JPH01110611A - Agent for permanent wave treatment - Google Patents

Abstract

PURPOSE:To obtain a permanent wave treatment agent giving a treated hair having improved smoothness, combing property, flexibility and luster, by compounding a specific silicone polymer, a cationic surfactant and a carboxylic acid-type anionic surfactant at specific ratios. CONSTITUTION:(A) A silicone polymer of formula I (R is H or trimethylsilyl; R1 is OH or methyl; R2 is 1-6C alkylene; R3 is 1-4C alkylene; x is 4-500; y is 1-15) is compound with (B) a cationic surfactant, e.g., a compound of formula II (R6X and R7 are methyl, ethyl or polyoxyethylene; R4 and R5 are 8-18C alkyl or alkenyl or R4 is 12-22C alkyl or alkenyl and R5 is R6, R7 or benzyl; X is halogen, methylsulfate, etc.) and (C) a carboxylic acid-type anionic surfactant (e.g., N-acylsarcosine-type or fatty acid soap-type surfactant) at a molar ratio (B/C) of 4/6-9/1, preferably 5/5-8/2. The contents of the components A and B are preferably 0.5-5wt.% and 0.05-2wt.%, respectively.

Description

[Detailed Description of the Invention] [Industrial Application Field 1] The present invention relates to a permanent waving agent, which significantly improves the feel and appearance of waves, such as smoothness, combing, suppleness, luster, etc. of hair after applying a permanent waving agent. It is characterized by improving.

[Prior art] The first agent for permanent waving is mainly composed of a reducing agent such as thioglycolic acid or its salt or cysteine, and an alkaline agent such as aqueous ammonia or monoethanolamine is added to the solution to adjust the pH of the solution. is used after adjusting it to 8 to 9.5. The second agent mainly contains an oxidizing agent such as sodium bromate, potassium bromate, or hydrogen peroxide.

The first agent cleaves cystine bonds in hair keratin to form cysteine residues, and in order to make this effect effective, the pH is set at 8 to 9.5.

The second agent recombines the cysteine residues generated by the first agent as cystine bonds, thereby fixing the wave. If the PT of the first agent is too high or if the first agent is applied for a long time on already damaged hair, the hair will be seriously damaged. If the hair is heated too much, cystic acid will not be formed in the hair, which will also damage the hair.

These hair damages caused by permanent waving agents can cause the hair to lose its luster, and the cuticle layer on the hair surface to become disordered and give a rough feel.
It is also normal for the hair to comb easily.

Many attempts have been made to prevent such hair damage and to improve the feel of the hair.

For example, a permanent waving agent that contains a keratin hydrolyzate and a cationic surfactant in the first part (Japanese Patent Application Laid-Open No. 57-85309), a cationic polymer in the first part, and a cationic polymer in the second part at the same time. A compound containing an anionic surfactant (Japanese Unexamined Patent Publication No. 56-100710) has been disclosed. Although the above-mentioned known permanent waving agents are effective to some extent in protecting hair from damage and improving the feel of the hair, the odor of the first agent may become worse, or the permanent waving agent may need to be applied several times. As a result, the hair may become hard and stiff, so it is not always sufficient. 'In general, hair damage caused by permanent waving agents is considered to be unavoidable to some extent since their effects are based on chemical reactions. Therefore, it provides excellent smoothness and antistatic effect to damaged hair, protects the hair from mechanical abrasions such as brushing and brushing after perm treatment, and takes care to prevent further hair damage. Conventionally, rinse agents, hair treatment agents, etc. have been applied after perm treatment for this purpose, but the treatment was complicated and time-consuming.

[Problems to be Solved by the Invention] In view of the above circumstances, the present inventors have developed a method that provides excellent feel to the hair, that is, smoothness, suppleness, and smoothness at the same time as perm treatment.
As a result of intensive research to find a permanent waving agent that provides moisturized and glossy wavy hair, we have developed a combination of a specific silicone polymer, a cationic surfactant, and a carboxylic acid type anion. The present inventors have discovered that these problems can be solved by blending a surfactant in a specific ratio, and have completed the present invention.

[Means for Solving the Problems] That is, the present invention provides a solution of the formula (a) (wherein R represents hydrogen or a trimethylsilyl group, and R1
represents a hydroxyl group or a methyl group, R2 represents an alkyl group having a carbon atom or 6, R3 represents an alkyl group having a carbon atom or 4, x represents a number from 4 to 500, and y represents 1 (representing a number of ~15); (b) one or more cationic surfactants; and (c) one or more carboxylic acid type anionic surfactants. Therefore, the molar ratio of (b)/(c) is 47
The purpose of the present invention is to provide a permanent waving agent characterized in that the ratio is in the range of 6 to 9/1.

The configuration of the present invention will be explained below.

The permanent waving agent of the present invention includes the first permanent waving layer agent and the second permanent waving layer agent.
means a drug. Generally, the first permanent wave layer agent is:
The main ingredient is a reducing agent that breaks cystine bonds in hair, such as thioglycolic acid or its salts, cysteine or bisulfite, and an alkaline agent such as aqueous ammonia, ethanolamine, or ammonium carbonate is added to this. The second agent is mainly composed of an oxidizing agent such as sodium bromate, potassium bromate, and aqueous hydrogen phosphate to recombine the cysteine residues in the hair that have been cleaved by the first agent.

The silicone polymer used in the present invention has the above general formula (
It is a compound represented by a), and among these, CTFA name (RD number 977069-1) represented by the following general formula
0-5) of Amodimethicone
ne) is particularly preferred.

CH2CH2NHCH2CH2HH2 X≧4 The cationic surfactant used in the present invention is particularly preferably a quaternary ammonium salt type cationic surfactant represented by the following general formula.

[In the formula, R6 and R7 represent a methyl group, an ethyl group, or a polyoxyethylene group, (i) R+ and R5 represent an alkyl group or an alkenyl group having 8 to 18 carbon atoms, or (i 1)
R4 represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, R5 represents a methyl group, an ethyl group, a polyoxyethylene group, or a benzyl group, and in both (i) and (i), X is a halogen atom or a methyl group. Represents a sulfate or ethyl sulfate residue. ] To specifically illustrate the above-mentioned quaternary ammonium salt type cationic surfactants, examples of (i) include distearyldimethylammonium chloride, dicocyldimethylammonium chloride, and the like. Examples of (ii) include stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, hehenyltrimethylammonium chloride, octyldihydroxyethylmethylammonium chloride, and the like.

The cationic surfactants used in the present invention are appropriately selected and blended in one or more types.

The present invention may use a composition containing a silicone polymer and a cationic surfactant. That is, Dow Corning Cationic Emulsion (D.

w-Corning Cationic Emulsi
on) 929, or TOμ Silicone 5148702C, a commercially available product containing amodimethicone, stearyltrimethylammonium chloride, and dicokoyldimethylammonium chloride.

The carboxylic acid type anionic surfactants used in the present invention are particularly preferably those represented by the following general formulas (i) to (iv).

(i) Formula % Formula % (wherein R8 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, a represents the number 1 or 2, M
represents one or more of alkali metals, organic amines, and basic amino acids. ) Specific examples include N-acylsarcosine type anionic surfactants such as N-lauroyl N-sarcosine sodium, N-lauroyl-N-methyl-
Examples include doacyl-β-alanine salt type anionic surfactants such as sodium β-alanine.

(ii) Formula % Formula % (In the formula, R9 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of alkali metals, organic amines, and basic amino acids.) Specifics Examples include N-acylglutamate type anionic surfactants such as disodium N-lauroriglutamate.

(iii) Formula % Formula % (wherein R10 represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, b represents 0 or a number from 1 to 16, M is an alkali metal, an organic amine, a basic (Represents one or more amino acids.) Specific examples include ether carboxylic acid type anionic surfactants such as polyoxyethylene (3 mole addition) tridecyl ether sodium acetate.

(iv) Formula % Formula % (In the formula, R11 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of alkali metals, organic amines, and basic amino acids.) Specifics Examples include fatty acid soap type anionic surfactants such as sodium laurate.

One or more types of carboxylic acid type anionic surfactants used in the present invention are appropriately selected and blended.

The content of the silicone polymer used in the present invention is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the total amount of the permanent waving agent.

If it is less than 0.1% by weight, the smoothness of the hair will be reduced, and if it exceeds 10% by weight, the smoothness of the hair will almost reach its upper limit, which is not economical and may impede the waving efficiency. Undesirable.

The content of the cationic surfactant used in the present invention is preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, based on the total amount of the permanent waving agent. If it is less than 0.01% by weight, the smoothness and frizziness of the hair will be reduced, and if it exceeds 5% by weight, the smoothness and suppleness of the hair will almost reach the upper limit, making it not economical and waving efficiency. This is not preferable as it may inhibit the

The compounding ratio of the cationic surfactant and the carboxylic acid type anionic surfactant used in the present invention is 476 to 9/molar ratio of cationic surfactant/carboxylic acid type anionic surfactant. 1, preferably 515 to 8/2. If the molar ratio is greater than 971, the smoothness of the hair will not be sufficient. Moreover, when the molar ratio is smaller than 476, the hair slipping is rapidly reduced.

When the permanent waving agent of the present invention is the first agent for permanent waving, the main reducing agent is thioglycolic acid, thiolactic acid, thiomalic acid or salts thereof, cysteine, doacetylcysteine, homocystine, etc. Examples include mercapto compounds or inorganic reducing agents such as sulfites, hydrogen sulfites, pyrosulfites, and thiosulfates. Counterion moieties of the above salts include alkali metals, ammonium, monoethanolamine, triethanolamine, 2 -amino-2-methyl-propatool,
Examples thereof include 2-amino-2-methyl-propanediol, isopropanolamine, diisopropanolamine, guanidine, and basic amino acids. These reducing agents may be used alone or in combination of two or more.

Naturally, in addition to the above ingredients, aqueous ammonia, monoethanolamine, triethanolamine, 2-amino-2-methyl-propanediol, 2-amino-2-methyl-propanediol, inpropanediol, diisopropanediol, Alkaline agents such as patoolamine, guanidine carbonate, guanidine hydrochloride, guanidine sulfate, basic amino acids, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. can be blended.

When the permanent waving agent of the present invention is a second permanent waving agent, examples of the main oxidizing agent include sodium bromate, potassium bromate, sodium perborate, and hydrogen peroxide. These oxidizing agents may be used alone or in combination of two or more types. Active agents, amphoteric surfactants, cationic polymers, amphoteric polymers, nonionic polymers, fats and oils such as animal oils and vegetable oils, hydrocarbons such as mineral oils, synthetic branched ester oils, waxes, silicone oils, Glycol-modified silicone, polyols such as glycerin and propylene glycol, amino acids and amino acid oligos or polypeptides, staining agents and hydrogen bond breakers such as ethyl alcohol, inpropyl alcohol, urea and alkyl urea, metal ion sequestrants, Various buffering agents,
Flavorings, colorings, etc. can be added.

[Effect of the invention] The permanent waving agent of the present invention can be used to smooth hair,
(It has significantly improved texture, suppleness, shine, and appearance of waves.)

[Example] Next, the present invention will be explained in detail with reference to Examples. The present invention is not limited to these. The blending amount is in weight%. Prior to Examples, effectiveness tests and evaluation methods will be explained.

Puno no 21 10% shampoo liquid (unscented, uncolored) for women in their 20s with black hair (perm, hair conditioning - no bleach treatment)
After washing with water and rinsing thoroughly with running water, let it air dry indoors.

Align the roots and tips of the hair, tie 12 hairs together at the roots, and use this as a hair sample. Immerse it in a prototype of one of the perm agents described later at 30°C for 15 minutes, then rinse it under running water for 3 minutes.
After washing for 0 seconds, the samples were immersed in the two-agent prototype at 30°C for 20 minutes. Finally, wash it under running water for 30 seconds, then hang it indoors to air dry. These hair samples were tested using a friction and abrasion tester model NRF (
The coefficient of kinetic friction (μK) with respect to the aluminum pulley was measured using the Nippon Rheology Instruments Co., Ltd.). The same sample was measured 10 times and the average was taken. In addition, the coefficient of kinetic friction (μ, D: 24°C) of the treated hair when dry is
, 40±5χR were measured in two cases: old and wet (μX, W), respectively. It is considered that when the coefficient of dynamic friction (μ, o) is small, the feel of dry hair after perming is smooth. Similarly, the coefficient of kinetic friction (μ
3. It is considered that the smaller - is, the smoother the hair feels when wet with water.

Knee-1 Create the same hair sample as in (1) and cut the hair at 120H in the direction from the knot to the tip of the hair. Wrap the hair sample evenly around a glass tube (φ=7.5 mm) from the root, and press the end with a plastic stopper.

After immersing a prototype product of perm agent 1 (described later) at 30°C for 15 minutes and washing it with running water for 30 seconds, immersing it in a prototype product of perm agent 2 at 30°C.
Soak for 0 minutes. Finally, after washing with running water for 30 seconds, the hair is removed from the glass tube to form a hair coil. Diameter of hair coil when wet (dw, (no++)
), then after wiping off the excess water with absorbent paper,
Hang the hair coil and measure its length (1w, (m)). The same sample was measured 10 times, and the average was taken. Hair coil diameter (dw) and length N
It is considered that the smaller t, w) is, the higher the weave efficiency is.

10 Superiors ILfL Medical Hair bundles (15 cm in length, 3 cm in diameter, 1.5 g in weight) were created using hair that was in almost the same condition (thickness, hardness, degree of damage) as the hair, and a permanent waving agent was created. We conducted an evaluation. 1 mL prototype of the first perm agent described later
Apply it and wind it using end vapor and a rod. Apply 1d of agent 1 again and leave it in a constant temperature bath at 30°C. After 15 minutes, wash with lukewarm water at about 40° C. for about 30 seconds, wipe off excess water with a towel, apply prototype 1d of two perm agents to be described later, and let stand at room temperature for 5 minutes. Apply 1 mL of the second agent again and let stand for 15 minutes. Finally, remove the rod and wash it with lukewarm water of about 40℃ for about 30 seconds, wipe off the excess water with a towel and clean it as shown below.
Perform sensory evaluation.

(i) Evaluate A, combability, smoothness C, L/softness in a wet state. Thereafter, the hair strands are hung indoors and air-dried, and (ii) in the dry state, evaluations are made of d, threadability e, smoothness fl, smoothness g, and wave elasticity.

Sensory evaluation was performed using the following five-step evaluation method.

×: Bad Δ: Fair ○: Fairly good 0: Fairly good O: Very good Examples 1 to 6, Comparative Examples 1 to 3 Table 1 shows the prototype formulation and evaluation results of permanent wave layer agent 1. The two permanent wave layer agents used in this test were all the same, and their formulations are shown below.

2-drug prescription [A prescription] Sodium bromate 6.0 1st
Potassium phosphate 0.5 Disodium hydrogen phosphate dodecahydrate 0.05 Sodium benzoate 0.1 Purified water
93.35 (blank below) *Amodimethicone (manufactured by Toray Silicone Co., Ltd.) represented by the following formula.

As is clear from Table 1, all of the examples of the present invention are
The coefficient of friction is small in wet and dry conditions, and
As for the feel of the hair, it can be seen that it has excellent combability, smoothness, and suppleness, and also has good wave elasticity.

Examples 7 to 9, Comparative Examples 4 to 6 Table 2 shows the prototype formulation and evaluation results of the two permanent wave layer agents. The permanent wave layer agent 1 used in this test was all common, and the formulation is shown below.

1-drug prescription [B prescription] Ammonium thioglycolate 't1 13,
0 (Contains 50χ as thioglycolic acid) Ammonium hydrogen carbonate 3.4 Monoethanolamine 182 Disodium edetate
0.1 purified water
82.3 (blank below) As is clear from Table 2, the coefficients of dynamic friction of the examples of the present invention are small in both wet and dry conditions, and in terms of the feel of the hair, it is easy to comb through and slip. It can be seen that it has excellent curl, suppleness, and elasticity of waves.

Example 10 Permanent wave layer agent 1 agent (thioglycolic acid type) Ammonium thioglycolate solution 12.0 (
Contains 50% as thioglycolic acid) Monoethanolamine 1.5 Ammonium bicarbonate 3.0 Amodimethicone 12.0 Stearyltrimethylammonium chloride 1
o, tacocoyldimethylammonium monochloride*
0.15 Trauroyl N-methyl-β-alanine sodium 0.1
3 polyoxyethylene (10 mol) nonylphenol”
0.03 Disodium edetate 0.05 Purified water
Remaining portion *: These components are contained in TOμ Silicone 5M8702C (manufactured by TOμ Silicone Co., Ltd.).

Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable first agent.

When I applied Crystal 80Ile to my hair (leaved for 10 minutes) and used the second agent (formulation A) 80mtj (leaved for 20 minutes), it was very smooth, supple, and elastic waves were formed. . After drying with a hairdryer, the waves were very smooth, had a smooth texture, and were elastic and shiny.

Example 11 Permanent wave layer agent 1 agent (cystine type) L-cysteine 6.0 Ammonium thioglycolate solution 2.0 (Contains 50% as thioglycolic acid) Monoethanolamine 2.5 Ammonia water reagent special grade (2
8%) 1.0 Amodimethicone 12.0 Stearyltrimethyl chloride 7 Nitium 9
o, dicocoyldimethylane(nium monochloride)”
0.15 polyoxyethylene (10 moles)
Nonylphenol
o, o3 Trau 0yl-N-Methy Tori-sarcosine sodium o, 12 Edetate disodium 0.10 Purified water
Remaining portion*: These components are contained in Toichi Silicone 5M8702C (manufactured by Toshi Silicone Co., Ltd.).

Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable first agent.

Treatment on hair using crystal 80+++i (leave for 15 minutes)
However, when 80d of the second agent (prescription A) was used (left for 20 minutes), very smooth, supple, and elastic waves were formed.

Example 12 Curling agent 1st agent Sodium bisulfite 5.0 Monoethanolamine 2.5 Isopropyl alcohol 5.0 Amodimethicone 44.0 Stearyltrimethylammonium chloride 6
0.2 Dicocoyldimethylammonium chloride 8
0.3 polyoxyethylene (10 ml) nonylpheno-ha O,0
Sodium B lauryl fatty acid 0.19
Purified water Remainder*: These components are contained in TOμ Silicone 5M8702C (manufactured by TOμ Silicone Co., Ltd.).

Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable first agent.

Treatment on hair using 80wt crystal (hair dryer -60℃)
When I used 80ml of the second agent (prescription A) (left for 10 minutes), it was very smooth and supple.
A soft wave was formed.

Example 13 Permanent wave layer agent 1 agent (cystine type) DL-cystine 3. O
N-acetyl-L-cysteine 3.
0 ammonium thioglycolate solution 2.0 (
Guanidine carbonate (contains 50% as thioglycolic acid)
1.0 Monoethanolamine 1.0 Ammonia water reagent special grade (2
8%) 1.0 Amodimethicone”
2. O1m stearyltrimethylammonium”
0.1 Dicocoyldimethylammonium chloride 9
0.15 polyoxyethylene (
10 (le) noninfueno 46
0. o: 3 polyoxyethylene (3 mol) tridecyl ether Q1=M sodium”
0.17 Edetate disodium 0
．． 10 Purified water Remainder*: These ingredients are TOμ Silicone 5M8702C
(manufactured by TO-μ Silicone Co., Ltd.).

:Mo*: Nikkor ECTD-3NEX (manufactured by Nikko Chemicals Co., Ltd.) Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable first agent.

Using 80mL of ice crystals, apply the treatment to your hair (leave it for 20 minutes),
When 80 ml of the second agent (Formulation A) was used (leaved for 20 minutes), very smooth, easily combed, and supple waves were formed.

Example 14 Permanent wave layer agent No. 1 (sodium bromate type) Sodium bromate 7.0 No. 1
Potassium phosphate 0.5 Disodium hydrogen phosphate dodecahydrate 0.05 Sodium benzoate 0.05 Amodimethicone*2.0 Lambda thearyltrimethylammonium chloride 9
0.1 dicocoyldimethylammonium chloride”
0.15 polyoxyethylene (10 zol) nonylphenol”
0.03 N-lauroyl-N-methyl-sarcosinate sodium 0.12 Purified ice Residue B.

::These ingredients are Toμ Silicone 5148702
Contained in C (TOμ Silicone Co., Ltd.).

Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable second agent.

When I applied 80ml of the first agent (prescription B) to my hair (leaved for 10 minutes) and applied Ice Crystal 80rrL (leaved for 15 minutes), the hair was very smooth, easy to comb, and had supple waves. Completed formation.

Example 15 Permanent wave layer agent 2nd agent (hydrogen peroxide type) Hydrogen peroxide solution (30%) 9.0 Monobasic potassium phosphate 0.3 Methylparaben 0.1 Amodimethicone 12.0 Stearyltrimethylammonium chloride 1
0.1 Dicocoyldimethylammonium chloride*
o, 15 polyoxyethylene (10 mol) nonynepheno-360,03 polyoxyethylene (3 mol)
Tridisyl ether-sodium acetate 0
．． 15 Purified water Remainder*: These ingredients are Toμ Silicone 5148702
C (manufactured by TO-μ Silicone Co., Ltd.).

Manufacturing method The above compositions were combined and stirred to obtain a uniformly cloudy and stable second agent.

When I used 80trL of the first agent (prescription B) and applied it to my hair (leaved for 10 minutes), and used Ice Crystal 80Tn (leaved for 5 minutes), the results were very smooth, easy to comb, and supple waves. was formed.

Patent applicant Shiseido Co., Ltd. Procedural amendment (voluntary) Commissioner of the Patent Office Kunio Ogawa 1, Address indicated in the case 7-5-5 Ginza, Chuo-ku, Tokyo “
"Claims" column and "Detailed Description of the Invention" column.

5. Contents of the amendment (1) Correct the $(no tnu) in the words ``1'' to Mr. 3.
゜(2) Change “Pepji≠” to “Pepji≠” on page 18, line 12 of the specification.
Peptide” is corrected.

(3) On page 18, line 14 of the specification, "Layering agent and" shall be deleted.

(4) The third line of page 25 of the specification is amended as follows.

(5) In the 9th line from the bottom of page 25 of Meisho M, ``same'' is amended to ``shu''.

(6) Meisho M, page 25, line 6 from the bottom, “elasticity” is replaced by “efficiency”
and correct it.

(7) On page 28 of the specification, line 5, "elasticity" is corrected to "efficiency."

(8) Delete “First agent” on page 30, line 18 of the specification.

(9) Substitute “1st agent” with “2nd agent” line 9 of line 1’3 of the specification.
Corrected to "agent".

αω Specification page 34 line 17 “Methyl paraben 0.1
Delete j.

Above (separately) 2. Claim (a) Formula (wherein R represents hydrogen or a trimethylsilyl group, R+
represents a hydroxyl group or a methyl group, R2 represents an alkyl L/7 group having 1 to 6 carbon atoms, R3 represents an alkytoe group having 1 to 4 carbon atoms, and X represents 4 to 5
00 and y represents a number from 1 to 15), (b) one or more cationic or ionic surfactants, and (c) a carboxylic acid type anionic surfactant. A permanent waving agent, which contains one or more of (hereinafter referred to as Zenshiro) and two or more types, and the molar ratio of (b)/(c) is in the range of 476 to 9/1. .

(2) A cationic surfactant represented by the following general formula:
The permanent waving agent according to claim 1, which is an ammonium salt type cationic surfactant.

[wherein R6 and R7 represent a methyl group, an ethyl group, or a polyoxyethylene group, (i) R4 and R5 represent an alkyl group or an alkenyl group having 8 to 18 carbon atoms, or (ii) R
4 represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, R6 represents a methyl group, an ethyl group, a polyoxyethylene group, or a benzyl group, and (i) and (
ii) In both cases, X represents a halogen atom or a methyl sulfate or ethyl sulfate residue. (3) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is an N-acylsarcosine type anionic surfactant represented by the following general formula.

CH3 R8-C0)l-(CH2) --COO)4 (in the formula,
R8 represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms, a represents a number of 1 or 2, and the space between represents one or more of alkali metals, organic amines, and basic amino acids. )(4) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is an N-acylglutamate type anionic surfactant represented by the following general formula.

(5) Carboxylic acid type The permanent waving agent according to claim 1, wherein the anionic surfactant is an ether carboxylic acid type anionic surfactant represented by the following general formula.

R10(QC)I2CH2)bOc)12COOH (wherein R10 represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, b represents ○ or a number from 1 to 16, M is an alkali metal, an organic amine, (6)-Carboxylic acid type anionic surfactant is a fatty acid soap type anionic surfactant represented by the following general formula.Claim 1: Permanent waving agent as described.

Rr + COOM (In the formula, R11 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and the space between represents one or more types of alkali metals, organic amines, and basic amino acids.)

Claims (6)

[Claims] (1) (a) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents hydrogen or trimethylsilyl group, R_
1 represents a hydroxyl group or a methyl group, R_2 represents an alkyl group having 1 to 6 carbon atoms, R_3 represents an alkyl group having 1 to 4 carbon atoms, and X is 4 to 50
0 and y represents a number from 1 to 15), (b) one or more cationic surfactants, and (c) a carboxylic acid type anionic surfactant. containing one or more types, and the molar ratio of (b)/(c) is 4/
A permanent waving agent characterized in that the ratio is in the range of 6 to 9/1. (2) A cationic surfactant represented by the following general formula:
The permanent waving agent according to claim 1, which is an ammonium salt type cationic surfactant. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_6 and R_7 represent a methyl group, an ethyl group, or a polyoxyethylene group, (i) R_4 and R_5 are an alkyl group or an alkenyl group having 8 to 18 carbon atoms. or (ii
) R_4 represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, R5 represents a methyl group, an ethyl group, a polyoxyethylene group or a benzyl group, (i)
and (ii) X represents a halogen atom or a methyl sulfate or ethyl sulfate residue. ] (3) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is an N-acylsarcosine type anionic surfactant represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_8 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, a represents the number of 1 or 2,
M represents one or more of an alkali metal, an organic amine, and a basic amino acid. ) (4) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is an N-acylglutamate type anionic surfactant represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_9 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of alkali metals, organic amines, and basic amino acids. .) (5) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is an ether carboxylic acid type anionic surfactant represented by the following general formula. R_1_0(OCH_2CH_2)_bOCH_2CO
OM (wherein R_1_0 represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, b represents 0 or a number of 1 to 16, and M represents one or two of an alkali metal, an organic amine, or a basic amino acid. (represents the above) (6) The permanent waving agent according to claim 1, wherein the carboxylic acid type anionic surfactant is a fatty acid soap type anionic surfactant represented by the following general formula. R_1_1COOM (In the formula, R_1_1 represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and M represents one or more types of alkali metals, organic amines, and basic amino acids.)