JPH0565484B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a permanent wave intermediate treatment agent composition, more specifically, a composition that suppresses hair deterioration caused by permanent wave treatment, imparts good texture to hair, and improves permanent wave forming ability. In addition, the permanent wave agent itself,
Alternatively, the present invention relates to a hair treatment agent having the effect of removing mercapto odor and ammonia odor generated by permanent wave treatment. [Prior art and its problems] The permanent wave method for imparting desired waves to hair uses a permanent wave first agent (hereinafter referred to as "first agent") whose main ingredients are reducing agents such as thioglycolic acid and cysteine. ) to reductively open the S-S bonds in hair, and then bromate,
Permanent wave second agent (hereinafter referred to as “second agent”) whose main component is an oxidizing agent such as perborate or hydrogen peroxide
This is a method of oxidative closure with However, with this method, the hair is exposed to adverse conditions such as oxidation and reduction, which causes phenomena such as a decrease in the strength of the hair and deterioration of the texture. When brushing, the brush or comb does not go through well, causing snags, etc.
The hair is damaged by peeling of the epidermis, split ends, and cut hair. Hair deterioration phenomena occur at each stage of permanent wave processing. That is, since the first agent is mainly composed of a reducing agent and an alkaline agent, the hair is swollen by these agents, the keratin protein in the hair is destroyed, and the protein and amino acids are eluted into the treatment solution. This swollen hair is then damaged by an oxidizing agent in treatment with a second agent. However, this phenomenon caused by the first agent is unavoidable due to reduction and opening of the S-S bonds in the hair, and therefore, it has been difficult to prevent hair deterioration due to permanent wave treatment. . Conventionally, a method for preventing hair damage caused by permanent waving agents has been to incorporate an oil agent, a humectant, etc. into the first and/or second agent, but this method is still unsatisfactory. It wasn't something. In addition, in the permanent wave method, during the process, bad odors such as thioglycolic acid contained in the drug, mercaptan caused by the decomposition of keratin in the hair, and ammonia used as an alkali agent are generated, causing discomfort. I often gave. [Means for Solving the Problems] Under these circumstances, the present inventor conducted intensive research to overcome the above-mentioned drawbacks in permanent wave treatment, and as a result, developed a method using a specific keratin hydrolyzate and a quaternary ammonium salt. Contains, first agent and second agent
If hair is treated with a composition that does not contain the reducing agent and oxidizing agent contained in the agent between the first and second agent treatments, prevention of hair damage and removal of bad odor can be achieved at once. The present invention was completed based on this discovery. That is, the present invention provides the following components (A) and (B): (A) A keratin hydrolyzate obtained by hydrolyzing a keratin substance, which has an average molecular weight of 200 to 5000 and a cystine residue content of 0.5 mol% or more. (B) Quaternary ammonium salt represented by the following general formula () (In the formula, 1 or 2 of R ₁ to _{R 4} has a carbon number of 8 to 22
The remainder is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, and X is a halogen atom or an alkyl sulfate having 1 or 2 carbon atoms. ), contains no reducing agent or oxidizing agent, and has a pH of 2.
-7, a permanent wave intermediate treatment agent is provided. The keratin hydrolyzate used in the present invention is obtained by hydrolyzing keratin materials. Examples of the keratin material used as a raw material include animal hair, hair, feathers, nails, horns, hooves, scales, etc. Among them, wool, hair, and feathers are particularly preferred. These keratin materials can be subjected to hydrolysis as they are, but if necessary, they may be cut or crushed into appropriate sizes, or pretreated such as washing and degreasing. Hydrolysis of keratin substances is not particularly limited and can be carried out by conventional methods, examples of which are as follows. (1) Hydrolysis with acids Examples of acids include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, and hydrobromic acid; and organic acids such as acetic acid, formic acid, and oxalic acid. Compared to alkaline hydrolysis, those obtained by acid hydrolysis do not cause any changes in the polypeptide chains of keratin other than hydrolysis, and therefore better results can be obtained. (2) Hydrolysis with alkali As the alkali, inorganic alkalis such as sodium hydroxide, potassium hydroxide, lithium hydroxide, barium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium silicate, and borax are used. . (3) Hydrolysis by enzymes As enzymes, acidic proteolytic enzymes such as pepsin, protease A, and protease B; neutral proteolytic enzymes such as papain, promelain, thermolysin, trypsin, pronase, and chymotrypsin are used. Of the above hydrolysis (1) to (3), (2) hydrolysis with alkali tends to cause destruction of cystine residues,
Furthermore, the obtained hydrolyzate also has some problems in terms of color and odor, and the enzymatic hydrolyzate (3) has the problem of having a small amount of cystine residues, so acid hydrolysates are particularly preferred. The average molecular weight of keratin hydrolyzate is 200-5000,
Particularly preferred is 500 to 3000. Furthermore, disulfide bonds in the keratin hydrolyzate must be present in an amount of 0.5 mol% or more as cystine residues, and particularly preferably 2 mol% or more. For this purpose, it is desirable to use a highly pure keratin material and to perform the hydrolysis under mild conditions. In addition, as the quaternary ammonium salt, those represented by the formula () are used, but especially
A mono-long-chain alkyl type quaternary ammonium salt in which only one of R ₁ to _{R 4} is a long-chain alkyl group having 8 to 22 carbon atoms is preferred. The amount of keratin hydrolyzate blended into the permanent wave intermediate treatment agent composition of the present invention is 0.01 to 50.
Weight% (hereinafter simply expressed as %), particularly preferably 0.1 to 20%, and the amount of the quaternary ammonium salt is
0.1-10%, especially 0.2-5% is preferred. To adjust the pH of the composition of the present invention to 2 to 7,
Weak acids with a pKa value of 7 or their salts are used as buffers, alone or in combination. Examples of weak acids include citric acid, succinic acid, acetic acid, lactic acid, tartaric acid, glycine, and aspartic acid. The PH of the composition can be adjusted by changing the ratio of weak acid and weak acid salt, or by appropriately adding an acid such as hydrochloric acid or phosphoric acid or an alkali such as sodium hydroxide or ammonia. The above buffering agent has a weak acid ion concentration of 0.05 to 10 in the composition.
%, especially preferably 0.1 to 5%. In addition to the above-mentioned essential components, the intermediate treatment agent composition of the present invention may contain commonly used surfactants, solvents, oils, wetting agents, colorants, emulsifiers,
Arbitrary ingredients such as fragrances can be blended. Examples of surfactants include non-containing surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene stearate, glycerol fatty acid ester, castor oil or ethylene oxide adduct of lanolin. An ionic surfactant is used, and as a solvent, alcohols or glycols such as ethanol, isopropanol, propylene glycol, polyethylene glycol, diethylene glycol, triethylene glycol, etc. are used. Furthermore, cationic polymers and amphoteric polymers described in JP-A No. 56-92812 can be blended to enhance the hair protection effect. The intermediate treatment agent composition of the present invention is prepared by dissolving the above-mentioned essential components and optional components in water or an aqueous solvent to form a solution, emulsion, aerosol, or the like. [Effects of the Invention] When hair is treated with the permanent wave intermediate treatment agent composition of the present invention between the first and second agents, the bad odor disappears, the hair feels good, and the ability to form permanent waves is improved. improves. [Example] Next, reference examples and examples will be given and explained. Reference Example Production of keratin hydrolyzate: (a) 10 g of wool fiber was immersed in 300 g of a 75% phosphoric acid aqueous solution, and a hydrolysis reaction was carried out at 120 to 130°C for 7 hours. After cooling and removing the insoluble portion by filtration, 4 to 5 times the amount of water was added and the insoluble portion was further removed by centrifugation. Next, calcium carbonate or barium hydroxide was added to adjust the pH to 6.7, and the precipitate was collected and dried to obtain 8.0 g of a hydrolyzate with a molecular weight of 900 and a cystine residue content of 7 mol%. . (b) 100 g of feathers was heated under pressure in a high-pressure container at 6 kg/cm ² with superheated steam at 240° C. for 6 minutes, and then rapidly released into the atmosphere to obtain a porous expanded product. After crushing this puffed material, add 0.3N caustic soda 3,
After carrying out the hydrolysis reaction at 60°C for 18 hours, the reaction solution was neutralized with 1N hydrochloric acid and filtered. Salt in the resulting solution was removed by ultrafiltration using a membrane with a molecular weight cutoff of 500, and the keratin hydrolyzate aqueous solution was concentrated and lyophilized to obtain 7.2 g of keratin hydrolyzate. Ta. The molecular weight of this substance was determined by gel filtration method.
1800, and the cystine residue content was 7.2 mol%. Example 1 In the method of permanent wave treatment using the following cold wave first agent and second agent, hair is treated with the permanent wave intermediate treatment agent composition shown in Table 1 between the first agent and the second agent. A beautician was asked to evaluate the mercapto odor and ammonia odor. The results are shown in Table 1. Chemicals used: (1) Cold Wave 1st agent Ammonium thioglycolate 7.0 (%) Water, aqueous ammonia (for PH adjustment) 93.0 (%) (Adjust PH to 9.0 with ammonia water) (2) Cold Wave 2nd agent Agent Sodium bromate 5.0 (%) Water 95.0 Treatment conditions: For 7 permanent wave panelists,
Following the usual method, apply 80ml of cold wave agent 1 to the entire hair wrapped in a rod, leave it for 10 minutes, remove the cap, apply 40ml of the intermediate treatment agent shown in Table 1, and apply the perm immediately after application. The odor was evaluated. Next, apply 100ml of Cold Wave 2nd agent,
After leaving the hair for 10 minutes, the hair was removed from the rod, thoroughly rinsed with tap water at 40°C, dried, and the perm odor after finishing was evaluated. (Evaluation criteria) ◎: Not felt 〇: Hardly felt △: Slightly felt ×: Strongly felt

[Table] Example 2 Using the intermediate treatment agent for cold perm shown in Table 2, the first cold wave agent shown in Example 1 was used.
Hair was treated between the agent and the second agent, and the adsorption of the keratin hydrolyzate to the hair after cold wave treatment with the second agent was observed under a scanning electron microscope, and at the same time, the feel of the hair was examined. was also evaluated. Furthermore, the feel of the hair after shampooing was evaluated. The results are shown in Table 2. Evaluation criteria:

【table】 (ii) Sensory evaluation ◎ Very good 〇 Good △ Fairly good × Not good

[Table] Example 3 The first permanent intermediate treatment agent composition of the present invention
When the hair is treated between the agent and the second agent, and when the keratin hydrolyzate (A) and the quaternary ammonium salt (B) are included in the permanent wave agent 1 or 2, the hair is treated with a permanent wave. The degree of mercapto odor and ammonia odor, as well as the adsorption degree of keratin hydrolyzate and the feel of the hair after shampooing were compared in the case of aging. The results are shown in Table 3. Drugs used: (1) Present invention Same as Example 1 and Example 2. (2) Comparative Example 1 The same cold wave first agent as in Example 1 except that the components listed in Table 3 were added, and the cold wave second agent described in Example 1 were used. Comparative Example 2 The same cold wave second agent as in Example 1 was used except that the cold wave first agent described in Example 1 and the components listed in Table 3 were added. Hair treatment method and evaluation method: (1) Present invention Same as Example 1 and Example 2. (2) Comparative Examples 1 and 2 Same as Example 1 and Example 2 except that hair treatment was not performed between the first and second agent treatments.

【table】

[Table] Example 4 Hair was treated with the intermediate treatment agent shown below (containing keratin hydrolysates with different molecular weights) between the cold wave first agent and second agent treatments shown in Example 1, and the hair was permanently treated. The wave effect was evaluated. The results are shown in FIG. Intermediate treatment agent: Keratin hydrolyzate 5.0 (%) Lauryltrimethylammonium chloride 1.0 Citric acid 3.0 Potassium hydroxide Adjusted to PH3.5 Ion-exchanged water balance 100 How to measure the degree of wave: Bleach and perm each according to the usual method 1
10 strands of 15 cm Japanese hair were wrapped into a bundle, wrapped around a glass tube (10 mm in diameter), and placed in the first agent at 30°C.
Soaked for 15 minutes. After immersing this in the intermediate treatment agent for 10 minutes, immersing it in the second agent for 10 minutes, and rinsing thoroughly with water, the hair bundle is removed from the glass tube, and the hair becomes coiled. The length of the hair coil at this time was measured, and the degree of waving was determined by the following formula. Wave degree (%) = Y/X-Y x 100 3.2 mol%) B Cationized cellulose 1.0 (Commercial product name Polymer JR400 "Union Carbide") C Benzalkonium chloride 0.5 D Cetyltrimethylammonium chloride 0.5 E Glycine 10.0 E' Hydrochloric acid Adjusted to PH4.0 F Fragrance 0.1 G Ion exchange water Balance 100 After dissolving B well in ion exchange water, C, D
Add a solution of F to and stir well, then add A and E.
and E′. This intermediate treatment agent further improved the feel after perming compared to when keratin hydrolyzate was used alone. Example 6 (Aerosol type) A Keratin hydrolyzate 10.0 (%) (Average molecular weight 900, cystine content 0.5 mol%) B Stearyltrimethylammonium chloride
0.5 C Citric acid 3.0 C' Ammonia water (28%) Adjusted to PH3.2 D Polyoxyethylene (20) Lauryl ether 0.1 E Fragrance 0.1 F Ethanol 20.0 G Ion exchange water balance 100 After dissolving A in ion exchange water ,F,B,D
Add a solution of E to and stir well, then add C and
C' was added to make a stock solution. Furthermore, for 90 parts of this stock solution,
The propellant (Freon 12/LPG) was filled to 10 parts and manufactured. Since this intermediate treatment agent covered the hair with foam, the deodorizing effect of mercapto odor and ammonia odor was improved. Example 7 (Emulsified type) A Keratin hydrolyzate 20.0 (%) (Average molecular weight 1500, cystine content 1 mol%) B Stearyltrimethylammonium chloride
0.3 C distearyltrimethylammonium chloride
0.1 D Setanol 1.0 E Polyoxyethylene (10) oleyl ether 0.2 F Citric acid Adjusted to PH3 G Fragrance 0.2 H Propylene glycol 10.0 I Ion exchange water balance 100 B, C, D, E, H mixed and dissolved by heating was added to ion-exchanged water, stirred, and then A and G were added to produce the product. By using this intermediate treatment agent on hair immediately after perm treatment, it was possible to deodorize and deodorize residual mercapto odor and ammonia odor.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between the molecular weight of the keratin hydrolyzate blended into the permanent wave intermediate treatment agent composition of the present invention and the degree of waving.

Claims (1)

[Scope of Claims] 1. Components (A) and (B), (A) Hydrolyzed keratin with an average molecular weight of 200 to 5000 and a cystine residue content of 0.5 mol% or more obtained by hydrolyzing a keratin substance. (B) Quaternary ammonium salt represented by the following general formula () (In the formula, 1 or 2 of R ₁ to _{R 4} has a carbon number of 8 to 22
The remainder is an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a benzyl group, and X is a halogen atom or an alkyl sulfate having 1 or 2 carbon atoms. ), contains no reducing agent or oxidizing agent, and has a pH of 2.
7. A permanent wave intermediate treatment agent composition.