JPH0160448B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention provides a permanent wave second agent composition,
More specifically, the present invention relates to a permanent wave second agent composition that suppresses hair deterioration caused by permanent wave treatment, imparts good texture to the hair, and has excellent permanent wave retention properties. [Prior art and its problems] The permanent wave method for imparting desired waves to hair uses a permanent wave first agent (hereinafter referred to as "first agent") whose main ingredients are reducing agents such as thioglycolic acid and cysteine. ) to open the S-S bonds in the hair, and then bromate,
Permanent wave second agent (hereinafter referred to as “second agent”) whose main component is an oxidizing agent such as perborate or hydrogen peroxide
This is a method of oxidative closure with However, with this method, the hair is exposed to adverse conditions such as oxidation and reduction, which causes phenomena such as a decrease in the strength of the hair and deterioration of the texture. When brushing, the brush or comb does not go through well, causing snags, etc.
The hair is damaged by peeling off the epidermis, split ends, and cut hair. Hair deterioration phenomena occur at each stage of permanent wave processing. That is, since the first agent is mainly composed of a reducing agent and an alkaline agent, the hair is swollen by these agents, the keratin protein in the hair is destroyed, and the protein and amino acids are eluted into the treatment solution. This swollen hair is then damaged by an oxidizing agent in treatment with a second agent. However, this phenomenon caused by the first agent is unavoidable because it reduces and opens the S--S bonds in the hair. Therefore, in order to prevent hair deterioration due to permanent wave treatment, the second agent is
It is important to minimize oxidative damage to the agent. Conventionally, a method for preventing hair damage caused by the second agent has been to incorporate an oil agent, a humectant, etc. into the composition, but this method has not yet been satisfactory. [Means for Solving the Problems] As a result of various studies on reducing hair damage caused by permanent waving agents, especially second agents, the present inventors found that a specific keratin material decomposed in the base of the second agent. By incorporating the derivative, a second part composition can be obtained which suppresses hair deterioration due to elution of proteins and amino acids, imparts a preferable feel to the hair, and has an excellent wave retention effect compared to conventional second part compositions. The present invention was completed based on this discovery. That is, the present invention provides a second agent in which one or more decomposed derivatives of keratin substances selected from the group consisting of oxidative decomposition products of keratin substances and derivatives in thiol groups of reductive decomposition products of keratin substances are blended into the second agent base. A two-drug composition is provided. The decomposed derivatives of keratin substances of the present invention can be obtained either by oxidatively decomposing the keratin substance and converting it into an alkali salt if necessary; Manufactured by any of the following methods: Examples of the keratin material used as a raw material include animal hair, hair, feathers, nails, horns, hooves, scales, etc. Among them, wool, hair, and feathers are particularly preferred. These keratin materials can be subjected to oxidation or reduction reactions as they are, but if necessary, they may be cut or crushed into appropriate sizes, or pretreated such as washing and degreasing. Decomposition of keratin substances is carried out by one of the following methods. (1) Oxidation reaction Keratin materials are oxidized by various methods known per se [NHLeon; Textile Progress, Vol. 7, p. 1 (1975)]. As an oxidizing agent, the disulfide bond (SS bond) in the keratin structure
Preference is given to organic or inorganic oxidizing agents of the type that act electrophilically to Among them, organic peracids such as peracetic acid, performic acid, and perbenzoic acid are particularly preferred. The oxidation reaction is carried out in a liquid medium using an oxidizing agent in an excess amount relative to the disulfide bonds in the keratin material, usually at least 2 equivalents, preferably 4 to 10 equivalents per disulfide bond. The reaction can be carried out in either acidic or alkaline conditions, but
It is preferable to carry out under acidic, especially weakly acidic conditions. Conditions such as reaction temperature and pressure vary depending on the oxidizing agent used, the type of keratin material, etc., and are not particularly limited. Room temperature is generally sufficient, but heating can be used if necessary. Also, normal pressure is sufficient, but it may also be carried out under reduced pressure or increased pressure. In doing so, the disulfide bonds of the keratin material are cleaved to produce sulfonic acid (-SO ₃ H). (2) Reductive decomposition and chemical modification reactions Reducing agents used to reduce keratin materials are those that cleave the disulfide bonds in the structure to give thiol groups (-SH), and are generally used to reduce the disulfide bonds. Organic or inorganic reducing agents of the type that act nucleophilically are preferred. Specifically, organic reducing agents such as mercaptoethanol, thioglycolic acid, benzyl mercaptan, 1,4-dithiothreitol, and tributylphosphine; sulfides such as sodium bisulfite and sodium hydrosulfide; and lithium aluminum hydride, etc. Examples include inorganic reducing agents such as metal hydrides. The amount of reducing agent used is generally 2 to 10 times equivalent to the disulfide bonds in the keratin material. The pH of the reaction system is preferably in the range of 2 to 12, particularly 6 to 11; anything outside of this range is not preferred since hydrolysis may also occur. Room temperature is sufficient for the reaction temperature, but the reaction time can also be shortened by heating.
The reaction time usually requires 2 to 3 hours or more. It is also necessary that the thiol groups produced by this reduction are not substantially oxidized, and therefore good results are obtained if the operation is carried out in an inert gas atmosphere. The thus obtained reductive decomposition product of the keratin substance is converted into a derivative by chemically modifying its thiol group (hereinafter referred to as a "reduced derivative of the keratin substance").
shall be. Examples of the derivatives of the thiol group include the following. −SCH ₂ COOH, −SCH ₂ CH ₂ COOH,

【formula】

【formula】

[Formula] −SO ₃ H, −SSO ₃ H, − SCH ₂ CH ₂ SO ₃ H,

【formula】

[Formula] − SCH ₂ CH ₂ SO ₂ CH ₂ COOH In this, −
SCH ₂ COOH,

[Formula] is particularly preferred. The chemical modification method of thiol group is carried out by means known per se,
For example, NHLeon;Textile Progress, Volume 7,
1 page (1975), "Organic Sulfur Compounds" by Shigeru Oki, published by Kagaku Dojin (1968), and "Polymer Experimental Course" by Masami Oku, vol. 12, Kyoritsu Shuppan (1957). Typical methods include the following. Method using nucleophilic substitution reaction of SH group K-SH+R-L→K-S-R+HL (In the formula, K is a keratin compound residue, R is a chemical modification group to be introduced, L is a halogen atom, an acid Examples of compounds reacted by this method include halogenated compounds such as iodoacetic acid, bromoacetic acid, and chloroacetic acid. Method using nucleophilic addition reaction to carbon-carbon double bond of SH group (In the formula, at least one of R ₁ , R ₂ , R ₃ and R ₄ represents a group having a carboxyl group or a sulfonic acid group therein, and the remainder represents an alkyl group or a hydrogen atom. K is as defined above. Compounds reacted by this method include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, vinylcarboxymethylsulfonic acid, vinylsulfonic acid, styrenesulfonic acid, 2-acrylamide-2- Examples include methylpropanesulfonic acid. Method using substitution reaction between SH group and sulfite compound K-SH+NaHSO ₃ →K-S-SO ₃ H K-SH+Na ₂ SO ₃ ---→ Air K-S-SO ₃ H (wherein K is Method of oxidizing SH group to sulfonic acid group K-SH ---→ oxidation K-SO ₃ H (in the formula, K has the above-mentioned meaning) As the oxidizing agent used in this reaction, for example, Mention may be made of halogens and permanganates. Although these keratin substance decomposition derivatives can be blended as they are in the second agent, good results are obtained when they are blended in the form of an alkali salt or in combination with an anionic surfactant or an amphoteric surfactant. Examples of the alkali salts of oxidative decomposition products of keratin substances and reduced derivatives of keratin substances include salts of inorganic alkali metals such as sodium and potassium, ammonium salts, ethanolamine, diethanolamine, triethanolamine, 2-amino-2-
Examples include salts with organic bases such as methylpropanol, aminomercaptopropanediol, triisopropanolamine, glycine, histidine, and arginine. Although these can be prepared in a separate system and blended into the second agent base, the oxidative decomposition product of the keratin substance or the reduced derivative of the keratin substance and the alkaline substance can be blended into the second agent base and added to the second agent base. It can also be used to make salt. Examples of the alkaline substances in this case include inorganic alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate, as well as ammonia, ethanolamine, diethanolamine, triethanolamine, 2-
Examples include amino-2-methylpropanol, aminomethylmercaptopropanediol, triisopropanolamine, glycine, arginine, histidine, etc., which are effective against carboxyl groups and sulfonic acid groups in oxidative decomposition products of keratin substances or reduced derivatives of keratin substances. It is preferable to add and blend in an amount of 0.1 to 8 equivalents. Examples of anionic surfactants used in combination with keratin substance decomposition derivatives include the following. (1) Straight-chain or branched-chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 10 to 16. (2) A polyoxyalkylene alkyl ether sulfate salt having a linear or branched alkyl group having an average of 8 to 20 carbon atoms and having an average of 0.5 to 8 moles of ethylene oxide and/or propylene oxide added to each molecule. (3) An alkyl sulfate ester salt having a linear or branched alkyl group having an average carbon number of 10 to 20. (4) Olefin sulfonate having an average of 10 to 20 carbon atoms in one molecule. (5) Alkanesulfonate having an average of 10 to 20 carbon atoms in one molecule. (6) An alkyl ethoxycarboxylate having a linear or branched alkyl group having an average carbon number of 10 to 20 and an average of 0.5 to 8 moles of ethylene oxide added to each molecule. (7) The following formula, (In the formula, R ₅ represents an alkyl group or alkenyl group having 6 to 20 carbon atoms, and X ₁ and X ₂ each represent a counter ion or a hydrogen atom.) A succinic acid derivative represented by the following formula. (8) A fatty acid salt having a linear or branched saturated or unsaturated hydrocarbon chain with an average carbon number of 10 to 20. (9) The following formula, [In the formula, A is

[Formula] or

〔Example〕

Next, the present invention will be described with reference to reference examples and examples. Reference Example 1 Synthesis of oxidatively decomposed derivatives of keratin substances: (a) 10 g of wool fiber was immersed in 700 g of an 8% aqueous peracetic acid solution at room temperature for one day to carry out an oxidation reaction. The obtained oxidized wool is filtered, washed with water,
When immersed in 700 g of 0.1N ammonia water at room temperature for one day, about 90% of the wool was solubilized in the ammonia water. Approximately 1 g of insoluble portion was removed by filtration, and 2N hydrochloric acid was added to the ammonia aqueous solution of keratose, which is an oxidative decomposition product of wool keratin, to pH 4.0.
Then, α-keratose precipitated out. This was filtered, washed with acetone, and dried to obtain 5.4 g of α-keratose. (b) The wool fibers were heated under pressure in a high-pressure container with 6 kg/cm ² of saturated steam for 6 minutes, and then rapidly released into the atmosphere to obtain a porous expanded product. 10 g of the crushed product, 250 g of formic acid, and 50 g of a 30% aqueous hydrogen peroxide solution were placed in a 500 ml three-necked flask and immersed for one day at room temperature. At this time, there was no powder form, and foam-like masses were floating in the upper layer. The reaction mixture was filtered, the liquid was poured into 1.5 liters of water, and the pH was adjusted to 4 with hydrochloric acid. Collect the precipitate and add water
After washing with 500 ml, 4.5 g of α-keratose was obtained.
Furthermore, add 350 ml of water to the insoluble part from which the reactant was removed,
The pH was adjusted to 11 with ammonia water and immersed for one day at room temperature. After this, add hydrochloric acid to the liquid part to make the pH 4.
The precipitate was collected and α-keratose
0.7g was obtained. The 1.4 g of insoluble portion was mainly β-keratose. Reference Example 2 Synthesis of reductively decomposed derivatives of keratin substances: (a) 10 g of wool fiber was immersed in 600 ml of an aqueous solution containing 8 M urea and 0.01 M Tris buffer, and after adding 6 ml of 2-mercaptoethanol as a reducing agent, The pH was adjusted to 10 with a 5N aqueous solution of potassium hydroxide, and the reduction reaction was carried out at room temperature under a nitrogen stream. After about 3 hours, the wool was about 85% solubilized in the reaction solution. Then, while adjusting the pH of the system with a 5N caustic potassium aqueous solution so that it does not fall below 7, 16.5 g of iodoacetic acid is added.
was gradually added, the pH of the system was finally adjusted to 8.5, and the carboxymethylation reaction was carried out at room temperature for 2 hours.
The reaction solution was filtered to remove insoluble portions, and the resulting solution was placed in a cellulose tube and dialyzed against ion-exchanged water to remove low-molecular impurities including urea. As urea is dialyzed,
Inside the cellulose tube is a water-insoluble component
HGT (component with high content of glycine and tyrosine) precipitates and becomes cloudy. After the dialysis, HGT was removed by centrifugation, and SCMKA was obtained from the resulting neutral transparent aqueous solution of S-carboxymethylkeratin (SCMKA) by isoelectric precipitation. That is, by adjusting the pH of the system to 4.4 with 1N hydrochloric acid.
SCMKA becomes insoluble and precipitates out. This was separated, washed with ethanol, and dried to obtain 4.2 g of SCMKA. (b) In Reference Example 2 (a), a porous material obtained by heating feathers instead of wool fibers in a high-pressure container with superheated steam at 240°C for 6 minutes at 6 kg/cm ² and then rapidly releasing them into the atmosphere. Reference Example 2 except that 17.5 g of maleic acid was used instead of iodoacetic acid.
By the same operation as in (a), 5.3g of S-(1,2
-dicarboxyethyl)-keratin was obtained. (C) In Reference Example 2 (A), 4.2 was prepared by the same procedure as in Reference Example 2 (A), except that pulverized horse hoof was used instead of wool fiber and 11 g of acrylic acid was used instead of iodoacetic acid. g of S-(2-carboxyethyl)-keratin was obtained. (d) Reference example 2 except that 28 g of styrene sulfonic acid was used instead of iodoacetic acid in reference example 2 (a).
4.8 g of S-(sulfophenylvinyl)-keratin was obtained by the same operation as in (a). (e) 8g of wool fiber, 300ml of n-propanol,
After dispersing in 300 ml of 0.1N Tris buffer and purging with nitrogen, 3.2 ml of tri-n-butylphosphine was added, and the mixture was stirred at room temperature for 24 hours. After this was taken, 400 ml of water, 9.28 g of maleic acid and about 30 ml of 5N potassium hydroxide were added to the insoluble portion to adjust the pH to 8.0, followed by stirring at room temperature for 6 hours. About 20 ml of 28% ammonia aqueous solution was added to adjust the pH to 11.5, and the mixture was further stirred at room temperature for 18 hours. The reaction solution was filtered to remove insoluble materials, and the resulting solution was placed in a cellulose tube and dialyzed against ion-exchanged water to remove low-molecular impurities. After dialysis, insoluble components in the cellulose tube are removed by centrifugation.
The resulting neutral transparent aqueous solution was adjusted to pH 4.4 by adding about 5.5 ml of 1N hydrochloric acid, and the precipitate was collected, washed with ethanol, and dried to give 3.9 g of S-(1,
2-dicarboxyethyl)-keratin was obtained. (F) In Reference Example 2 (E), instead of wool fibers, wool was heated in a high-pressure container with 6 kg/cm ² of saturated steam for 6 minutes, and then rapidly released into the atmosphere. 4.5 g of keratin-S-(2
-acrylamide-2-methylpropanesulfonic acid) was obtained. Example 1 Permanent wave treatment was performed using a first agent and a second agent having the compositions shown below, and the degree of hair damage during the treatment was determined by measuring the change in hair weight before and after the treatment. The hair weight measurement method and evaluation criteria are as shown below. [Composition] (First agent formulation) Thioglycolic acid 7.0% Polyoxyethylene hydrogenated castor oil 1.0 Fragrance 0.2 Ammonia water, water balance (pH adjusted to 9.0 with ammonia water) (Second agent formulation) Second agent base Sodium bromate 5.0% Ampholytic surfactant ("Milanol C ₂ M-SF" manufactured by Milanol) 0.5 Cationized cellulose ("Polymer JR400")
(manufactured by UCC) 0 or 0.5 Fragrance 0.1 Decomposed keratin derivatives (Table 1) 2.0 Water Balance [Hair weight measurement method] Virgin hair 10 cm long was washed with a 0.5% aqueous solution of sodium lauryl sulfate and air-dried, and then tested. It was made into hair. Approximately 1 g of this hair was bundled, placed in a desiccator using phosphorus pentoxide as a drying agent, and further dried under reduced pressure for one week.The weight of the hair at the time was defined as the absolute dry weight of virgin hair. Next, this hair is immersed in the first agent at 30℃ for 10 minutes, rinsed thoroughly with water, and then soaked in the permanent wave agent 2 at 30℃.
Soaked for 10 minutes. After thoroughly rinsing with water, the hair was air-dried and dried again in the same manner as described above to determine the bone dry weight of permanent wave hair. [Evaluation Criteria] Evaluation Details ◎ Bone dry weight difference between virgin hair and permanent wave hair is less than 1% 〇 Bone dry weight difference between virgin hair and permanent wave hair is 1% or more and less than 5% × Virgin hair and permanent wave hair The absolute dry weight difference of 5% or more [Results]

[Table] Example 2 A second agent composition having the following composition was prepared, and its feeling in use was sensory evaluated. The test method was to permanently wave 10g of tress using the first agent of Example 1 and the second agent below in the same manner as in Example 1, rinse twice with warm water, and air dry.
The evaluation was conducted by a panel of female experts who conducted a sensory evaluation of the feel of the hair and how it combed. The results are shown in Table 2. Second agent composition: Sodium bromate 5.0% Keratin substance decomposition derivative (Table 2) 2.0 2-amino-2-methyl-1-propanol
0.5 Fragrance 0.1 Water Balance (PH7.0) Results:

〔composition〕

2nd agent base Sodium bromate 5.0% Ampholytic surfactant ("Milanol C ₂ M-SF" manufactured by Milanol) 0.5 Cationized cellulose ("Polymer JR400")
(Manufactured by UCC) 0.5 Fragrance 0.1 Keratin substance decomposition derivative (Table 3) 5.0 Water balance (PH7.0) [Measurement method] Wave degree and wave retention measurement test: (i) Wave the following 20 hairs as one bundle Fix it to the cylinder of the measurement plate (a plate with thin cylinders with a diameter of 2 mm and a length of 1.5 cm arranged in two rows). This is immersed in the first agent having the composition shown in (A)(i) for 10 minutes at 30℃, rinsed thoroughly with water, and then immersed in each of the second agents shown in Table 1 for 10 minutes at 30℃. . After rinsing thoroughly with water, remove it from the wave degree measurement plate and calculate the wave degree using the following formula in still water. Hair: 20cm long virgin hair washed with a 0.5% aqueous solution of sodium lauryl sulfate and air-dried. Wave degree (%) = X-Z/X-Y x 100
Length of the hair fixed between AB: Y: Distance between AB: Z: Distance between the points where the hair was in contact with A and B in still water after being removed from the measurement plate (ii) Used in (i) The washed hair was washed five times under the following washing conditions, and the degree of wave at that time was compared with the degree of wave before washing, and this was taken as wave retention. Wave retention (%) = Wavy degree after 5 times of hair washing / Wave degree before hair washing ×
100 Hair Washing Conditions Leave the hair immersed in a 0.5% aqueous solution of sodium lauryl sulfate for 1 minute and gently move the hair to wash, rinse thoroughly with water, and air dry for 1 day. 5 of this operation
When repeating for the second time, after rinsing thoroughly with water, the above-mentioned Z is measured in still water to determine the degree of wave. 〔result〕

【table】

Claims (1)

[Scope of Claims] 1. One or two types of keratin substance decomposition derivatives selected from the group consisting of thiol group derivatives of oxidative decomposition products of keratin substances and reductive decomposition products of keratin substances in the permanent wave second agent base. A permanent wave second agent composition comprising the above components. 2 The amount of keratin substance decomposition derivative is 0.01 to 10
% by weight of the permanent wave second agent composition according to claim 1.