JP2584260B2 - Agent for permanent wave - Google Patents

Description

The present invention relates to a permanent wave agent,
It is excellent in wave efficiency, low in irritation, and markedly improves the feeling of smoothness, comb, and suppleness of hair and the appearance of waves after perm treatment.

[Prior Art] The first agent of a permanent wave agent generally contains a reducing agent such as thioglycolic acid or a salt thereof or cysteine as a main component, and further adds an alkaline agent such as aqueous ammonia or monoethanolamine to form a liquid. It is used after adjusting the pH to about 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 the cystine bond in hair keratin to form a cysteine residue, and the pH is set to about 8 to 9.5 to make this effect more effective. The second agent is to re-bond the cysteine residue generated by the first agent as a cystine bond to fix the wave. If the pH of the first part is set too high or the treatment time of the first part is increased for hair that has already been damaged, the hair is considerably damaged. If the second agent is made to act longer than necessary or is heated too much, cysteic acid is formed in the hair, and the hair is also damaged.

These hair damages, which are based on permanent waving agents, usually cause the hair after the perming treatment to lose its luster, give the surface a cuticle layer that is rough and rough, and also have poor combing. is there.

It is generally believed that hair damage due to permanent wave agents is unavoidable to some extent as long as the action is based on chemical reactions. Therefore, it is necessary to give the smoothness and antistatic effect to the damaged hair once, protect the hair from mechanical friction such as brushing and brushing performed after the perm treatment, and take measures to prevent the hair damage from further progressing. . For this reason, after the perm treatment, a rinsing agent, a hair treatment agent, and the like were applied, but this also involved a large number of steps in the treatment and was troublesome.

Therefore, in order to prevent damage to the hair and to improve the feel of the hair, attempts have conventionally been made to directly incorporate a cationic surfactant into a permanent waving agent. However, although the cationic surfactant has an effect of improving the feel of the hair to some extent, it is irritating to the skin and tends to inhibit the wave efficiency, so that the amount of the cationic surfactant is limited. That is, although there has been a demand for a product having excellent wave efficiency, low irritation, and good hair feel after perm treatment, a product which satisfies these requirements has not been obtained.

[Problems to be solved by the invention] In view of such circumstances, the present inventors have low irritation,
As a result of intensive research on whether a permanent waving agent that gives excellent hair efficiency at the same time as hair treatment and gives excellent feeling to hair at the same time as perm treatment, ie, smoothness, suppleness, and combability, was obtained. It has been found that these problems can be solved by blending an ammonium salt-type cationic surfactant and a carboxylate-type anionic surfactant in a specific ratio, and have completed the present invention.

[Means for Solving the Problems] That is, the present invention provides one or more quaternary ammonium salt type cationic surfactants and one or more carboxylate type anionic surfactants The present invention provides an agent for permanent wave, wherein the agent has a / molar ratio in the range of 4/6 to 8/2.

 Hereinafter, the configuration of the present invention will be described.

The permanent wave agent of the present invention refers to a permanent wave agent first agent and a permanent wave agent second agent. Generally, the first agent for a permanent wave mainly comprises a reducing agent such as thioglycolic acid or a salt thereof, cysteine or bisulfite, which cuts a cystine bond in hair, to which ammonia water, ethanolamine, ammonium carbonate, etc. The second agent is an oxidizing agent for recombining cysteine residues in the hair cleaved by the first agent, that is, sodium bromate, potassium bromate, hydrogen peroxide, etc. Is a main component.

Although the quaternary ammonium salt type cationic surfactant used in the present invention is not particularly limited, a monoalkyl type quaternary ammonium salt type cationic surfactant represented by the following general formula (A) and a general formula (B) Imidazoline type quaternary ammonium salt type cationic surfactant represented by:
The quaternary ammonium salt type cationic surfactant represented by the general formula (C) is preferable.

(In the formula, R ₁ represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, R ₂ , R ₃ and R ₄ represent a methyl or ethyl group, and X represents a halogen atom or a methyl sulfate residue.) (In the formula, R represents an alkyl group or alkenyl group having 12 to 22 carbon atoms, and X represents a halogen atom or an anionic group selected from lower alkyl sulfate groups having 1 to 2 carbon atoms in the alkyl group.) (Wherein R ₁ represents an alkyl group having 16 to 22 carbon atoms, R ₂ represents an alkyl group having 1 to 2 carbon atoms or an alkyl group having 16 to 22 carbon atoms, X represents a halogen atom, Is 1
And an anionic group selected from 2 or lower alkylsulfate groups, wherein m and n are each an integer of 1 or more, and their sum is 2-30. Specific examples of the quaternary ammonium salt type cationic surfactant used in the present invention include monoalkyl type quaternary ammonium salt type cationic surfactants represented by the general formula (A): stearyl trimethyl Ammonium chloride, myristyltrimethylammonium bromide, palmityldimethylethylammonium ethylsulfate and the like. Examples of the quaternary ammonium salt type cationic surfactant represented by the general formula (C) include dipolyoxyethylene (2 mol addition). ) Stearylethylammonium bromide, dipolyoxyethylene (4 mol addition) behenylmethylammonium chloride and the like. One or more of these are arbitrarily selected and used.

Examples of the carboxylate type anionic surfactant used in the present invention include: i) a general formula RCOOM (where R is an alkyl group or alkenyl group having 8 to 22 carbon atoms, M is an alkali metal, an organic amine, or a base) One or two or more types of acidic amino acids.) A fatty acid soap-type anionic surfactant such as sodium laurate, potassium myristate, sodium oleate, sodium stearate, and triethanolamine behenate; ii) formula _{R (OCH 2 CH 2) nOCH} 2 COOM ( wherein, R is an alkyl group or an alkylaryl group having 8 to 22 carbon atoms, n represents 0 or 1 to 16 integer, M is an alkali metal organic amines, basic A polyoxyethylene (3 mol addition) sodium lauryl ether carboxylate represented by one or more amino acids 6 mol adduct) ether carboxamide acid salt such as myristyl ether carboxylate-type anionic surfactant, iii) the general formula (Wherein R represents an alkyl or alkenyl group having 8 to 18 carbon atoms, M represents one or more of an alkali metal, an organic amine, and a basic amino acid) N-lauroyl sarcosine potassium, N N-acyl sarcosine salt type anionic surfactants such as stearoyl sarcosine triethanolamine salt or iv) a general formula (Wherein, R represents an alkyl or alkenyl group having 8 to 18 carbon atoms, M represents one or more of an alkali metal, an organic amine, and a basic amino acid.) N-lauroylglutamate potassium, N -A general formula represented by a condensate of a higher fatty acid such as N-acyl glutamate such as palmitoyl glutamic acid triethanolamine salt and an amino acid such as sarcosine, β-alanine, glutamic acid, glycine, valine and leucine; Anionic surfactants having a -COO ^- group can be exemplified.

In the present invention, one or more of these are used.

In the present invention, the molar ratio of / is in the range of 4/6 to 8/2, preferably in the range of 5/5 to 7/3. In this composition, if the molar ratio is less than 4/6, the effect of improving the feel of the hair and the wave efficiency are inferior, and if the molar ratio is more than 8/2, the irritation to the skin is strong and the wave efficiency is also inferior. Absent. The total amount of + is 0.02 to 20% by weight, preferably 0.1 to 10% by weight, based on the total amount of the composition. If the amount is less than 0.02% by weight, the surfactant is insufficient, so that it is not possible to obtain a sufficient effect in improving the feel of the hair and the wave efficiency. If the amount exceeds 20% by weight, irritation to the skin may occur. It is not preferable because it becomes strong.

In the present invention, in addition to the above essential components, the incorporation of the amphoteric surfactant into the agent for permanent wave further enhances the stability of the product at low temperatures against separation of the system and the like. It is desirable to do. Specifically, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium,
-Cocoyl-2-imidazolinium hydroxide-1-
Imidazoline amphoteric surfactants such as carboxyethyloxy-2-sodium, betaine amphoteric surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and betaine lauryldimethylaminoacetate, or alkyl betaine ,
Examples include aminobetaine and sulfobetaine. One or more of these amphoteric surfactants may be used. The amount is preferably from 0.1 to 20% by weight, more preferably from 1 to 10% by weight, based on the total amount of the composition.

When the agent for permanent wave of the present invention is the first agent for permanent wave, the reducing agent as the main agent may be thioglycolic acid, thiolactic acid, thiomalic acid or salts thereof, cysteine, N-acetylcysteine, homocysteine. Such as mercapto compounds or sulfites, bisulfites, pyrosulfites, inorganic reducing agents such as thiosulfates, and the like, as the counter ion portion of the salts, alkali metals, ammonium, monoethanolamine, triethanolamine, Examples include 2-amino-2-methyl-propanol, 2-amino-2-methyl-propanediol, isopropanolamine, diisopropanolamine, guanidine, basic amino acids and the like. These reducing agents may be used alone or in combination of two or more.

Naturally, in addition to the above components, ammonia water, monoethanolamine, triethanolamine, 2-amino-2-methyl-propanol, 2-amino-2-methyl-propanediol, isopropanolamine, diisopropanolamine, carbonate An alkaline agent such as guanidine, guanidine hydrochloride, guanidine sulfate, a basic amino acid, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide, or lithium hydroxide can be blended.

When the agent for permanent wave of the present invention is the second agent for permanent wave, examples of the oxidizing agent as the main agent include sodium bromate, potassium bromate, sodium perborate and aqueous hydrogen peroxide. These oxidizing agents may be used alone or in combination of two or more.

Further, the permanent wave agent of the present invention can also contain components and additives commonly used in permanent wave agents. That is, nonionic surfactants such as polyoxyethylene alkyl ethers and alkyl glycosides, fats and oils such as animal oils and vegetable oils, higher alcohols, silicone oils, liquid paraffins, oils such as esters, and polyhydric alcohols such as glycerin and propylene glycol , Amino acids and oligo or polypeptides of amino acids, ethyl alcohol, alcohols such as isopropyl alcohol, urea, hydrogen bond breaking agents such as alkyl urea,
Glycol-modified silicone, natural extracts of plants and animals and their derivatives, sequestering agents, various buffers, fragrances and pigments can be added.

[Effects of the Invention] The present invention is excellent in wave efficiency and wave elasticity, low in irritation, and significantly improved the feeling of smoothness, comb-like and suppleness of hair after perm treatment and the appearance of waves. A permanent wave agent is provided.

[Examples] Next, the present invention will be described in more detail with reference to examples.
The present invention is not limited by these. The compounding amount is% by weight. Prior to the examples, an effect test and an evaluation method will be described.

(1) Measurement of wave effect Wash healthy 20-year-old female black hair (without perm and hair color bleach treatment) with 10% shampoo (non-scented, non-colored), rinse well with running water, and indoors Allow to air dry. Align the roots of the hair with the tip of the hair, tie 12 hairs at the root, and cut the hair 120mm from the knot to the tip of the hair. From the root of the hair sample, place a glass tube (φ = 7.5m
m) and wrap the ends uniformly with a plastic stopper. Immerse in a prototype of one perm agent to be described later at 30 ° C for 15 minutes and wash with running water for 30 seconds.
Let soak for a minute. Finally, after washing with running water for 30 seconds, the hair is removed from the glass tube and a hair coil is formed. Measure the diameter (dw, (mm)) of the hair coil while wet with water,
Next, excess water is wiped off with water-absorbing paper, and then the hair coil is hung and its length (lw, (mm)) is measured. The same sample was measured 10 times, and the average was taken. It is considered that the smaller the diameter (dw) and length (lw) of the hair coil, the higher the weave efficiency.

(2) Sensory evaluation Using hair of almost the same condition (thickness, hardness, degree of damage), hair bundle (length 15 cm, width 3 cm, weight 1.5)
g) was prepared, and the agent for permanent wave was evaluated. 1 ml of a prototype of the first permanent agent described later is applied, and winding is performed using an end paper and a rod. 1 ml of one agent is applied again and left in a thermostat at 30 ° C. Fifteen minutes later, after washing with warm water of about 40 ° C. for about 30 seconds and wiping off excess water with a towel, apply 1 ml of a two-permeant prototype described later and let stand at room temperature for 5 minutes. Apply 1 ml of the two agents again and let stand for 15 minutes. Finally, the rod is removed, washed with lukewarm water of about 40 ° C. for about 30 seconds, excess water is wiped off with a towel, and a sensory evaluation is performed as follows.

a. Slipperiness b. Smoothness c. Suppleness d. Elasticity of wave The sensory evaluation was evaluated by the following four-step evaluation method.

×: Poor △: Normal ○: Slightly good ◎: Very good (3) Skin irritation It is possible to evaluate skin irritation by the strength of protein denaturing power of surfactants and surfactant compositions (protein denaturation rate). It is known (JP-B-59-42038), and the skin irritation of the composition of the present invention was evaluated by the protein denaturation rate based on this evaluation method.

Protein denaturation rate Using an aqueous high-performance liquid chromatography, the denaturation rate of ovalbumin when a sample was added to a buffer concentration of 1% in ovalbumin pH7 buffer solvent was measured using an absorption peak at 220 nm.

Ho: Height of the 220 nm absorption peak of ovalbumin Hs: Height of the 220 nm absorption peak when the sample was added to the ovalbumin buffer solvent The evaluation was performed in the following four steps.

◎: Very low skin irritation-less than 30% ovalbumin denaturation ○: Low skin irritation-30% ovalbumin denaturation
Not less than 60% △: Moderate skin irritation-60% ovalbumin denaturation
Not less than 80% ×: skin irritation is strong-ovalbumin denaturation rate is not less than 80% Examples 1 to 8, Comparative Examples 1 to 7 Table 1 shows the formulation and evaluation results of one permanent wave agent. . Note that the two permanent wave agents used in this test were all common, and the formulations are shown below.

Two-part formulation [Formulation A] Sodium bromate 6.0 Monobasic potassium phosphate 0.5 Disodium hydrogen phosphate dodecahydrate 0.05 Sodium benzoate 0.1 Purified water 93.35 As is clear from Table 1, all of the examples of the present invention are excellent in wave efficiency, good in hair feeling such as combability, smoothness and suppleness, and low in skin irritation.

Examples 9 to 11 and Comparative Examples 8 to 10 Table 2 shows the trial product formulations and evaluation results of two permanent wave agents. In addition, the one agent for permanent wave used in this test is all common, and the formulation is shown below.

One agent formulation [B formulation] Ammonium thioglycolate solution (containing 50% as thioglycolic acid) 13.0 Ammonium hydrogen carbonate 3.4 Monoethanolamine 1.2 Disodium edetate 0.1 Purified water 82.3 As is clear from Table 2, all of the examples of the present invention are excellent in wet efficiency, good in hair feel such as combability, smoothness, and suppleness, and low in skin irritation.

Example 12 Permanent Wave Agent First Agent (Thioglycolic Acid) Ammonium Thioglycolate Solution (Containing 50% as Thioglycolic Acid) 12.0 Monoethanolamine 1.5 Ammonium Bicarbonate 3.0 Lauryldimethylaminoacetate Betaine (30%) 20.0 Stearyl Trimethylammonium chloride 1.04 N-lauroyl-N-methyl-β-alanine sodium
0.62 Disodium edetate 0.05 Purified water Remainder Manufacturing method The above compositions were combined and stirred to obtain a uniform, transparent and stable first agent.

Using 80ml of this product, perform hair treatment (leave for 10 minutes),
When 80 ml of the preparation (Formulation A) was used (leave for 20 minutes), a very smooth and flexible wave was formed. Neither the practitioner nor the subject used irritation.

Example 13 Permanent Wave Agent First Agent (Cysteine System) L-cysteine 6.0 Ammonium thioglycolate solution (containing 50% as thioglycolic acid) 2.0 Monoethanolamine 2.5 Ammonia water reagent special grade (28%) 1.0 Lauryldimethylaminoacetic acid Betaine (30%) 15.0 Myristyltrimethylammonium bromide 0.5 N-Lauroyl-N-methyl-β-alanine sodium
0.31 Disodium edetate 0.10 Purified water Remainder Manufacturing method The above compositions were combined and stirred to obtain a uniform, transparent and stable first agent.

Using 80ml of this product, perform hair treatment (leave for 15 minutes),
When 80 ml of the preparation (Formulation A) was used (leave for 20 minutes), a very smooth and flexible wave was formed. Neither the practitioner nor the subject used irritation.

Example 14 First Curling Agent Sodium Bisulfite 5.0 Monoethanolamine 2.5 Isopropyl Alcohol 5.0 Betaine Lauryldimethylaminoacetate (30%) 10.0 Stearyltrimethylammonium Chloride 0.52 Sodium Laurate 0.22 Disodium Edetate 0.10 Purified Water Remainder The first mixture was mixed and stirred to obtain a uniformly transparent and stable first agent.

Using 80ml of this product, hair treatment (dryer 60 ℃
After 10 minutes) and using 80 ml of the second agent (Formulation A) (leaving for 10 minutes), a very smooth and flexible wave was formed. Neither the practitioner nor the subject used irritation.

Example 15 Agent for permanent wave first agent (cysteine type) DL-cysteine 3.0 N-acetyl-L-cysteine 3.0 ammonium thioglycolate solution (containing 50% as thioglycolic acid) 2.0 guanidine carbonate 1.0 monoethanolamine 1.0 ammonia water Reagent special grade (28%) 1.0, betaine lauryl dimethylaminoacetate (30%) 15.0 Stearyl trimethyl ammonium chloride 1.04 N-lauroyl-N-methyl-β-alanine sodium
0.62 Production Method The above compositions were combined and stirred to obtain a uniform, transparent and stable first agent.

Using 80ml of this product, perform treatment on hair (leave for 20 minutes)
When 80 ml of the preparation (Formulation A) was used (leave for 20 minutes), a very smooth, supple and elastic wave was formed. Neither the practitioner nor the subject used irritation.

Example 16 Permanent wave agent First agent (cysteine type) L-cysteine 6.0 Ammonium thioglycolate solution (containing 50% as thioglycolic acid) 2.0 Monoethanolamine 2.5 Ammonia water reagent special grade (28%) 1.0 Lauryldimethylaminoacetic acid Betaine (30%) 15.0 Stearyltrimethylammonium chloride 0.52 N-Lauroyl-N-methyl-β-alanine sodium
0.31 Disodium edetate 0.10 Purified water Remainder Manufacturing method The above compositions were combined and stirred to obtain a uniform, transparent and stable first agent.

Using 80ml of this product, perform treatment on hair (leave for 20 minutes)
When 80 ml of the preparation (Formulation A) was used (leave for 20 minutes), a very smooth, supple and elastic wave was formed. Neither the practitioner nor the subject used irritation.

Example 17 Permanent Wave Agent Second Agent (Sodium Bromate) Sodium Bromate 7.0 Monobasic Potassium Phosphate 0.5 Disodium Hydrogen Phosphate / 12 Sodium Salt 0.05 Sodium Benzoate 0.05 Lauryl Dimethylaminoacetate Betaine (30%) 15.0 Stearyl trimethylammonium chloride 1.04 Potassium myristoyl glutamate 0.87 Purified water Remainder Manufacturing method The above compositions were combined and stirred to obtain a uniform, transparent and stable second agent.

Use 80ml of the first agent (Prescription B) and apply to the hair
After 10 minutes) and using 80 ml of this product (15 minutes left), a very smooth, supple and elastic wave was formed. Neither the practitioner nor the subject used irritation.

Example 18 Permanent Wave Agent Second Agent (Hydrogen Peroxide) Hydrogen Peroxide (30%) 9.0 Potassium Monophosphate 0.3 Methylparaben 0.1 Lauryldimethylaminoacetate Betaine (30%) 20.0 Stearyltrimethylammonium Chloride 2.09 N- Lauroyl-N-methyl-β-alanine sodium
1.23 Purified Water Remaining Manufacturing Method The above compositions were combined and stirred to obtain a uniform, transparent and stable second agent.

Use 80ml of the first agent (Prescription B) and apply to the hair
After 10 minutes), 80 ml of this product was used (5 minutes left), and a very smooth, supple and elastic wave was formed. Neither the practitioner nor the subject used irritation.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yasunari Naka 1050 Nippa-cho, Kohoku-ku, Yokohama-shi, Kanagawa Prefecture

Claims (1)

(57) [Claims] Claims: 1. A composition comprising one or more quaternary ammonium salt type cationic surfactants and one or more carboxylate type anionic surfactants,
Is in the range of 4/6 to 8/2, and does not contain the silicone polymer represented by the general formula (A). (Wherein, R represents hydrogen or a trimethylsilyl group, R ¹ represents a hydroxyl group or a methyl group, R ² represents an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 1 to 4 carbon atoms. Represents a group, x represents a number from 4 to 500,
y represents a number from 1 to 15)