JPH0322846B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel hair treatment agent. [Prior Art and its Problems] A permanent wave method that transforms hair is known as one of the methods for semi-permanently modifying or treating hair. The most common method for giving hair a desired wave is to first use a permanent wave dye containing a reducing agent such as thioglycolic acid or cysteine as the main ingredient.
The liquid is used to reduce and open the SS bonds in the hair to release the amino acid side chains, facilitating the formation of waves, and then using oxidizing agents such as bromate, perborate, and hydrogen peroxide as the main ingredients. This is a permanent wave method in which the waves are fixed by oxidizing and closing the bonds with a second liquid for permanent waves. The most commonly used reducing agent in the first liquid for permanent waves is thioglycolic acid, but this has a bad odor, causes discomfort to the user, is highly irritating, and is also harmful to the hair. The drawback was that it caused a lot of damage. In addition, a first solution using cysteine as a main ingredient instead of thioglycolic acid has been developed and is now in practical use. However, although this has an improved odor compared to thioglycolic acid, it has a weak reducing power and cannot provide sufficient waves, and cysteine is easily oxidized in the air to produce water-insoluble cysteine, which can cause hair damage. There were problems such as adhesion to the skin, impairing the appearance and feel, and causing skin irritation. On the other hand, other methods for semi-permanently modifying or treating hair have not been used other than changing hair color using permanent hair dyes or bleaching agents using oxidative dye precursors. In particular, attempts have been made to improve the feel, moisturizing properties, luster, luster, etc. of damaged hair using oils and polypeptides added to treatments, conditioners, etc. All of these had shortcomings, such as having only temporary effects that washed away with shampoo or washing with water, and that the effects did not last unless they were used repeatedly. [Means for Solving the Problems] Under such circumstances, the present inventor conducted intensive research and found that the following general formula (), R-CONH-(CH ₂ )n-SH () (in the formula, R is an andric acid or uronic acid residue,
The present invention was completed based on the discovery that N-mercaptoalkyl sugar amide represented by (n represents a number from 1 to 3) is less irritating, has a good odor, and has excellent hair deforming and modifying effects. . That is, the present invention provides a hair treatment agent containing N-mercaptoalkyl sugar amide () as a main component. The N-mercaptoalkyl sugar amide () of the present invention is produced, for example, by reacting a sugar lactone compound with an aminoalkanethiol. Examples of sugar lactone compounds include those obtained by intramolecular dehydration and cyclization of aldonic acids or uronic acids, such as D-glucose, D-galactose, D-allose, D-altrose, and D-mannose. , D-Growth, D
- Lactones of aldonic acids derived from reducing monosaccharides such as idose and D-talose; lactones of aldonic acids derived from reducing disaccharides such as maltose, cellobiose, lactose, xylobiose, isomaltose, nigerose, cordibiose; Lactones of aldonic acids derived from reducing trisaccharides such as ose, panose, and isomaltotriose; lactones derived from reducing oligosaccharides of tetrasaccharide or higher and urons such as D-glucuronic acid, L-iduronic acid, and mannuronic acid. Examples include acid lactones. These can be used alone or as a mixture. The reaction is carried out by mixing or suspending a sugar lactone compound and an aminoalkanethiol, preferably in a solvent,
This is carried out by heating under reflux with stirring, or by first dissolving the aminoalkanethiol in a solvent and then adding the sugar lactone compound little by little to the reaction system. As the solvent, polar solvents are preferred, and lower alcohols such as methanol, ethanol, n-propanol, and iso-propanol are particularly preferred. Aminoalkanethiol can be added to the reaction system as it is, but
It may be produced in a reaction system by reacting the carboxylate or mineral acid salt with a tertiary amine such as triethylamine. Note that the presence of water in the reaction system is undesirable because it decomposes the sugar lactone compound and produces the corresponding acid, and it is desirable to remove water from the reaction system and use a dry solvent. After the reaction, the produced N-mercaptoalkyl sugar amide has low solubility in alcohols, so it can be crystallized and decomposed by removing a portion of the solvent from the reaction mixture and cooling. Among the N-mercaptoalkyl sugar amides thus obtained, N-mercaptoalkylgluconamide is particularly preferred. The hair modification agent of the present invention can be in the form of a first solution of a cold two-bath permanent waving agent, a heated one-bath permanent waving agent, or an intermediate treatment agent exclusively for cold perms. The two-bath type first liquid treatment agent is prepared by dissolving N-mercaptoalkyl sugar amide in water to a concentration of 1 to 20%, preferably 2 to 10%, and using a buffer to dissolve the N-mercaptoalkyl sugar amide at pH 4 to 4.
11, preferably by adjusting the pH to 7-9. In addition, the single-bath treatment agent contains 0.1 to 5.0% of N-mercaptoalkyl sugar amide, preferably
It is produced by dissolving it in water to a concentration of 0.5 to 3.0% and adjusting the pH to 6 to 10, preferably 7 to 9, using a buffer. In addition, an intermediate treatment agent exclusively for cold perm is prepared by dissolving N-mercaptoalkyl sugar amide in water to a concentration of 1 to 20%, preferably 2 to 10%, and adjusting the pH to 2 to 7, preferably 3 to 6. It is made by Buffers used in cold two-bath or heated permanent wave agents include, for example, citric acid/disodium hydrogen phosphate, hydrochloric acid/sodium barbital/sodium acetate, hydrochloric acid or maleic acid/trishydroxyaminomethane, phosphoric acid. Potassium or sodium dihydrogen/dipotassium or sodium hydrogen phosphate, hydrochloric acid or potassium or sodium dihydrogen phosphate/sodium tetraborate, potassium or sodium dihydrogen phosphate/sodium or potassium hydroxide, hydrochloric acid/collidine, boric acid/
Sodium carbonate or sodium tetraborate, hydrochloric acid/
Aminomethylpropanediol, glycine/sodium or potassium hydroxide, boric acid/sodium hydroxide, hydrochloric acid/sodium dimethylglycine, sodium bicarbonate/sodium carbonate, sodium tetraborate/sodium hydroxide, sodium bicarbonate/sodium hydroxide or Examples include water-soluble ammonium salt/ammonia combinations. Among these, combinations of water-soluble ammonium salts/ammonia, combinations of water-soluble ammonium salts/basic amino acids such as arginine, lysine, etc. are considered to be less likely to leave alkaline agents in the hair, skin, etc. and cause less hair damage or skin irritation. is preferred, and as the water-soluble ammonium salt, hydrochloride, carbonate, and bicarbonate are preferred. Buffers used in intermediate processing agents exclusively for cold perms include glycine/hydrochloric acid, potassium hydrogen phthalate/hydrochloric acid, citric acid/sodium citrate, acetic acid/sodium acetate, succinic acid, fumaric acid, tartaric acid, and maleic acid. Examples include combinations of organic acids such as acids and potassium hydroxide. These buffering agents are incorporated in the processing agent of the present invention in a total amount of 0.05 to 10%, preferably 0.1 to 5%. The hair treatment agent of the present invention contains the following (i) peptides or derivatives thereof, (ii) divalent metal salts, (iii) cationic or amphoteric polymers, etc., for the purpose of improving wave-forming effects and preventing hair damage. It is preferable to use one type or a combination of two or more types. (i) Peptides or derivatives thereof Dimeric or higher peptides synthesized from one or two basic amino acids (e.g. lysine, arginine), or one or two acidic amino acids (e.g. glutamic acid, aspartic acid) Synthesized dimer or higher peptides; keratin proteins of wool, feathers, hooves, horns, etc., JP-A-57-88111
Hydrolyzed cationized products of keratin, albumin, globulin, conglycinin, casein proteins or decomposed derivatives of soybean protein, etc., as described in JP-A-57-85308; or physiologically active peptides such as insulin, oxidized glutathione, etc. Among these, polylysine with a molecular weight of 10,000 or less, preferably 5,000 or less; hydrolysates of keratin protein, soybean protein, etc.; and insulin are particularly preferred. These peptides or their derivatives may be used alone or in combination of 0.01 to 50% in the hair deforming treatment agent.
Weight% (hereinafter simply expressed as %), preferably 0.1~
Contains 10%. (ii) Divalent metal salt The following general formula AB ₂ /m (wherein A is Ba ²⁺ , Ca ²⁺ , Zn ²⁺ , Ni ²⁺ and
B is a cation selected from the group consisting of Mg ²⁺ .
F ^- , Cl ^- , Br ^- , I ^- , SO ² ₄ ^- , PO ³ ₄ ^- , OH ^- and CO ² ₃
^- represents an anion selected from the group consisting of (m represents the valence of B), or acetate, citrate, lactate, succinic acid of the above divalent metal (A) Examples include organic acid salts such as salts and tartrates, and particularly preferred are acetates or chlorides of calcium, zinc, nickel, magnesium, and barium. These divalent metal salts can be used alone or in combination of two or more, and in the final use form, 10
It is blended at ~5000ppm, preferably 100~1000ppm. (iii) Cationic or amphoteric polymers The following polymers are water-soluble or water-soluble in the presence of inorganic or organic salts as described in JP-A-56-92812. Copolymer of acidic vinyl monomer and basic vinyl monomer Typically, 45 to 55 mol% of acidic vinyl monomer or its salt, 45 to 55 mol% of basic vinyl monomer or its salt Examples include amphoteric copolymers obtained by copolymerizing a monomer mixture consisting of can. The molar ratio referred to here refers to the case where each vinyl monomer has one acidic group or basic group in one molecule, and the molar ratio refers to the case where each vinyl monomer has one acidic group or basic group in one molecule. In this case, the molar ratio is appropriately adjusted so that the net charge is approximately 0. Acidic vinyl monomers have acidic groups such as carboxyl groups, sulfonic acid groups, and phosphoric acid groups in one molecule,
A compound having a polymerizable vinyl group, such as acrylic acid, methacrylic acid, crotonic acid,
Vinylbenzoic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 3-methacrylpropanesulfonic acid,
and unsaturated dibasic acids such as itaconic acid, maleic acid, and fumaric acid, and monoesters thereof. In addition, examples of the salts include sodium salts, potassium salts, ammonium salts, and the like. A basic vinyl monomer is a compound having a basic group such as a primary amino group, a secondary amino group, or a tertiary amino group and a polymerizable vinyl group in one molecule, such as dimethyl Aminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylamide, dimethylaminopropylacrylamide, 2-vinylpyridine, 4-vinylpyridine,
Dimethylallylamine, diallylmethylamine, etc. and quaternized products thereof can be mentioned. Examples of quaternized products include hydrides, methylated products, ethylated products, and compounds whose counter anions are halogen ions such as chloride ions and bromine ions, hydroxyl ions, and methyl sulfate groups. Polymers of amphoteric monomers Typically, an amphoteric monomer represented by the general formula () is reacted with 20
Examples include amphoteric polymers obtained by polymerization in a temperature range of ~120°C. (In formula (), R ₄ , R ₇ and R ₈ are hydrogen atoms or methyl groups, R ₅ and R ₆ are methyl groups or ethyl groups,
A is -O- or -NH-, X is _-CO2 , _-SO3 or _-PHO3 , and m and n are integers of 1 to 3. ) The amphoteric monomer represented by the general formula () can be synthesized by reacting a suitable aminoalkyl ester or aminoalkyl amide of acrylic acid or methacrylic acid with a lactone, sultone or cyclic phosphite. Examples of these compounds include 3-dimethyl(methacroyloxyethyl)ammonium propanesulfonate and 3-dimethyl(methacroylamidopropyl)ammonium propanesulfonate. The polymerization reaction can be carried out by conventionally known methods, such as bulk polymerization, aqueous solution polymerization, reversed-phase suspension polymerization, and precipitation polymerization, at a reaction temperature of 20 to
The polymerization is carried out smoothly at 150°C in the presence of a radical polymerization initiator. As a radical polymerization initiator, sodium persulfate, potassium persulfate, ammonium persulfate, 2,
2'-azobis(2-amidinopropane) dihydrochloride, benzoyl peroxide, hydrogen peroxide, sodium peracetate, cumene hydroperoxide, azobisisobutylnitrile, and the like are used. The amount of the radical polymerization initiator to be used varies depending on its type, but is generally preferably about 0.01 to 5% by weight based on the total monomers.
These cationic or amphoteric polymers may be used alone or in combination of 0.01~
20% by weight (hereinafter simply expressed as %), preferably 0.1~
Contains 10%. Furthermore, other conventionally known ingredients may be added to the hair treatment agent of the present invention within a range that does not impede the effects of the present invention. Examples of other components include higher alcohols, cationic, anionic, and amphoteric surfactants, silicones, aluminum compounds such as aluminum stearate, and alum, organic acids such as citric acid and malic acid, and inorganic acids such as hydrochloric acid. acids, basic amino acids such as ethylenediamine, mono-, di- or tri-ethanolamine, morpholine, arginine, lysine, glutamic acid,
Acidic amino acids such as aspartic acid, ammonia,
Examples include alkaline agents such as caustic soda, hair nourishing agents, bactericidal agents, coloring agents, fragrances, and the like. When the hair treatment agent of the present invention is used as the first liquid of a cold two-bath permanent waving agent, it is carried out in a conventional manner using a commonly used second liquid. When used as a heated one-bath permanent waving agent, the following method is used. That is, first, a treatment agent is applied to the hair. Before applying the treatment agent to the hair,
It is preferable to form the desired waves by wrapping them around a rod, curler, heatable hand-held setting device, etc. However, if you want gentle waves, use a hair dryer or brush to create the desired waves. Customization can be done by finishing method. The amount of application varies depending on conditions such as heating temperature, but it is usually preferably 10 to 150 ml per application. The hair is then heated to 40-160°C. The heating temperature and time will vary depending on the degree of hair damage, the type of peptide used, the type of buffer, the pH, and the formulation of the treatment agent. For this reason, treatment at high temperatures is advantageous, but in consideration of damage to the hair due to heating, temperatures between 40 and 160°C, particularly between 40 and 80°C, are preferred. Furthermore, it is effective to cover the hair with a cap and further humidify it to prevent moisture from evaporating from the hair during heating. As for the heating time, the lower the temperature, the longer the heating time is required, but for the same reason, the heating time is preferably 30 minutes or less, and preferably between 3 and 10 minutes. On the other hand, for chemically treated hair that has been permed, dyed, bleached, etc., it is desirable to select milder treatment conditions. Further, as for the intermediate treatment agent for cold perm, apply 10 to 100 ml of the first liquid of a conventional cold permanent waving agent and before treating with the second liquid. [Effects of the Invention] By using the hair treatment agent of the present invention, strong waves can be formed on the hair in a relatively low temperature and in a short time by simple operations. In addition, in particular, the heated single bath method does not use highly concentrated alkaline agents, reducing substances, or oxidizing substances, so it can reduce hair damage caused by elution of hair proteins, and is less irritating to the skin. It has the advantage of being good in storage stability and solving various handling problems of conventional permanent waving agents. [Example] Next, the present invention will be described with reference to synthesis examples and examples, but the present invention is not limited thereto. Synthesis Example 1 In a reaction flask equipped with a stirrer, thermometer and reflux condenser, 45.7 g of glucono-δ-lactone
(0.27mol), 2-aminoethanethiol 24.7g
(0.32mol) and methanol 400ml for 6 hours.
The mixture was stirred under reflux. The reaction mixture was ice-cooled, and the precipitated crystals were separated. The obtained crystals were recrystallized in ethanol to obtain 59.7 g of N-(2-mercaptoethyl) gluconamide. The analysis and identification results of this compound are as follows. Melting point: 135-136℃ Infrared absorption spectrum (KBr tablet method): The spectrum includes the HS stretching vibration at 2580 and 2540 cm ^-1 , the stretching vibration of the carbonyl group of the secondary amide at 1655 cm ^-1 (amide absorption band), and The NH bending vibration of the secondary amide (amide absorption band) is observed as a characteristic signal at 1540 cm ^-1 . Mass spectrometry spectrum (FD method): m/e=255 was detected. This signal is N
Corresponds to the signal of the parent ion of -(2-mercaptoethyl)gluconamide. Elemental analysis value: C ₃ H ₁₇ NO ₆ Calculated value (%) C37.64, H6.71, N5.49, S12.56 Analysis value (%) C37.56, H6.59, N5.55, S12 .31 Based on the above analytical results, this compound is identified as N-(2-mercaptoethyl)gluconamide. Synthesis Example 2 34.0 g of maltobionolactone in a reaction flask equipped with a stirrer, thermometer and reflux condenser.
(0.1mol), 2-aminoethanethiol 9.3g
(0.12mol) and methanol 200ml for 7 hours.
The mixture was stirred under reflux. The reaction mixture was dropped into 1 part of isopropyl alcohol, and the precipitate was separated. The obtained product was dissolved in a small amount of methanol and dropped into 1 part of isopropyl alcohol again to separate the precipitate, and N-(2-mercaptoethyl)
24.1 g of maltobionamide was obtained. The analysis results of this compound were as follows. Melting point: 92-97℃ Infrared absorption spectrum (KBr tablet method): The spectrum includes the stretching vibration of the carbonyl group of the secondary amide (amide absorption band) at 1650 cm ^-1 and 1540 cm -1
The NH bending vibration of the secondary amide (amide absorption band) is observed as a characteristic signal at cm ^-1 . Mass spectrometry spectrum (FD method): m/e=418 was detected. This signal is N-
Corresponds to the signal of the parent ion of (2-mercaptoethyl)maltobionamide. Synthesis Example 3 25.0 g of glucuronic acid lactone in a reaction flask equipped with a stirrer, thermometer and reflux condenser.
(0.14mol), 2-aminoethanethiol 10.8g
(0.14mol) and methanol 200ml for 2 hours.
The mixture was stirred under reflux. The reaction mixture was dropped into acetone 2 and the precipitate was separated to remove N.
- 35.0g mercaptoethyl glucuronic acid amide
Obtained. In the infrared absorption spectrum of N-mercaptoethylglucuronic acid amide, absorptions characteristic of amide bonds were observed at 1650 and 1540 cm ^-1 . Example 1 A first solution of a cold two-bath permanent wave agent having the composition shown in Table 1 was prepared, and the stability of the solution, perming, odor, and feel of treated hair were evaluated. The results are shown in Table 2.

[Table] <Evaluation method> (1) Stability After adjustment, the solution was left sealed at room temperature for one week, and changes in the properties of the liquid compared to those immediately after production were observed. Evaluation criteria: 〇 Transparency × Precipitate formation (2) Perm effect Using samples immediately after production and samples that had been left for one week, healthy Japanese hair tresses wrapped around rods were immersed and left at 30°C for 10 minutes. After that, rinse with water, then soak in Cold Wave 2nd solution (5% sodium bromate, 95% water) at room temperature for 15 minutes, rinse with water, remove the hair from the rod, and evaluate the formation of waves with the naked eye. did. Evaluation criteria: ◎ Slightly strong 〇 Fair △ Slightly weak × Weak (3) Feel of treated hair The damage to the hair after the perm treatment in (2) was evaluated based on the difference in the feel of untreated hair. Evaluation criteria: Smoothness 〇 Same as untreated hair △ Slightly bad × Bad (4) Odor of perm agent and perm treatment The mercapto odor of the liquid immediately after production and the mercapto odor during the perm treatment process were evaluated. Evaluation criteria: 〇 None △ Slightly felt × Strongly felt

【table】

〔Measuring method〕

Wave degree and wave retention measurement test (i) Ten 15cm Japanese healthy hairs were made into a bundle, wrapped around a glass tube (diameter 10mm), and placed in each treatment agent.
The samples were immersed at 30°C, 50°C, and 80°C for 20 minutes each. After 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. The wave degree was calculated from the following formula. Wave degree (%) = Y / X - Y × 100 0.5% of sodium lauryl sulfate after 40℃
The sample was immersed in the aqueous solution for 1 minute and then gently moved for cleaning. This was then thoroughly rinsed and the length of the hair coil was measured again. The wave retention force was evaluated by the wave retention rate determined by the following formula. Wave retention rate (%) = Wave degree after hair washing / Wave degree immediately after treatment x 100

[Table] Example 3 The following heating one-bath permanent waving agent was prepared. Prescription example 1: A 2-mercaptoethylgluconamide
2.0 (%) B Keratin protein hydrolyzate (M.W630)
1.0 C Stearyltrimethylammonium chloride 1.0 D Polyoxyethylene lauryl ether (E.
O.23 mol) 1.0 E Ammonium bicarbonate 3.0 F Arginine Adjust to PH8.5 G Fragrance 0.2 H Ion exchange water Balance 100.0 Add A, B, E, and F to the nitrogen-substituted ion exchange water and stir to dissolve uniformly. After that, add a solution of G to C and D, and finally adjust the pH with F to manufacture. Prescription example 2: A 2-mercaptoethylgluconamide
1.5 (%) B Calcium chloride 1.0 C Cetyltrimethylammonium chloride 2.0 D Ammonium chloride 2.5 E Ammonia water (28%) PH9.0 F Fragrance 0.1 G Ion exchange water Balance 100.0 A, B, D in nitrogen-substituted ion exchange water After adding and stirring to uniformly dissolve, add a solution in which F is dissolved in C, and finally adjust the pH with E to produce. Formulation example 3: A 2-mercaptoethylgluconamide
2.0 (%) B Cationized cellulose [Commercial product name: Polymer JR400 (Union Carbide)] 0.5 C Stearyltrimethylammonium chloride 2.0 D Glycyl-glycine 3.5 E Lysine Adjusted to PH8.0 F Fragrance 0.1 G Ion exchange water Balance 100.0 Nitrogen A, B, and D are added to the substituted ion-exchanged water and stirred to uniformly dissolve, then a solution in which F is dissolved in C is added, and finally the pH is adjusted with E to produce. All of Formulation Examples 1 to 3 have superior wave-forming effects and feel better after treatment compared to formulations containing only a reducing agent. Example 4 Using an intermediate treatment agent exclusively for cold perm with the following composition,
Hair was treated between the first agent and the second agent containing sodium bromate as the main ingredient, and 10 hairdressers evaluated the feel of the hair after perming and shampooing. As a control, ion-exchanged water and a buffer solution obtained by removing 2-mercaptoethylgluconamide from the intermediate treatment agent were used instead of the intermediate treatment agent. The results are shown in Table 4. Composition: 2-Mercaptoethylgluconamide 5.0 (%) Lauryltrimethylammonium chloride 1.0 Citric acid 3.0 Sodium hydroxide Ion exchange water adjusted to PH3.0 Balance 100.0 Chemicals used: (1) Cold Wave 1st agent thioglycolic acid ammonium salt 7.0 (%) Water, ammonia water (for PH adjustment) 93.0 (PH adjusted to 9.0 with ammonia water) (2) Cold wave second agent Sodium bromate 5.0 (%) Water 95.0 Treatment conditions: First agent at 30℃ After immersing the hair tresses in the solution for 10 minutes, immersing them in an intermediate treatment agent at 30℃ for 10 seconds, and then immersing them in the intermediate treatment agent at 30℃.
The sample was immersed in the second agent for 10 minutes, washed with water, and then dried.
Furthermore, it was shampooed and dried. Evaluation criteria: Good 2 points Slightly good 1 point No change 0 points Slightly bad -1 point Bad -2 points

【table】

Claims (1)

[Claims] 1. General formula R-CONH-(CH ₂ )n-SH (wherein R represents an aldonic acid or uronic acid residue,
(n represents a number from 1 to 3) A hair treatment agent containing an N-mercaptoalkyl sugar amide as a main component.