JPS6229413B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to the removal of unpleasant odors generated by the use of permanent waving agents containing mercapto compounds. Conventionally, in waving treatments using the permanent set method, the disulfide bonds between keratin molecules in the hair are reductively cleaved using a reducing agent (usually referred to as the first agent) such as thioglycolic acid or cysteine, and then bromate, perborate, or hydrogen peroxide is used. Oxidizing agents such as (usually referred to as two agents)
A widely used method is to reform disulfide bonds by oxidation with However, the above-mentioned reducing agent containing a mercapto compound has the disadvantage that when used, hydrogen sulfide having a characteristic unpleasant odor is generated, which causes an unpleasant feeling to the surrounding people. In contrast, masking with fragrance is generally used, which alleviates the odor of the permanent wave agent to some extent, but it is almost impossible to suppress the hydrogen sulfide odor, which is an unpleasant odor that occurs when it reacts with hair. . [Prior Art] Various countermeasures have been proposed to overcome these drawbacks. That is, in British Patent No. 674195, as a method for removing hydrogen sulfide generated by permanent wave treatment, a tetramine salt of zinc, copper, nickel, or cobalt is included in a permanent wave agent containing thioglycolate as the main ingredient. It is proposed that. However, this method is not preferable because it removes the zinc salt and forms a colored chelate with thioglycolic acid, etc., and further oxidizes the thioglycolic acid. In addition, zinc salts require a large amount to remove unpleasant odors, and because they form strong complexes with thioglycolic acid, they have the drawback of reducing the wave-forming ability, which is the purpose of permanent wave agents. Furthermore, a special public patent application using unsaturated carboxylic acids
No. 37013, Japanese Patent Publication No. 49-48740 using honey, and Japanese Patent Application Publication No. 154116-1988 using porous material and an airtight cap have also been proposed, but it is difficult to expect sufficient effects from any of them. [Structure of the Invention] The present inventors have conducted various studies in order to take advantage of the advantages of permanent wave agents based on mercapto compounds with strong reducing power such as thioglycolic acid and cysteine, and to solve the above-mentioned disadvantages. It has been found that by using small amounts of antimony and bismuth compounds, the unpleasant odor peculiar to mercapto compounds and the unpleasant odor and residual odor of hydrogen sulfide generated by permanent wave treatment can be easily removed. Furthermore, these compounds were difficult to form a complex with a mercapto compound, and the thiol group was not blocked and the wave-forming ability was not reduced. In addition, there was no difference from conventional products in terms of wave retention, texture, long-term stability of chemical solutions, and hair strength tests. The gist of the present invention is a deodorizing agent for permanent waving, the main ingredient of which is a mercapto compound, which is characterized by comprising at least one of germanium, antimony, and bismuth compounds. One embodiment is a deodorizing agent containing the above germanium compound etc. in a permanent waving agent containing a mercapto compound as a main ingredient, and the other embodiment is a deodorizing agent containing the above germanium compound etc. in a permanent waving agent containing a mercapto compound as a main ingredient. This is a deodorizing agent that uses germanium compounds, etc. In the present invention, the substance (referred to as a deodorizer) that has the effect of removing unpleasant odors generated when using a permanent wave agent containing a mercapto compound as a main ingredient is one selected from germanium, antimony, and bismuth compounds. As mentioned above, these compounds are preferably those that are compatible with water, mercapto compounds, and alkaline agents, and specific examples include germanium dioxide, germanium tetrachloride, sodium metagermanate, antimony chloride, antimony sulfate, antimonicarium tartrate, and nitric acid. Examples include bismuth, bismuth subnitrate, and bismuth oxychloride. Next, in the present invention, examples of the mercapto compound used as a reducing agent in the permanent waving agent having a mercapto compound as a main ingredient, which is to be deodorized, include thioglycolic acid, cysteine, thiolactic acid, salts thereof, thioglycerin, glycerin monomer, etc. Examples of alkaline agents include thioglycolic acid, ammonia,
Monoethanolamine, diethanolamine, triethanolamine, isopropanolamine,
Examples include ammonium bicarbonate and ammonium carbonate. Among these, ammonium odor caused by alkaline agents can be masked by the use of flavoring agents such as fragrances. The first aspect of the present invention is carried out by incorporating a deodorizing agent such as germanium into a permanent waving agent containing a mercapto compound as a main ingredient. The concentration of the deodorizing agent is preferably such that the compound is contained in an amount of about 0.01 to 5% by weight, particularly 0.05 to 2% by weight as a metal content. In a second embodiment, a deodorizing agent such as germanium is used, for example, in the form of an aqueous solution, and hair is treated as a pre-treatment agent before using a permanent waving agent containing a mercapto compound as a main ingredient in the usual form. It is carried out in the form of The concentration in this case is in the same range as in the first embodiment. Permanent wave agents are generally used in alkaline ranges because of their wave forming ability, which is usually used in acidic to alkaline ranges. In any of the embodiments of the present invention, it is possible to exhibit a remarkable effect of inhibiting the generation of hydrogen sulfide, and also to remove residual odor after permanent wave treatment. In the present invention, the compound such as germanium reacts with generated hydrogen sulfide to produce a metal sulfur compound, which is thought to suppress the generation of unpleasant odor. In the present invention, the permanent waving agent includes pigments, fragrances, penetrants, hair protectants, hair tonics,
Other useful substances that are usually added to permanent wave agents can be added. In addition, as an applied aspect of the present invention, the deodorizer can also be used by coating or impregnating end paper, caps, etc. for permanent wave treatment. Next, the present invention will be specifically explained using test examples and examples. Test example 1 Hydrogen sulfide production test generated from hair by permanent wave treatment Attached Figure 1 is a hydrogen sulfide sampling device, Figure 2 is a schematic diagram of the same measuring device, a is a 250ml air washing bottle (containing 100ml of liquid paraffin), b is a 250ml sample bottle, c is a 250ml absorption bottle (contains 100ml of absorption liquid), d is a three-way container for acid main use,
e is a 200ml flush flask (liquid paraffin 100ml
), f is a 200ml sample flask, and g is a detection tube. First, using the hydrogen sulfide extraction device shown in Figure 1, take 5 g of hair in a constant temperature room at 25°C, add 50 ml of the conventional first agent for permanent waves, soak the hair thoroughly, seal it, and leave it for 15 minutes. After reacting for 15 minutes, add dilute sulfuric acid from step d to adjust the pH of the solution to 2 to 2.5.
Continuous suction for c min. Hydrogen sulfide was determined by applying JIS K0108 2(1) volumetric method (iodine titration method) to the absorbed liquid. H ₂ S generated from 100 g of hair = total amount of H ₂ S captured - blank test/hair x 100 = 2.98 x 10 ^-3 -0.94 x 10 ^-3 /5
×100 = 4.1×10 ^-2 g (Note) Hair: Untreated hair was treated with sodium lauryl sulfate.
Washed with 0.5% aqueous solution, thoroughly rinsed with water, and then air-dried. Note that the amount of H ₂ S generated varies somewhat depending on the properties of the sample hair. Example 1 Using a first agent for permanent waves of the present invention containing a deodorizing agent and a conventional first agent for permanent waves, the amount of hydrogen sulfide, which is an unpleasant odor generated during permanent wave treatment, was detected and compared. The hydrogen sulfide measuring device shown in FIG. 2 was used. Test method Hair is washed with a 0.5% sodium lauryl sulfate aqueous solution, thoroughly washed with water, air-dried, and 1 g of hair is tied into bundles. 1 g of the hair bundle was wrapped around a rod and fixed in a constant temperature room at 25°C, and immersed for 30 seconds in 20 ml of the first agent for permanent waves of the present invention having the following formulation and the first agent for conventional permanent waves. Immediately after cutting, the sample was placed in f in Fig. 2, sealed, and allowed to react for 15 minutes. The hydrogen sulfide generated was measured using g, applying the JIS K0108 2(3) detection tube method. The following examples are carried out in the same way.

[Table] The PH of this first agent is 9.3, and the concentration is weight % based on the total volume. The results are shown in Table 1. The values in the table are ppm.

【table】 Example 2

[Table] The PH of this first agent is 9.3, and the concentration is weight % based on the total volume. The results are shown in Table 2. The values in the table are ppm.

【table】 Example 3

[Table] The pH of this first agent is approximately 7.6, and the concentration is in weight % based on the total volume. The results are shown in Table 3. The values in the table are ppm.

【table】 Example 4

【table】

[Table] The PH of this first agent is 9.3, and the concentration is weight % based on the total volume. The results are shown in Table 4. The values in the table are ppm.

[Table] Example 5 Sulfurization that occurs when a liquid containing the deodorizing agent of the present invention is used as a pretreatment agent for permanent wave treatment, and when treatment is performed with a conventional first agent for permanent wave treatment, and when no pretreatment is performed. Hydrogen detection was compared. Test method: 20 cm long hair is treated with 0.5 sodium lauryl sulfate.
% aqueous solution, thoroughly rinsed with water, air-dried, and bundled 3 g of hair. After wrapping 3 g of the hair bundle in water into a rod with a diameter of 10 mm and air drying, apply the pre-treatment agent of the present invention (formulation below) evenly with a 1.2 ml dropper, and then apply 2.4 ml of the conventional first agent for permanent waves evenly in the same way. Immediately place it in the container f in Figure 2, seal it, and place it in a constant temperature room at 30℃.
The mixture was allowed to stand for 15 minutes to react, and hydrogen sulfide generated was measured using g according to the JIS K0108 2(3) detection tube method. Formula (wt%) (17) Germanium dioxide 0.3 Monoethanolamine 0.3 Sorbitol 7.5 Emacol VF (mentioned above) 5.0 Purified water remaining amount 100 (18) Antimonylpotassium tartrate 3.0 Emacol VF (mentioned above) 5.0 Purified water remaining amount 100 (19) Vizimus oxychloride 1.4 Hydrochloric acid 1.6 Disodium edetate 2.0 28% ammonia water 3.4 Emacol VF (mentioned above) 5.0 Purified water Remaining amount 100 The pH of this pretreatment agent is approximately 7th, and the concentration is based on the total volume. % by weight. The results are shown in Table 5. The numerical values in the table are in units of ppm.

【table】

[Table] In this example, an aqueous solution of the deodorizing agent was used as the pretreatment agent, but the form thereof may be liquid, cream, or gel. From the above results, it was found that the deodorizing agent of the present invention, that is, the first agent for permanent waving containing germanium, antimony, and bismuth salts and its pretreatment agent, removes hydrogen sulfide more significantly than conventional products. The present invention can also be applied to hair straighteners, hair removal agents, shampoos, hair rinses, hair treatment agents, etc., as long as the purpose is to remove hydrogen sulfide odor caused by mercapto compounds. Next, the stability test results of the first agent for permanent waves of the present invention will be shown. Test Example 2 Using 6.0% ammonium thioglycolic acid as the thioglycolic acid (TG) content, germanium dioxide, antimonyl potassium tartrate, or bismuth oxychloride was added, and 28% aqueous ammonia was added.
Adjust the pH to 9.3 and use it as the first agent for permanent waves. Store the first agent in a thermostat at room temperature and 40°C,
After several months, thioglycolic acid concentration and alkalinity were measured. The results are shown in Table 6.

【table】

[Table] From the above results, it was observed that there was almost no change even after storage for 3 months at room temperature or in a 40°C incubator.

[Brief explanation of the drawing]

Figure 1 is a schematic diagram of the hydrogen sulfide sampling device, and Figure 2 is a schematic diagram of the same measuring device, where a is an air washing bottle, b is a sample bottle, c is an absorption bottle, d is a three-sided pot for acid injection, e is an air washing flask, f is a sample flask and g is a detection tube.

Claims (1)

[Scope of Claims] 1. A deodorizing agent for permanent waving, the main ingredient of which is a mercapto compound, characterized by comprising at least one of germanium, antimony, and bismuth compounds. 2. The deodorizer according to claim 1, which is contained in a permanent waving agent containing a mercapto compound as a main ingredient. 3. The deodorizing agent according to claim 1, which is used for pretreatment of a permanent waving agent containing a mercapto compound as a main ingredient.