JPS6213322B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new one-component hair permanent waving agent, and more specifically, the present invention relates to a novel one-component hair permanent waving agent. A new one-component hair permanent waving agent that does not contain the main ingredient or is used in a much smaller amount, is odorless, harmless, can be operated in a short time, and is completely free from damage. More specifically, it consists of a sulfide, hydrosulfide or mercaptan compound as a main component, and an air oxidation promoter, and further contains a sulfite, and the sulfite has a sulfide, hydrosulfide or mercaptan compound. A one-component hair permanent waving agent having a molar ratio of 1.0 or more, the agent containing a free alkali and having a molar ratio of 8 to 11
This invention relates to a novel one-component hair permanent waving agent, which exhibits a PH value of
It is useful for giving permanent waves to cold hair. Furthermore, the present invention relates to a method of imparting a permanent wave shape to hair using the hair permanent wave agent. Hair permanent waving agents that are currently widely used around the world are classified into the following two main groups with respect to their application methods, as already described in US Pat. No. 4,192,863. (1) Two-component hair permanent waving agent This agent is widely used in professional beauty salons, and its application method is approximately 60 mm with a diameter of approximately 2 to 10 mm.
The hair is coated with a first liquid containing 5 to 8% by weight of alkali thioglycolate or its modified product as a practical main ingredient and is tightly wound around a rotary or curler. This winding operation takes about 20 minutes. The curled hair is then reapplied with the formulation and a vinyl cap is placed over the user's head for approximately 10 to 30 minutes until the formulation dissolves and softens the hair surface. Then, a second liquid containing about 2 to 6% by weight of a strong oxidizing agent such as potassium bromate, sodium bromate, hydrogen peroxide, etc. or oxygen gas is applied to the hair for about 20 to 30 minutes to fix and deodorize the dissolved and softened hair. It is something to do. The hair is then removed from the rod or curler and
Rinse with warm water for ~10 minutes. The hair is then applied with a hair setting lotion and wound around 30 to 60 curlers with a diameter of 1 to 3 cm, resulting in large curls with a diameter of 2 to 6 cm, depending on preference. This will take approximately 20 minutes. The hair is then approximately
Dry with hot air at a temperature of 45°C for about 25 minutes, then remove the hair from the curlers, brush and style with a comb and hair pins to complete the hair styling. (2) One-component hair permanent waving agent This agent has almost the same composition as the first component above, dissolves and softens the hair, and then fixes the hair through air oxidation. In this method, the second liquid is used to remove bad odors such as hydrogen sulfide generated by the decomposition of thioglycolate during use. Otherwise, the bad odor cannot be removed at once, and it will be necessary to thoroughly wash the hair with water and allow it to naturally deodorize in the air for about 4 weeks. Therefore,
Conventional one-component hair permanent waving agents are not truly one-component, but actually belong to two-component formulations. As can be seen from the above, conventional two-component or one-component solutions take at least 120 minutes to finish permanently waving hair, and such a long usage time represents a troublesome drawback. Furthermore, conventional hair permanent waving agents generally contain 1 to 10% by weight in order to dissolve and soften the hair.
Using thioglycolic acid, cystine and by-product cysteine in the hair are eluted, and by reaction with heat or strong oxidizing agents, hydrogen cyanide and other cyanide compounds are generated as contaminants, causing diseases such as pernicious anemia and liver cirrhosis. Chemical poisoning can occur, and the thioglycolic acid retained in the hair makes it porous, coarse, dull, and discolored. The hair permanent waving agent is patented in the U.S. Patent No.
No. 3025218 (Strain et al.), No. 2631965 (Shunel), No. 3148126 (Martin) and No.
It is disclosed in No. 4192863 (Kondo) and Japanese Patent No. 299121 (Special Publication No. 36-450) (Kondo). U.S. Patent No. 3,025,218 is a two-component method, in which a large amount of acetalic acid is used simply to lower the pH of the hair permanent waving agent, and it dissolves and softens the hair.
It still has a bad odor and therefore requires oxidizing fixatives, which are very damaging to the hair. In U.S. Patent No. 2,631,965,
1 to 10% by weight of thioglycolic acid and a large amount of oxyorganic ammonium salts are contained in the alkaline aqueous solution, which discolors the hair and produces a bad odor. And in order to quickly deodorize in a beauty salon, it is necessary to use a fixative oxidizing agent to remove the bad odor, so the preparation is actually a two-part preparation that damages the hair. US Patent No.
No. 3148126, the hair permanent waving agent contains 1 to 15% by weight of thioglycolate and monoethanolamine, also containing a fixing oxidizing agent (containing hydrogen peroxide and acetic acid), 150° to
Heating at a high temperature of 200 °C or sending oxygen gas under the helmet covering the scalp is necessary for rapid deodorization and hair fixation. Therefore, this hair permanent waving agent is naturally a two-component agent, whereby the hair on which it is used is highly damaged. The hair permanent waving agent of Japanese Patent No. 299121 is a one-component permanent waving agent, which contains 3 to 3.5% by weight of thioglycolic acid and 0.01% by weight of thioglycolic acid.
~0.03% by weight oxyorganic acid and 1-2% by weight
of ethyl alcohol and add less than 0.1% by weight of caustic alkali to adjust the pH of the preparation from 7.0 to 11.0.
I have to. However, this preparation also produces a foul odor and is not very effective. The hair permanent waving agent of U.S. Patent No. 4,192,863 has a content of oxyorganic acid ranging from 0.01 to 0.03% by weight to 0.1 to 0.1% by weight in order to improve the deodorizing and waving effects of the agent of Japanese Patent No. 299121.
0.4% by weight and 0.01% of monoethanolamine or triethanolamine or mixtures thereof.
~1.0% by weight and 1.0 to 10.0% by weight of ethyl alcohol are added, but as shown in the comparative examples below, results are unsatisfactory in terms of odor, elongation of treated hair, tensile strength, etc. As a result of repeated research and experiments on suitable drugs to eliminate the above-mentioned drawbacks, the present inventor obtained new knowledge that is completely different from the conventional hair wave theory, and completed the present invention. That is, the conventional and present hair waving theories are as follows. Conventional permanent waves consist of cystine in keratin, a type of protein that makes up hair.

Cysteine (HS-CH ₂ CH
(NH ₂ )COOH) is generated and then fixed by oxygen atoms contained in the second liquid (oxidizing agent such as potassium bromate, etc.) or oxygen in the air to restore the sulfur bond. It is as shown in the following formula.

[Table] +
(sulfur bond) (water)
In the above case, the reducing agent thioglycolic acid is used in an amount of 1 to 10% by weight in the preparation, but if less than 5% is used, sulfur bond cleavage of cystine can only be done by heating. It is believed that. In fact, the first solution elutes some of the cystine and softens the hair, but it also makes the hair porous, thin, dull and discolored. The hair is then curled and fixed by the oxidizing agent in the second liquid, as is common with proteins. At the same time, dissolved cystine or its derivatives may react with excess second liquid oxidizing agent to produce sulfite compounds and cyanide compounds, resulting in chemical poisoning. Furthermore, the treated hair requires rinsing to remove odors such as sulfite compounds, cyanide compounds, and hydrogen sulfide. On the other hand, the hair permanent wave of the present invention uses sulfide, hydrosulfide or thioglycolate, and sulfite contained in the liquid to remove cystine in the hair without using a second liquid. The sulfur bond of is cleaved in a short time as described below.

[Table] For the purpose of explanation, M and M' are each an alkali metal group or an ammonium group. The resulting cysteine salt and cysteine are combined by the air oxidation promoting effect of hexamethylenetetramine, iodine, bromine, alkali metal, or ammonium iodide or bromide, or a mixture thereof, which is simultaneously contained in the alkaline liquid. , the sulfur bond is restored and fixed as follows.

[Table] is cysteine)
However, M is as defined above. In this case, the content of main components such as sulfides, hydrosulfides, or thioglycolates is much lower than in conventional one-component and two-component systems, and as can be understood from the reaction mechanism above. Since this is an irreversible reaction, the reaction proceeds immediately when applied to the hair to be treated.Since no strong oxidizing agent is used on the hair, this waving agent does not generate hydrogen cyanide, etc. It does not damage the hair or create hair porosity, while the production costs are very low. The generation of bad odors such as hydrogen sulfide from sulfides etc. before or during application is very small, but if necessary, reducing sugars such as sucrose, glucose, fructose, etc.
This is prevented by adsorption with organic amines, lower aliphatic saturated alcohols, etc., and an almost odorless hair permanent waving agent can be obtained. The above-mentioned reducing saccharides are used as reducing aids and as inhibitors of the hair-dissolving action peculiar to sulfides, hydrosulfides, or thioglycolates, which are the main components of the hair permanent waving agent of the present invention, and the above-mentioned organic amines are used as a hair-dissolving agent. It can also be used as a penetration enhancer. Next, the suppleness and shine of the hair are greatly influenced by the moisture contained in the hair, and in order to retain the moisture and prevent skin inflammation and hair dissolution damage, lower aliphatic saturated alcohols are added to the hair permanent of the present invention. By incorporating it into a waving agent, it can use its affinity for water to give hair a beautiful appearance. At this time, the alcohols can also be used as polar solvents and hair swelling agents. Furthermore, for the purpose of suppressing oxidation during the cleavage of the sulfur bond of cystine in the hair and maintaining the pH of the hair permanent waving agent of the present invention at 8 to 11, citric acid,
It is necessary to contain aliphatic oxyorganic acids such as acetalic acid, but if the above-mentioned lower aliphatic saturated alcohols are also contained, the fatty acid esters produced by the reaction with them may be used as neutral soaps and may be harmful to the skin. Moreover, it is possible to perform a cleaning action on the hair without destroying the hair tissue, and to further improve the beauty of the hair. Furthermore, to promote hair fixation, hexamethylenetetramine, iodine, bromine, alkali metal or ammonium iodides or bromides, or mixtures thereof, must be added as air oxidation promoters. In summary, the present invention does not arise from the prior art, and its particular advantages are as follows. (1) The hair permanent waving agent of the present invention is:
Create truly elastic, damage-free, non-porous, shiny, smooth and soft hair in a short time.
It is applied regardless of the type and condition of the hair, whereas conventional hair permanent waving agents are suitable for all operations (application, curling, further application, vinyl capping, oxidation or deodorization, rinsing, re-curling and drying steps). The total time required is 2 hours or more and also causes all types of hair to become porous and/or discolored. (2) The hair permanent waving agent of the present invention is harmless and does not generate toxic compounds caused by the use of strong oxidizing agents and/or neutralizing agents or by rapid air oxidation, so it will never cause chemical poisoning caused by cyanide compounds, etc. Does not occur. Conventional hair permanent waving agents may cause chemical poisoning such as pernicious anemia and liver cirrhosis due to cyanide compounds, hydrogen sulfide, etc. generated during the permanent waving operation. (3) In the hair permanent waving agent of the present invention, based on the hair waving theory of the present invention, the content of main components such as sulfides, hydrosulfides, or thioglycolates is lower than that of conventional one-component and two-component formulas. However, it is very effective, harmless, and virtually odorless when used, whereas conventional hair permanent waving agents contain very high amounts of main ingredients such as thioglycolate. , causing hair discoloration and the foul odor of hydrogen sulfide, and even when using oxidizing agents or air oxidation for hair fixation in conventional one-component hair permanent waving products, toxic cyanide compounds are produced. Repeated use can be harmful to human health, damaging hairdressers' fingertips and fingernails, and even a single use can damage hair, making it rough and lackluster. do. (4) Since there is no discoloration due to the use of the hair permanent waving agent of the present invention even immediately after hair dyeing, hair dye can be applied in advance to give beautiful hair dyeing.
On the other hand, conventional hair permanent waving agents are
It cannot be used immediately after dyeing the hair as it always dissolves the surface of the dyed hair. The hair permanent waving agent of the present invention preferably contains a reducing agent such as an alkali metal or ammonium sulfide, hydrosulfide or thioglycolate as a main component in order to cleave the sulfur bond of cystine in the hair, Also, as an acceptor for the extra sulfur atoms generated by the cleavage reaction, at least equimolar
Preferably, it contains a sulfite of an alkali metal or ammonium, and a mixture of sucrose, glucose, fructose, or the like may be used as a reducing agent to prevent the generation of bad odor before or during use.
The reducing agent, which is the main component, may be used in excess, but more than the same mole of sulfite will simply be wasted, so it is usually 0.16 to 0.4% by weight, and even 0.2% by weight.
The weight percentage is good, and the equivalent sulfite is 0.14
equimolar amounts of 0.5% by weight or more,
Preferably it is about 0.8% by weight. sucrose, glucose,
When fructose or a mixture thereof is used, the amount is preferably up to 0.3% by weight. Aliphatic oxyorganic acids such as chelic acid and acetic acid are used as oxidation inhibitory agents during the above-mentioned sulfur bond cleavage, and to form esters with lower aliphatic saturated alcohols that may be contained, and in the hair permanent of the present invention. 0.01 to maintain the pH of the wave agent at 8 to 11 by acting as a buffering agent.
Contain ~0.3% by weight. Furthermore, hair retains moisture,
For molecular swelling and formation of esters with polar solvents and the above-mentioned oxyorganic acids, 0.6 to 10% by weight of lower aliphatic saturated alcohols such as ethyl alcohol, propyl alcohol, glycerin, ethylene glycol, and diethylene glycol, or a mixture thereof, is contained. It's okay. Furthermore, monoethanolamine, diethanolamine or triethanolamine, or a mixture thereof, can be used as a hair penetration enhancer and deodorizer for the main ingredients of sulfide, hydrosulfide or thioglycolate, and as an air oxidation activator. Organic amines such as 0.01 to 1.0% by weight may be used, and in order to promote hair fixation, be sure to use hexamethylenetetramine, iodine, bromine, potassium iodide, sodium iodide, ammonium iodide, potassium bromide, bromide. Sodium, ammonium bromide, or a mixture thereof as an air oxidation promoter from 0.02 to
1.0% by weight, preferably 0.6% by weight should be used, and the rest should be pure water, making it ideal for obtaining hair that is odorless, harmless, can be operated in a short time, and is completely undamaged, which was previously unattainable. The hair permanent waving agent of the present invention can be obtained. In order to further clarify this fact, the following comparative experimental example is shown. All indications are by weight. Comparative experiment example Approximately 10 untreated human hairs (virgin hairs) sufficiently moistened with each test solution were placed in a lot with a diameter of approximately 0.45 cm.
Tightly wrap the hair around it and leave it at about 30℃ for about 10 minutes (capture time), then heat the hair wrapped around the rod to about 40℃
After rinsing the hair with warm pure water and gently wiping it with absorbent paper, air dry the hair with a hair dryer, remove the curly hair from the rod, and heat the hair in a beaker at 40°C.
After rinsing with warm pure water and air drying on blotter paper, the final diameter, tensile strength and elongation of the curls were measured as shown in the table below.

【table】

[Table] The hair permanent waving agent of the present invention can be used in beauty salons, for example, as follows. (1) Wrap the hair tightly in the desired hairstyle around about 60 rods or curlers having a diameter of 0.5 to 1 cm, and secure with a rubber band, while optionally applying 30 ml of the permanent wave agent of the present invention, Let's do it. For curly hair, apply an additional 50ml of the product. (2) Cover the user's head with a vinyl cap for approximately 10 minutes, then remove the cap. (3) Rinse your curly hair with warm water, wipe it off with a towel, and
After leaving it for 15 minutes, remove it from the rod or curler.
Finish by air drying or drying with a hairdryer while styling your hair. (4) Before the above treatment (3), if desired, remove all the hair or part of the hair at the front, top and nape from the rod or curler and rewind it on a curler with a diameter of 1 to 2 cm; Blow hot air through your hair to create the big curls you want. The large curls maintain almost the same diameter as the curler even after washing. Additionally, other additives such as fragrances and coloring agents can be added. According to the above method, it is actually odorless, shiny,
Permanently curled hair, which is non-porous and undamaged, is easily obtained, the curls having a diameter of 2 to 6 cm and which are especially appreciated from an aesthetic point of view, even after washing after 6 months. There is no need for a setting step, and there is no risk of chemical poisoning due to cyanide compounds, etc., as is the case with methods using conventional hair permanent waving agents. The hair permanent waving agent of the present invention also includes:
It can be applied to naturally curly hair to make it permanently straight, and can also be used to create shiny hairpieces and wigs, or to finish hair waves when making dolls. I can do it. The following example is illustrative of a hair permanent waving agent of the invention, which is prepared by mixing the components together at room temperature. Of course, various other preparations may be made in accordance with the guiding principles and teachings contained herein, and the examples set forth herein are therefore in no way intended to limit the full scope of the invention. isn't it. All indications are by weight.

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Claims (1)

[Scope of Claims] 1. The main components are sulfide, hydrosulfide or mercaptan compound, and an air oxidation promoter, and further contains a sulfite compound to produce the sulfide, hydrosulfide or mercaptan compound of the sulfite compound. A hair permanent waving agent having a molar ratio of 1.0 or more to a mercaptan compound, which agent contains a free alkali and exhibits a pH of 8 to 11, and further contains the above compound and a water carrier for the alkali. A one-component hair permanent waving agent. 2 Contains or does not contain sucrose, glucose or fructose, or mixtures thereof; alkali metal or ammonium sulfides, hydrosulfides or thioglycolates; alkali metal or ammonium sulfites; aliphatic oxyorganic acids; As an air oxidation promoter, hexamethylenetetramine, iodine, bromine,
alkali metal or ammonium iodides or bromides, or mixtures thereof; lower aliphatic saturated alcohols; organic amines; The molar ratio of sulfide or thioglycolate is
The hair permanent waving agent according to claim 1, characterized in that the pH is 1.0 or more and is in the range of 8 to 11. 3 0-0.3% by weight of sucrose, glucose or fructose, or mixtures thereof; 0.16-0.4% by weight of potassium, sodium or ammonium sulfides, hydrosulfides or thioglycolates; 0.8% potassium, sodium or ammonium sulfites. ~8.0% by weight; 0.01-0.3% by weight of chelic acid or citric acid;
0.02-1.0% by weight of hexamethylenetetramine, iodine, bromine, potassium iodide, sodium iodide, ammonium iodide, potassium bromide, sodium bromide, ammonium bromide, or a mixture thereof; ethyl alcohol, propyl alcohol, glycerin , ethylene glycol, diethylene glycol, or a mixture thereof; 0.01 to 1.0% by weight of a mixture of monoethanolamine, diethanolamine, triethanolamine, or the like; and the remaining amount of pure water. A hair permanent waving agent as described in . 4 Sucrose 0.2% by weight; sodium hydrosulfide 0.2% by weight; sodium sulfite 0.8% by weight; saltic acid
0.08% by weight of potassium iodide; 0.6% by weight of potassium iodide; 0.4% by weight of glycerin; 0.6% by weight of ethyl alcohol; 0.03% by weight of monoethanolamine; and the remaining amount of pure water. agent.