JP2006273729A - Hair treating agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hair treating agent which can exhibit high permanent wave processing performance in a broad pH region (weak acidity to weak alkalinity). <P>SOLUTION: The hair treating agent comprises (i) at least one compound represented by formula (1) (wherein X is any one structure of -O-, -S-, -NH-, and -NR<SP>1</SP>-; R<SP>1</SP>is a 1-6C alkyl group; R<SP>2</SP>is hydrogen or a 1-6C alkyl group; Y is oxygen or sulfur; and R is a divalent organic group which may have a mercapto group) and (ii) at least one compound selected from the group consisting of thioglycolic acid, thiolactic acid, cysteine, acetylcysteine, cysteamine, acylcysteine, a salt thereof, and an ester derivative thereof. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel hair treatment agent containing a cyclic mercapto compound.

  It is known that a permanent wave is formed by two processes. That is, there are a step of reducing and cleaving the cystine (disulfide) bond of hair by the action of the reducing agent, and a subsequent neutralization or fixing step using an oxidizing agent, and the latter step restores the cystine (disulfide) bond.

  Conventionally, compounds generally used as keratin reducing substances such as thioglycolic acid, cysteine, acetylcysteine, and salts thereof have been used as compounds used in permanent processing of hair. Since these conventional compounds, which are also called keratin reducing substances, have practical performance under alkaline conditions for the permanent processing of hair, many permanent liquids are adjusted to be alkaline with a pH of about 9.5. However, it is known that perm liquid adjusted to alkaline causes damage to hair and scalp, and in order to solve these disadvantages, a neutral to slightly acidic pH range (pH: 3 to 7.5, 25). The development of keratin reducing substances that can be used at 0 ° C is underway.

For example, use of a monoglycerol ester of thioglycolic acid as a keratin reducing substance used in such a pH range has been studied (for example, Patent Document 1). In addition, the use of mercaptoglycolamide derivatives and mercaptolactic acid amide derivatives has also been studied for the purpose of solving skin disorders observed with thioglycolate esters (for example, Patent Document 2 and Patent Document 3). Furthermore, the use of cysteamine, which is considered to be effective with weak acidity, has also been studied. (For example, Patent Document 4)
Japanese Patent Application Laid-Open No. 08-291031 Special Table 2000-507272 Special table 2003-528901 gazette JP 03-271214 A

  However, the thioglycolic acid monoglycerol ester proposed in Patent Document 1 is in a liquid state and is excellent in terms of handleability and odor, but there is also a report of sensitization presumed to be derived from a hydroxyl group in the structure. It has not reached.

  The mercaptocarboxylic acid amide proposed in Patent Document 2 is already known to have skin irritation, and the same sensitization is also a concern with the mercaptocarboxylic acid amide derivative proposed in Patent Document 3, Furthermore, there is a problem that there is a concern about lack of purification, sensitization by raw material amine released during storage, and skin irritation.

The cysteamine proposed in Patent Document 4 has insufficient problems such as weakly acidic to acidic wave performance, and furthermore, the hair after permanent treatment has a unique odor.
As described above, the keratin reducing substances that have been proposed in the past show the desired wave performance when used in the weakly alkaline region, but if the permanent wave processing is performed in the weakly alkaline region, the skin and hair will be affected. For example, the hair may be discolored or crushed.

  For this reason, even if the conventional hair treatment agent is used in a neutral / weakly acidic region with less influence, in such a pH region, the wave performance is not always sufficient, and if a large amount is used to maintain the wave performance, On the other hand, it is impossible to remove the odor, and the reducing substance may damage the skin, and a hair treatment agent having a desired wave performance has not been obtained.

  That is, an object of the present invention is to provide a hair treatment agent that can satisfactorily perform permanent wave processing of hair even in acidic, neutral, and weakly alkaline pH regions with less irritation to skin and hair. There is.

As a result of extensive research, the present inventors have found that when a specific mercapto compound is used as a keratin reducing substance, it has higher wave performance than a known compound in a neutral to acidic pH range. As a result of further studies, it has been found that if it is used in combination with another keratin reducing substance, it has high wave performance over a wide pH range, and the present invention has been completed. That is, the configuration of the present invention is as follows.
[1] (i) at least one compound represented by the following formula (1);

(X represents a structure of any of —O—, —S—, —NH—, and —NR ¹ —. R ¹ represents an alkyl group having 1 to 6 carbon atoms. R ² represents a hydrogen atom or 1 carbon atom. And Y represents an oxygen atom or a sulfur atom, and R represents a divalent organic residue which may have a mercapto group.
(ii) A hair treatment agent comprising thioglycolic acid, thiolactic acid, cysteine, cysteamine, and at least one compound selected from the group consisting of salts, ester derivatives or amide derivatives thereof.
[2] The hair treatment composition according to [1], wherein the content of the compound (ii) is 0.01 to 50% by mass of (ii) / (i + ii) with respect to the total amount of the compounds (i) and (ii).
[3] The hair treatment agent according to [1] or [2], wherein the pH of the hair treatment agent is in the range of 3 to 8.
[4] The hair treatment agent according to [3], wherein the compound (ii) is cysteamine, a salt thereof, or an ester derivative thereof.
[5] The hair treatment agent according to [1] to [4], wherein X in the formula (1) is “—O—”, “—NH—”, “—NCH ₃ —” or “—S—”.
[6] The hair treatment agent according to [1] to [5], wherein Y in formula (1) is an oxygen atom.
[7] The hair treatment agent according to [1] to [6], wherein R in the formula (1) is an alkylene group.
[8] The hair treatment agent according to [1] to [7], wherein R in the formula (1) is an alkylene group having one or more mercapto groups.
[9] The compound represented by the formula (1) is:
2-mercapto-4-butyrolactone, 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone and 2-mercapto-6-hexa The hair treatment agent according to [1] to [8], which is at least one selected from the group consisting of noractam.
[10] The content (total amount) of the compounds (i) and (ii) above is 0.2 to 30% in terms of the content of reducing substances (as thioglycolic acid) [1] to [9] Hair treatment agent.
[11] The hair treatment agent according to [1] to [10], wherein the hair treatment agent is a permanent waving agent.
[12] A method for permanently waving hair using the hair treatment agent according to [11].

  The hair treatment agent of the present invention is often used as a permanent waving agent, particularly a cyclic mercapto compound having excellent permanent processing performance in a neutral to acidic pH range, and a neutral to weakly alkaline pH range. And a mercapto compound having an excellent performance for permanent wave processing. For this reason, according to the present invention, high permanent waving performance can be exhibited in a wide pH range (acidic to weakly alkaline). In addition, since it has excellent permanent wave processing practical performance even when the cyclic mercapto compound-containing concentration is low, the amount of the drug itself can be reduced, and the general-purpose permanent wave can be used in the pH range from neutral to acidic. Stable wave efficiency is obtained compared to processing chemicals, so there is less skin irritation and less sensitization during treatment.

  Therefore, the pharmaceutical composition of the present invention is extremely useful as a hair treatment agent, particularly for permanent wave processing of hair.

Hereinafter, the present invention will be specifically described.
The hair treatment agent according to the present invention includes a treatment agent that is widely applied to hair, and has an excellent effect particularly in hair wave formation or hair wave correction, and is broadly referred to as “permanent wave processing agent”. . Specific examples include permanent wave agents with strong wave forming ability, curling agents with weak wave forming ability, and wave lengthening agents such as hair straighteners, straight permanent wave agents, eyelash straighteners, and bed rest straighteners. .

The hair treatment agent according to the present invention includes (i) a specific cyclic mercapto compound and (ii) another mercapto compound.
(i) Cyclic mercapto compound The hair treatment agent of the present invention is characterized by containing at least one cyclic mercapto compound represented by the following formula (1).

(X represents a structure of any of —O—, —S—, —NH—, and —NR ¹ —. R ¹ represents an alkyl group having 1 to 6 carbon atoms. Y represents an oxygen atom or a sulfur atom. (2) R in the formula represents a divalent organic residue which may have a mercapto group, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As X, “—O—”, “—NH—”, “—NCH ₃ —”, and “—S—” are relatively high in solubility in the permanent liquid used as an aqueous solution, and in terms of liquid preparation preferable. Y represents an oxygen atom or a sulfur atom, and an oxygen atom is more preferable from the viewpoint of industrial raw material availability and handling.

Examples of R ² include a hydrogen atom, a methyl group, an ethyl group, and a propyl group. Among them, a hydrogen atom, a methyl group, and an ethyl group are preferable.
R represents a divalent organic residue which may have a mercapto group (—SH). R is not particularly limited as long as it is a divalent organic group, but is preferably an alkylene group. As the alkylene group, an alkylene group having 2 to 6 carbon atoms in the main chain is preferable. The divalent residue may have a branch / side chain. Examples of the side chain include an alkyl group and an alkenyl group.

When R has a mercapto group, the mercapto group may be singular or plural.
Among these, preferable R includes an ethylene group and a propylene group in terms of industrial availability.

Specific examples of the compound represented by the formula (1) include 2-mercapto-3-propiolactone, 2-mercapto-2-methyl-3-propiolactone, 2-mercapto-3-methyl-3-propio. Lactone, 2-mercapto-3-ethyl-3-propiolactone, 2-mercapto-2,3-dimethyl-3-propiolactone, 2-mercapto-3-propiolactam, 2-mercapto-2-methyl- 3-propiolactam, 2-mercapto-3-methyl-3-propiolactam, 2-mercapto-3-ethyl-3-propiolactam, 2-mercapto-2,3-dimethyl-3-propiolactam, 2-mercapto-3-propiothiolactone, 2-mercapto-2-methyl-3-propiothiolactone, 2-mercapto-3-methyl-3-propio Olactone, 2-mercapto-3-ethyl-3-propiothiolactone, 2-mercapto-2,3-dimethyl-3-propiothiolactone, 2-mercapto-4-butyrolactone, 2-mercapto-2-methyl- 4,4-dimethyl-4-butyrolactone, 2-mercapto-3- (2-propenyl) -4-butyrolactone, 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-2-methyl-4-butyrolactone, 2-mercapto-3-methyl-4-butyrolactone, 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-3,4-dimethyl-4-butyrolactone, 2-mercapto-2-ethyl-4-butyrolactone, 2-mercapto-3-ethyl-4-butyrolactone, 2-mercapto-4-ethyl-4-but Lolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-2-methyl-4-butyrothiolactone, 2-mercapto-3-methyl-4-butyrothiolactone, 2-mercapto-4-methyl -4-butyrothiolactone, 2-mercapto-3,4-dimethyl-4-butyrothiolactone, 2-mercapto-2-ethyl-4-butyrothiolactone, 2-mercapto-3-ethyl-4- Butyrothiolactone, 2-mercapto-4-ethyl-4-butyrothiolactone, 2-mercapto-4-butyrolactam, 2-mercapto-2-methyl-4-butyrolactam, 2-mercapto-3-methyl-4- Butyrolactam, 2-mercapto-4-methyl-4-butyrolactam, 2-mercapto-3,4-dimethyl-4-butyrolactam, 2-merca Put-2-ethyl-4-butyrolactam, 2-mercapto-3-ethyl-4-butyrolactam, 2-mercapto-4-ethyl-4-butyrolactam, 2-mercapto-5-valerolactone, 2-mercapto-2-methyl -5-valerolactone, 2-mercapto-3-methyl-5-valerolactone, 2-mercapto-4-methyl-5-valerolactone, 2-mercapto-5-methyl-5-valerolactone, 2-mercapto-2 -Ethyl-5-valerolactone, 2-mercapto-3-ethyl-5-valerolactone, 2-mercapto-4-ethyl-5-valerolactone, 2-mercapto-5-ethyl-5-valerolactone, 2-mercapto -5-valerolactam, 2-mercapto-2-methyl-5-valerolactam,
2-mercapto-3-methyl-5-valerolactam, 2-mercapto-4-methyl-5-valerolactam, 2-mercapto-5-methyl-5-valerolactam, 2-mercapto-2-ethyl-5-valero Lactam, 2-mercapto-3-ethyl-5-valerolactam, 2-mercapto-4-ethyl-5-valerolactam, 2-mercapto-5-ethyl-5-valerolactam, 2-mercapto-5-valerothiolactone 2-mercapto-2-methyl-5-valerothiolactone, 2-mercapto-3-methyl-5-valerothiolactone, 2-mercapto-4-methyl-5-valerothiolactone, 2-mercapto-5-methyl -5-valerothiolactone, 2-mercapto-2-ethyl-5-valerothiolactone, 2-mercapto-3-ethyl-5 Valerothiolactone, 2-mercapto-4-ethyl-5-valerothiolactone, 2-mercapto-5-ethyl-5-valerothiolactone, 2-mercapto-6-hexanolactone, 2-mercapto-2-methyl- 6-hexanolactone, 2-mercapto-3-methyl-6-hexanolactone, 2-mercapto-4-methyl-6-hexanolactone, 2-mercapto-5-methyl-6-hexanolactone, 2- Mercapto-6-methyl-6-hexanolactone, 2-mercapto-6-hexanolactam, 2-mercapto-2-methyl-6-hexanolactam, 2-mercapto-3-methyl-6-hexanolactam, 2-mercapto-4-methyl-6-hexanolactam, 2-mercapto-5-methyl-6-hexanolactam, 2-mercapto 6-methyl-6-hexanolactam, 2-mercapto-6-hexanothiolactone, 2-mercapto-2-methyl-6-hexanothiolactone, 2-mercapto-3-methyl-6-hexanothiolactone, 2- Mercapto-4-methyl-6-hexanothiolactone, 2-mercapto-5-methyl-6-hexanothiolactone, 2-mercapto-6-methyl-6-hexanothiolactone, 2-mercapto-7-heptanolactone, 2-mercapto-7-heptanothiolactone, 2-mercapto-7-heptanolactam, 2-mercapto-8-octanolactone, 2-mercapto-8-octanothiolactone, 2-mercapto-8-octanolactam, 2-mercapto-9-nonalactone, 2-mercapto-9-nonathiolactone, 2-mercap To-9-nonalactam and N-methyl or N-ethyl derivatives of these lactams can be mentioned.

Among these, 2-mercapto-4-butyrolactone (2-mercapto-4-butanolide), 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, 2-mercapto-4-methyl-4- Butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-5-valerolactone, 2-mercapto-5-valerolactam, 2-mercapto-6-hexanolactam have permanent performance and industrial production. From the viewpoint of

  These compounds can be produced according to known methods. For example, it can be synthesized by introducing a mercapto group after using a lactone compound or a lactam compound as a halogenated compound.

  Mercaptolactone and mercaptothiolactone are commercially available using a commercially available lactone or thiolactone. Am. Chem. Soc. 1945,. The halogen compound is synthesized by the method of 67.2218-2220. Synthetic halogen compounds or commercially available halogen compounds are described in Ann. A lactone derivative can be synthesized by synthesis according to the method of 1960, 639.146-56.

  Mercaplactams are described in J. Org. Am. Chem. Soc. 1958.80.6233-6237, a halogen compound was synthesized, and the resulting halogen compound was converted to Ann. A lactam derivative can be synthesized by synthesis according to the method of 1960, 639.146-56.

(ii) Other keratin reducing substances In the present invention, together with the cyclic mercapto compound, the keratin reducing substance includes (ii) thioglycolic acid, thiolactic acid, cysteine, cysteamine, and salts, ester derivatives or amide derivatives thereof. At least one compound selected from the group consisting of:

  Specific examples of the ester derivative include N-acetylcysteine and acylcysteine. Examples of the ester of polyhydric alcohol disclosed in Patent Document 1 include 1,2-propanediol. 1,3-propanediol, 1-methoxypropanol (-2), 1-ethoxypropanol (-2), 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol and the like. These may be glycol monoalkyl ethers such as monomethyl ether or monoethyl ether.

  Examples of the amide derivative include N-branched alkyl-substituted acetamide derivatives as shown in Patent Documents 2 and 3, and those containing a hydroxy group or an ether bond.

  The salt may be a carboxylic acid group constituting a salt, or an amine group may form a salt. Specifically, ammonium thioglycolate, monoethanolamine thioglycolate, cysteine hydrochloride Examples include salt.

Among these, when cysteamine and its derivatives are combined with the compound (i), it is preferable because high permanent wave processing performance can be exhibited even in a wide pH region and the amount of the drug can be reduced.
Composition of hair treatment agent The content of the compound (ii) in the hair treatment agent according to the present invention is such that ((ii) / (i + ii)) is 0.01 to the total amount of the compounds (i) and (ii). 50% by weight, preferably 5-50% by weight, more preferably 20
It is desirable to be in the range of ˜50 mass%.

When used in this range, a hair treatment agent that exhibits high permanent waving performance in a wide pH range from weakly acidic to weakly alkaline and has little effect on the skin can be obtained.
Although the reason is not clear, the mercapto compound (i) has a structure represented by the above formula (1) when used as a main component of a hair treatment agent. Has increased lipophilicity, improved permeability to hair, and has a ring structure that makes it easy to oxidize mercapto compounds, especially acidic to neutral and more easily oxidized. Unlike conventional mercapto compounds, they are considered to function as reducing agents without being alkaline.

It is known that hair is composed of a lipophilic cuticle layer, a hydrophilic cortex, and a medulla layer, and swells as the pH rises to widen the cuticle gap. The highly hydrophilic compound (ii) penetrates from the cuticle gap widened by swelling when used in the vicinity of pH 9, whereas the more lipophilic compound (i) is affected by pH. Although it penetrates through adsorption to the lipophilic cuticle surface, diffusion to the cortex and medulla layer derived from lipophilicity in addition to the decrease in permeability due to the addition of ionicity with the mercapto group is It is considered to be slower than the penetration of the compound.

For this reason, by combining the compound (i) having high permanent wave processing performance in the acidic to neutral pH region with the reduced product (ii) having high permeability in the weak alkali region, The present inventor believes that a high permanent wave processing performance is exhibited even in a wide pH range.

  In addition, the permanent wave processing chemical | medical agent containing only the compound of (i) (specific example: 2-mercapto-4-butyrolactone (MBL)) and the compound of (ii) alone (specific example: cysteamine hydrochloride) is used, When the change in permanent wave processing performance (wave efficiency) due to pH is evaluated, the result shown in FIG. 1 is obtained. FIG. 1 is a graph showing changes in wave efficiency due to pH when each compound corresponding to 2% in terms of thioglycolic acid reducing power is used alone.

As can be seen from FIG. 1, the permanent waving agent containing the compound (i) shows high wave efficiency in the acidic to neutral pH range, and when it becomes alkaline, the wave efficiency tends to decrease slightly. On the other hand, in the permanent wave processing agent containing the compound (ii), the wave efficiency is low when acidic, the wave rate increases linearly with pH, and the wave efficiency increases when alkaline. Therefore, by combining the compounds (i) and (ii), the permanent wave processing performance is exhibited in a wide pH range.

When the hair treatment agent of the present invention is used as a permanent waving agent, the total of the compounds of the above formulas (i) and (ii), the cyclic mercapto compound is preferably 0.2 to thioglycolic acid reducing power. It is contained in an amount of 30%, more preferably 1 to 15%, still more preferably 1 to 10%. Within this range, the wave efficiency can be kept high without damaging the hair and skin.

  If the thioglycolic acid reducing power is less than 0.2%, the performance as a permanent waving agent may not be obtained at all. On the other hand, if it exceeds 30%, hair damage may be increased by promoting extreme curly hair and partial peeling of the cuticle.

The thioglycolic acid reducing power conversion is a notation of the concentration of keratin reducing substance determined for each treatment in the permanent wave quality standard for quasi drugs, and the concentration measured according to the following method It is.
[Thioglycolic acid reducing power conversion]
10 mL of a sample is accurately taken into a 100 mL volumetric flask, and purified water (hereinafter simply referred to as “water”) conforming to the cosmetic raw material standards is added to make a total volume of 100 mL, which is used as a test solution.

Take exactly 20 mL of test solution, add 50 mL of water and 5 mL of 30% sulfuric acid, gently heat and boil for 5 minutes. After cooling, titrate with 0.1N iodine solution and use AmL (indicator: starch sample solution 3mL)
The obtained titration result is calculated as a thioglycolic acid content by the following formula.

Reducing substance content (as thioglycolic acid) (%) = 0.4606 × A
Moreover, the permanent wave liquid agent (curling agent) of cosmetics classification has set the self-regulatory value by the permanent wave liquid industrial association, and the usage amount is prescribed | regulated by the same measuring method.

In this case, 50% or more of the content expressed in terms of thioglycolic acid is preferably the cyclic mercapto compound (i), more preferably 50 to 95%, most preferably 50 to 80%. Is in range. If it is 50% or less, the wave efficiency between weak acidity and neutrality may not be sufficient. If it exists in the said range, the chemical | medical agent for permanent wave processing which has high wave efficiency in the acidic-weakly alkaline wide pH range will be obtained.

The permanent waving agent of the present invention is desirably used by dissolving, dispersing, emulsifying and suspending the compounds of formulas (i) and (ii) in a solvent. As the solvent, water is preferable.
The permanent wave processing agent of the present invention is not particularly limited in form as long as it contains the compounds (i) and (ii) described above, but for example, liquid, foam, gel, cream, paste, etc. Can be used. And according to the form, it can be used as various types of drugs such as liquid type, spray type, aerosol type, cream type and gel type.

In the hair treatment agent of the present invention, an ultraviolet absorber, a hair protecting agent and the like can be blended as other active ingredients.
The cyclic mercapto compound is usually in the form of an oil. Moreover, since it is difficult to mix with hydrophilic solvents, such as water, for example, two layers may be separated, surfactant may be contained.

  The surfactant may be anionic, cationic, amphoteric, or nonionic, and may be a silicon surfactant or a biosurfactant.

For example, anionic surfactants include fatty acid salts, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfonates, α-olefin sulfonates, dialkyl sulfosuccinic acid monodium salts, disodium alkylamidoethyl sulfosuccinic acid esters. , Α-sulfonated aliphatic alkyl ester salts, sodium N-methyl-N-oleyl taurine, sodium alkyl isethinate, petroleum sulfonate, alkyl sulfate, sulfated oil, polyoxyethylene alkyl ether sulfate, poly Oxyethylene alkyl phenyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl phosphate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, Polyoxyethylene alkyl ethers methyl carboxylates, such as naphthalene sulfonate formalin condensates and the like.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl glycol, polyhydric alcohol fatty acid partial ester, polyoxyethylene Ethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid mono (di) ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid dietenol amide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester, trialkylamine Examples include oxides.

Cationic surfactants include primary to tertiary fatty amine salts, tetraalkylammonium salts, trialkylbenzylammonium salts, alkylpyridinium salts, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium salts, N , N-dialkylmorpholinium salt,
Examples thereof include polyethylene polyamine fatty acid amide salts, salts of urea condensates of polyethylene polyamine fatty acid amides, halides such as quaternary ammonium salts of urea condensates of polyethylene polyamine fatty amides, oxo acid salts, and fatty acid salts.

Zwitterionic surfactants include N, N-dimethyl-N-alkyl-N-carboxymethylammoniobetaine, N, N, N-trimethyl-N-alkyleneammoniocarboxybetaine, N-acylamidopropyl-N ' , N'-Dimethyl-N'-β-hydroxypropylene ammoniosulfobetaine, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) ammoniobetaine, 2-alkyl-1-hydroxyethyl-1- Examples thereof include carboxymethylimidazolium betaine.

Examples of the silicon surfactant include dimethicone copolyol (polyoxyethylene / methylpolysiloxane copolymer).
An example of a biosurfactant is a sodium salt of surfactin. Surfactin is composed of a hydrophilic part of a cyclic peptide consisting of 7 molecules of amino acid and a hydrophobic part of a long fatty acid residue. There are two carboxyl groups at both ends of the ring. Have a charge. The cyclic peptide contains two molecules of D-leucine, and L-leucine may be substituted with L-valine or L-isoleucine. Further, the chain length and branching position are appropriately selected for the fatty acid.

When a surfactant is used, the diluent / solvent and the compounds (i) and (ii) can be mixed uniformly, and the mixed emulsion is difficult to separate. The cyclic mercapto compound (i) has a drawback that it is easily decomposed in the presence of water. However, if a surfactant is added, the cyclic mercapto compound is not in direct contact with water. Therefore, it is possible to extend the expiration date.

The compounding amount of the surfactant is appropriately selected according to the purpose of use and the viscosity of the composition, but is usually 0.01 to 200% by mass, preferably 0.02 to the total amount of (i) and (ii). Used in an amount of 150% by weight.

Furthermore, you may mix | blend various additives according to the objective and use form which improve the processing performance of hair.
As additives, swelling agents, penetration enhancers, buffers, oils, thickeners, hair protecting agents, wetting agents, emulsifiers, pH adjusters, fragrances, dyes, stabilizers, odor masking agents, etc. may be used. it can.

  Examples of swelling agents and penetration enhancers include ethanol, propanol, isopropanol, 1,2-propylene glycol, 1,3-butanediol, glycerin, ethyl carbitol, benzyl alcohol, benzyloxyethanol, urea, and 2-methylpyrrolidone. Can be mentioned.

Examples of the buffer include inorganic buffers and buffers containing basic amino acids such as arginine and lysine.
Examples of the oil include paraffin, liquid paraffin, beeswax, squalane, jojoba oil, olive oil, ester oil, triglyceride, petrolatum, lanolin and the like.

  Thickeners include carboxymethylcellulose, carboxyvinyl polymer, hydroxyethylcellulose, hydroxypropylcellulose, xanthan gum, carrageenan, alginate, pectin, tragacanth gum, lauryl alcohol, cetyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, behenyl alcohol, etc. Examples include higher alcohols, kaolin, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecyl acid, isostearic acid and other fatty acids, petrolatum, and the like.

Examples of the hair protecting component include hydrolysates such as collagen and keratin, and derivatives thereof.
Wetting agents or emulsifiers include glycerin, diglycerin, propylene glycol, dipropylene glycol, 1,3-butanediol, sorbitol, plant extract, vitamins, hyaluronate, chondroitin sulfate, cationic, anionic, amphoteric , Ether types such as nonionic surfactants and polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene nonyl ether Nonionic surfactant, dimethylpolysiloxane, methylphenylpolysiloxane, amino-modified silicone oil, alcohol-modified silicone oil, fluorine-modified silicone oil, polyester Ether-modified silicone oil, silicon derivatives such as alkyl-modified silicone oil.

  Examples of pH adjusters include organic acids such as hydrochloric acid, citric acid, malic acid, lactic acid, succinic acid, and oxalic acid, or sodium salts thereof, ammonia, diethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, sodium carbonate, Alkaline agents, such as sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, are mentioned.

Examples of the stabilizer include dithiodiglycolic acid and the like in addition to the disulfide of the reducing compound for the purpose of preventing excessive reduction.
The fragrance is not particularly limited, but acetyl diisoamylene, anis alcohol, undecalactone, ethyl maltol, orange oil, camphor, geraniol, geranyl nitrile, dimethyl octanol, cyclopentadecanolide, citral, citronellal, dimethyl octenol, Methyl dihydrojasmonate, dihydromyrsenol, cinnamic alcohol, spearmint oil, damascon, tansy oil, tripral, trimethylundecadienal, γ-decalactone, trimethylhexenal, nerol, nerolidol, γ-nonalactone, basil oil, pinene , Phenylethyl alcohol, phenylpropanal, fenkyl alcohol, hexenal, cis-3-hexenol, peppermint oil, bergamot oil, ben Zilfomate, benzaldehyde, borneol, methylionone, methylcinnamaldehyde, methoxycitronellal, mentholol, menthol, menthone, lime oil, raspberry ketone, linalool, linalool oxide, limonene, lemon oil, rosephenone, butylcyclohexyl acetate, isobornyl acetate, Dimethylphenylethyl carvinyl acetate, dimethylbenzyl carvinyl acetate, 4- (1-ethoxyvinyl) -3,3,5,5-tetramethylcyclohexanone, cis-p-menthan-7-ol, α, 3,3- Trimethylcyclohexanemethylfomate, 2,2,6-trimethylcyclohexanecarboxylic acid ethyl ester, 2,6,6-trimethyl-1-crotonylcyclohexane, 2-methyl-4- (2,2 3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -pentan-2-ol And at least one compound selected from the group consisting of 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol or an essential oil is preferably used. The These fragrances have a high masking effect of the mercapto compound of the above formula (i). In addition, there is little deterioration of the fragrance, and the aging stability is excellent over a long period of time. Also, after use, a good odor remains for a while after washing. More preferable results can be obtained when a plurality of the above compounds or essential oils are used in combination.

  Examples of other additives include edetic acid and its metal salt, glutamic acid 4 acetic acid and its metal salt, aspartic acid 4 acetic acid and its metal salt, propyldiamine tetraacetic acid and its metal salt as chelating agents.

Further, when the hair treatment agent according to the present invention is used as a hair straightening agent for curling, etc., in addition to improving hair combing, curling, and sleeping, there is no particular limitation on the use mode, for example Shampoos, rinses, conditioners, hair treatments, hair waters, hair waxes, hair mousses, hair gels, etc. are used in combination with the above compounds (i) and (ii). In the case of such a hair straightener, the oxidation treatment with bromate or hydrogen peroxide generally performed with a permanent wave processing agent is not required. When the hair treatment agent according to the present invention is used as a hair straightener, the total amount of the compounds (i) and (ii) is usually 0.01 to 30% by mass, more preferably 0.1 to 10% by mass. , More preferably 1-5
It is contained in an amount of mass%. If the total amount is within this range, the expected hair straightening effect can be sufficiently exhibited. When used as a hair straightener in this way, after application to the hair, it is possible to straighten the hair and curl in a relatively short time from styling or washing with a comb. Furthermore, if the hair straightener of this invention is used, it is also possible to improve the soft feeling of hair.

  The pH of the hair treatment agent of the present invention is not particularly limited, and may be used with an alkalinity of about pH 9, but is preferably used in the range of pH 3 to 8, more preferably pH 5 to 8. Even if the hair treatment agent of the present invention is alkaline, neutral, or weakly acidic, its effect remains unchanged and is excellent.

  When the pH of the drug is in the above range, there is little skin irritation and it does not cause damage to hair and scalp. In addition, the hair treatment agent according to the present invention can exhibit the practical performance of permanent wave processing even when the pH is used within the above range. In order to control the pH of the drug within the above range, for example, the pH adjuster can be added to the drug.

  In the present invention, since the cyclic mercapto compound described above is contained, the hair is excellent in the permanent wave processing performance in a neutral to weakly acidic pH range with little irritation to the skin.

In the present invention, a pharmaceutical composition prepared in advance so as to obtain a desired blending ratio as a hair treatment agent may be used, or it may be used in the adjustment of operations in which each chemical is mixed immediately before use. In the case of business adjustment, the compound of the above formulas (i) and (ii) and the fragrance are added to the pharmaceutical composition, the aforementioned diluent / solvent,
A method of mixing and dissolving a surfactant and a solution in which various compounding agents such as a swelling agent and a penetration enhancer described later are mixed may be used, and the drug composition is diluted with a diluent / solvent in advance. A method of mixing and dissolving may be used. Further, a solution obtained by mixing various compounding agents in (i) and (ii) may be mixed and dissolved.

[Permanent wave processing method]
Although there is no restriction | limiting in particular in the usage method of the hair treatment agent of this invention, For example, as a permanent wave processing chemical | medical agent, the method of the following can be used as a permanent wave processing method with respect to hair. The permanent wave process includes a permanent wave forming process, a wave spreading process using a permanent wave process, and a hair straightening process.
(1) A chemical solution containing the cyclic mercapto compound of the present invention is wetted on the hair and wound with a rod for shaping the hair.
Note that a rod is not used for straightening hair. Alternatively, the keratin reducing solution may be moistened after fixing the hair with a water roll or the like.
(2) Leave the drug solution at room temperature after wetting. In that case, it is preferable to heat to about 30 to 40 degreeC.
(3) The cyclic mercapto compound is oxidized with a composition containing an oxidizing agent to fix the hair.
(4) Remove the rod from the fixed hair, wash the hair, shampoo and dry.

In addition, as an oxidizing agent used by (3), about 3-8 mass% aqueous solution of sodium bromate generally used, and dilution liquids, such as hydrogen peroxide and sodium perborate, can be used.
According to the present invention, since the permanent wave processing agent described above is used, there is little influence on the skin, sensitization is weak, wave efficiency is excellent, and unpleasant odor is improved. So it is rich in workability.

In addition, the hair treatment agent containing the cyclic mercapto compound of the present invention may be referred to as a first liquid, and the composition containing an oxidizing agent may be referred to as a second liquid.
[Example]
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[Synthesis Example 1]
Preparation of 2-mercapto-4-butyrolactone 70% sodium hydrosulfide (49 g, 0.6 mmol, manufactured by Junsei Chemical Co., Ltd.), methyl alcohol (500 g, Junsei Chemical Co., Ltd., special grade) and purified water (ion exchange filter after distillation) Water, 500 g). The dissolved liquid was cooled to 10 ° C. or lower under ice cooling while stirring. To the cooled solution, 2-bromo-4-butyrolactone (100 g, 0.6 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over about 30 minutes. After the completion of the dropwise addition, the liquid was stirred for 10 minutes, and then the reaction liquid was concentrated to about half volume under reduced pressure. To the concentrated liquid, ethyl acetate (500 mL, manufactured by Junsei Chemical Co., Ltd., special grade) was added for extraction. The resulting aqueous phase was re-extracted with ethyl acetate (500 mL). These extracted organic phases were combined, concentrated under reduced pressure, and purified by distillation to obtain 2-mercapto-4-butyrolactone (23 g, bp. 94 ° C./0.3 kPa, yield 32%).
[Synthesis Example 2]
Preparation of 2-mercapto-4-methyl-4-butyrolactone 2-mercapto-4- according to Synthesis Example 1 except that 2-bromo-4-methyl-4-butyrolactone (97 g, 0.5 mol, Aldrich) was used. Methyl-4-butyrolactone (18 g, bp. 73 ° C./0.4 kPa, yield 25%) was synthesized.
[Synthesis Example 3]
Production of 2-mercapto-4-butyrothiolactone (1) Production of 2-bromo-4-butyrothiolactone 4-Butyrothiolactone (10 g, 0.098 mol, Aldrich) was dissolved in ethyl acetate (90 g, genuine Dissolved in Chemical Co., Ltd.) and heated to 63 ° C. Bromine (18 g, 0.11 mol, manufactured by Junsei Chemical Co., Ltd.) was added dropwise from the dropping funnel in 15 minutes. After completion of dropping, the reaction solution was stirred at 63 ° C. for 24 hours.

The reaction solution after the reaction was cooled to room temperature, water (50 g) was added little by little, and the mixture was stirred for 10 minutes. Furthermore, 100 g of ethyl acetate was added and extracted.
The aqueous phase obtained by separation of the organic phase was re-extracted with ethyl acetate (100 mL). These extracted organic phases are combined, dried over anhydrous sodium sulfate (manufactured by Junsei Chemical Co., Ltd.), and the organic phase from which sodium sulfate has been removed by filtration is concentrated and distilled under reduced pressure to give 2-bromo-4- Butyrothiolactone (7 g, bp. 62 ° C./0.2 kPa, yield 37%) was obtained.
(2) Production of 2-mercapto-4-butyrothiolactone The above 2-bromo-4-butyrothiolactone (7 g, 0.037 mol) was used and reacted according to Synthesis Example 1. The liquid after the reaction was purified by distillation to synthesize 2-mercapto-4-butyrothiolactone (2.2 g, bp. 62 ° C./0.2 kPa, yield 45%).
[Examples 1-3] [Comparative Examples 1-2]
Using the following permanent wave first liquid containing 2-mercapto-4-butyrolactone and the following second permanent wave liquid, the permanent wave treatment was performed to determine the wave efficiency.
Preparation of the first liquid for permanent wave Propylene glycol, polyoxyethylene (20) cetyl ether, sodium dihydrogen phosphate, disodium hydrogen phosphate, 2-mercapto-4-butyrolactone, cysteamine in a 100 mL polyethylene container according to Table 1 Add 50 g of hydrochloride and purified water (water passed through an ion exchange filter after distillation), mix well, gradually add monoethanolamine and purified water to adjust the pH to 100 g, and adjust to the first liquid for permanent wave. did. The contents of 2-mercapto-4-butyrolactone and cysteamine hydrochloride in the drug thus obtained correspond to 2% in terms of thioglycolic acid reducing power. (Comparative Examples 1, 3, 5, 7, 9, 11, and 12 do not contain cysteamine hydrochloride. Comparative Examples 2, 4, 6, 8, 10, 13, and 14 are cyclic mercaptos of formula (1). Does not contain compounds)
Preparation of second liquid for permanent wave 5 g of sodium bromate and 95% of purified water were mixed to obtain a second liquid for permanent wave.
The permanent wave processing wave efficiency was evaluated by the Kilby method according to the method described in the special issue of fragrance journal (1984, No. 5, page 442).

  First, Chinese hair (about 20 cm in length) was fixed to a Kilby instrument. The hair fixed in the following permanent wave first liquid heated to 40 ° C. was soaked for 20 minutes. After the treatment, the hair taken out from the first liquid was wiped lightly to such an extent that the liquid did not drip. The hair was moistened with the second liquid for permanent wave made of bromate and allowed to stand at 25 ° C. for 10 minutes. After the above-described treatment with the second liquid was completed, the hair was washed with running water, the hair was removed from the kilbies, and the hair was dried. The dry hair thus obtained was measured, and the wave efficiency was calculated by the following wave efficiency calculation formula.

Wave efficiency (%) = 100− [100 × (B−A)] ÷ (C−A)
A: Distance between the first and sixth rods of the Kilby device (actual measurement of the center point of the rods)
B: Length of 6 piles of curled hair
C: Length of six piles when curled hair is straightened
The unit of A, B, and C is cm
The results are shown in Table 1.

[Examples 4 to 6] [Comparative Examples 3 to 4]
According to Table 2, the permanent wave treatment was performed in the same manner as in Example 1 except that the pH was adjusted to 7.5. The results are shown in Table 2.

[Examples 7 to 9] [Comparative Examples 5 to 6]
According to Table 3, the contents of 2-mercapto-4-butyrolactone and cysteamine hydrochloride in the first liquid for permanent wave were adjusted to a thioglycolic acid reducing power equivalent to 6% and adjusted to pH 5 as in Example 1. Permanent wave treatment was performed. The results are shown in Table 3.

[Examples 10 to 12] [Comparative Examples 7 to 8]
According to Table 4, 2-mercapto-4-methyl instead of 2-mercapto-4-butyrolactone
A permanent wave treatment was performed in the same manner as in Example 1 except that 4-butyrolactone was used and the pH was adjusted to 5.5. The contents of 2-mercapto-4-methyl-4-butyrolactone and cysteamine hydrochloride in the first liquid for permanent wave correspond to 2% in terms of thioglycolic acid reducing power. The results are shown in Table 4.

[Examples 13 to 15] [Comparative Examples 9 to 10]
According to Table 5, permanent wave treatment was performed in the same manner as in Example 1 except that 2-mercapto-4-butyrothiolactone was used instead of 2-mercapto-4-butyrolactone and the pH was adjusted to 5.5. The contents of 2-mercapto-4-butyrothiolactone and cysteamine hydrochloride in the first liquid for permanent wave correspond to 2% in terms of thioglycolic acid reducing power. The results are shown in Table 5.

[Example 16] [Comparative Examples 11 to 14]
According to Table 6, instead of 2-mercapto-4-butyrolactone, 2-mercapto-4-methyl-
A permanent wave treatment was performed in the same manner as in Example 1 except that ammonium thioglycolate was used in place of 4-butyrolactone and cysteamine hydrochloride and the pH was adjusted to 7. The contents of 2-mercapto-4-methyl-4-butyrolactone and ammonium thioglycolate in the first liquid for permanent wave correspond to 2% in terms of thioglycolic acid reducing power. The results are shown in Table 6.

FIG. 1 is a graph showing changes in wave efficiency due to pH when the compounds (i) and (ii) are used alone.

Claims (12)

(i) at least one compound represented by the following formula (1);

(X represents a structure of any of —O—, —S—, —NH—, and —NR ¹ —. R ¹ represents an alkyl group having 1 to 6 carbon atoms. R ² represents a hydrogen atom or 1 carbon atom. And Y represents an oxygen atom or a sulfur atom, and R represents a divalent organic residue which may have a mercapto group.
(ii) A hair treatment agent comprising thioglycolic acid, thiolactic acid, cysteine, cysteamine, and at least one compound selected from the group consisting of salts, ester derivatives or amide derivatives thereof. The hair according to claim 1, wherein the content of the compound (ii) is such that (ii) / (i + ii) is 0.01 to 50% by mass relative to the total amount of the compounds (i) and (ii). Processing agent. The hair treatment agent according to claim 1 or 2, wherein the pH of the hair treatment agent is in the range of 3 to 8. The hair treatment agent according to claim 1, wherein the compound (ii) is cysteamine, a salt thereof, or an ester derivative thereof. The X in the formula (1) is “—O—”, “—NH—”, “—NCH ₃ —” or “—S—”, according to claim 1. Hair treatment agent. The hair treatment agent according to claim 1, wherein Y in the formula (1) is an oxygen atom. R of formula (1) is an alkylene group, The hair treatment agent in any one of Claims 1-6 characterized by the above-mentioned. The hair treatment agent according to any one of claims 1 to 7, wherein R in the formula (1) is an alkylene group having one or more mercapto groups. The compound represented by the formula (1) is
2-mercapto-4-butyrolactone, 2-mercapto-4-methyl-4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone and 2-mercapto-6-hexa The hair treatment agent according to any one of claims 1 to 8, wherein the hair treatment agent is at least one selected from the group consisting of noractam. The content (total amount) of the compounds (i) and (ii) is 0.2 to 30% in terms of the content of reducing substances (as thioglycolic acid). The hair treatment agent according to any one of the above. The hair treatment agent according to any one of claims 1 to 10, wherein the hair treatment agent is a permanent waving agent. A method for permanent waving hair, wherein the hair treatment agent according to claim 11 is used.

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