactivate pepsin, and then distilled water was added. A keratin hydrolyzate with a dry residue of 20% was obtained. The obtained keratin hydrolyzate was subjected to gel treatment in the same manner as in Example 1, and it was confirmed that the average molecular weight was approximately 4000.
When the concentration of cysteine residues was determined by the I1man) method, it was found that a peptide with a molecular weight of approximately 4000 contained mercapto groups equivalent to 10.8 cysteine per 100 units, and as a result, It was found that an average of 3.6 mercapto groups were contained per peptide having a molecular weight of 4000.

[Preparation of hair setting agent and results of its use] A hair setting agent having the following formulation was prepared using the keratin hydrolyzate obtained as described above.

Keratin hydrolyzate 4% Bromois W-52 (average molecular weight 2000) 1.5% ethyl alcohol 10% chelating agent (EDTA) 0.1% preservative
Appropriate amount of fragrance
Appropriate amount of purified water
This hair setting agent (remaining 100%) was placed in a metal aerosol container, and nitrogen gas was filled in at a rate of 5 [9/2].

Using this aerosol container, the hair setting agent was applied onto the hair that had already been set, and then dried with a hair dryer for 15 minutes. The hair treated with the hair setting agent in this way was not sticky and did not have dust attached to it, and could maintain its set state even after washing and drying the hair five times.

Promois W-52 used in this hair setting agent is the trade name of collagen-induced polypeptide (gelatin hydrolyzate, existing Ib chemical substance 8-585) manufactured by Seiwa Kasei Co., Ltd.

Comparative examples 3-4 A hair setting agent having the following formulation was prepared.

Comparative Example 3 Comparative Example 4 Polyvinylpyrrolidone 1
．． 5% acrylic resin alkanolamine liquid (50%) 3
．． 0% cetyl alcohol 0.04%
0.04% silicone oil 0.1%
0.1% Freon 11 25%
25% Freon 12 35%
35% fragrance (appropriate amount)
Appropriate amount of ethyl alcohol Remainder Remainder 100% 100% Next, the hair setting agents of Example 2, Comparative Example 3, and Comparative Example 4 were examined for curl retention, feeling of use, and dust adhesion.

Experimental Example 3 Curl Retention ◎ Test Hair Adjustment and Experimental Method A hair bundle prepared in the same manner as in Experimental Example 1 was wrapped around a plastic rod with a diameter of 2 foxes while applying a force of 30 weight, and fixed. The above-mentioned hair setting agent was applied separately to each of the hairs, and the hair was dried for 15 minutes using a hair dryer.

After drying, the curl was removed from the rod, the upper end of the curl was fixed and hung indoors, and the diameter of the curl was measured after a predetermined period of time had elapsed. The results are shown in Table 3. Table 3 Experimental Example 4 Feeling of use and dust adhesion The hair setting agents of Example 2 and Comparative Example 4 were each applied to a panel of five experts, and 6 hours after application, the presence or absence of any discomfort and the adhesion of dust were evaluated. The presence or absence of was investigated.

The results are shown in Table 4. Table 4 As shown in Tables 3 and 4, the hair setting agent of the present invention has curl retention properties that are equal to or better than conventional hair setting agents, and are particularly effective in terms of feeling of use and prevention of dust adhesion. In this respect, the hair setting agent of the present invention is superior to conventional hair setting agents.

Claims (1)

[Claims] 1. In a hair setting agent whose main components are a film-forming substance, water, and alcohol, keratin is reduced as a film-forming substance with mercaptans or sulfides in an alkaline range, and then hydrolyzed with an enzyme, resulting in 1 molecule containing keratin. A hair setting agent characterized by using a water-soluble keratin hydrolyzate having two or more mercapto groups.