JPS62205014A - Hair deformation treating agent - Google Patents

Abstract

PURPOSE:A hair deformation treating agent, containing a 3-mercapto-2- hydroxypropyltrialkylammonium salt as a principal ingredient and capable of forming firm waves in the hair at a relatively low temperature in a relatively short time by simple operation. CONSTITUTION:A hair deformation treating agent, containing a compound, expressed by the formula (R1 is 1-12C alkyl; R2 and R3 are alkyl; X is halogen) and having stable and high waving effect, e.g. 3-mercapto-2- hydroxypropyltrimethylammonium chloride, etc., as a principal ingredient and useful as the first solution of a two-bath cold permanent wave solution or heating type one-bath permanent wave solution. Since the above-mentioned treating agent has the above-mentioned effect and particularly no alkali agent or reducing substance and oxidizing substance in a high concentration are used in the heating type one-bath permanent wave solution, damage of the hair caused by elution of hair proteins can be reduced and the storage stability is good with slight irritancy to the skin.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a novel hair deformation treatment agent.

[Conventional technology and its problems]

The most common way to give R1 waves to your hair is to
First, a first liquid for permanent waves containing a reducing agent such as thioglycolic acid and cysteine is used to reduce and open the SS bonds in the hair to release bonds between amino acid side chains, thereby forming hair waves. 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 main component of which is an oxidizing agent such as bromate, perborate, or hydrogen peroxide. .

Thioglycolic acid has traditionally been used in large quantities as a rust starter in the first liquid for permanent waves, but this has a bad odor that causes discomfort to busy users and is highly irritating. The drawback was that it caused a lot of damage to my hair.

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 cysteine, which is insoluble in water. There have been problems such as adhesion to hair and skin, impairing the aesthetic appearance and feel, and causing skin irritation.

[Means for solving problems]

In such a situation, the present inventor conducted intensive research and found that the general formula (I), R8R,OH(I) (wherein, ltI represents an alkyl group having 1 to 12 carbon atoms, and R7
and 16 represents a lower alkyl group, and X represents a halogen atom) It was discovered that the 3-mercapto-2-hydroxyclobyl trialkylammonium salt represented by did.

Therefore, the present invention provides a hair modification treatment agent containing 3-mercapto-2-hydroxyclobyl trialkylammonium salt (1) as a main component.

The compound of formula (1) which is the main component of the present invention is 3
Examples include -mercapto-2-hydroxypropyl-trimethylammonium chloride, -dimethylethylammonium chloride, -dimethylbutylammonium chloride, -dimethylglobyl ammonium chloride, -dimethyloctylammonium chloride, -dimethyllauryl ammonium chloride, etc. It will be done.

These compounds (I) are disclosed in, for example, JP-A-55-5916.
It is prepared according to method No. 0 by reacting glycidyl trialkylammonium halide with sodium hydrosulfide in the presence of carbon disulfide and alcohol, and acidifying the reaction solution.

The hair modification treatment agent of the present invention can be in the form of a first solution of a cold/warm permanent waving agent or a warm/warm permanent waving agent.

The two-thermal @1-liquid treatment agent contains 1 to 20% of 3-mercapto-2- and droxypropyl trialkylammonium salt.
, preferably 2 to 10%, and dissolved in water using a buffer to a concentration of 4 to 11%, preferably 7 to 9%. 4. It is made by adjusting. In addition, the -bath type treatment agent is
3-mercap)-2-hydroxyclovir triplekylammonium salt from 0.1 to 5.0, preferably 0.5
It is prepared by dissolving it in water to a concentration of ~3.01% and adjusting the pH to -6 to 10, preferably 7 to 9, using a buffer.

Examples of buffering agents include citric acid/disodium hydrogen phosphate, hydrochloric acid/sodium parbital/sodium acetate, hydrochloric acid or maleic acid/trishydroxyaminomethane, phosphoric acid: potassium or sodium hydrogen phosphate/dipotassium hydrogen phosphate or sodium, Hydrochloric acid or phosphoric acid: potassium or sodium hydrogen/sodium tetraborate, phosphoric acid: potassium or sodium hydrogen/sodium or potassium hydroxide, hydrochloric acid/collidine, boric acid/sodium carbonate or sodium tetraborate, hydrochloric acid/aminomethyl Propanediol, glycine/sodium or potassium hydroxide, boric acid/
Examples include combinations of sodium hydroxide, hydrochloric acid/sodium dimethylglycine, sodium hydrogen carbonate/sodium carbonate, sodium tetraborate/sodium hydroxide, sodium hydrogen carbonate/sodium hydroxide, or water-soluble ammonium salt/ammonia. Among these, the combination of water-soluble ammonium salt/ammonia, water-soluble ammonium salt/arginine,
A combination of basic amino acids such as lysine is preferred, and the water-soluble ammonium salt is preferably hydrochloride, carbonate, or bicarbonate. These buffers are present in the processing agent of the present invention in a total amount of 0.
．． 05 to 10%, preferably 0.1 to 5%.

The hair deformation treatment agent of the present invention includes the following (:) peptides or derivatives thereof, (l+) divalent metal salts, (+ii) cationic or amphoteric polymers, etc. for the purpose of improving wave forming effects and preventing hair damage. It is preferable to use 1#i or a combination of two or more.

(1) Peptides or derivatives thereof ■ Basic amino fR (e.g. lysine, arginine) 1
Dimeric or higher peptides synthesized from a or two species, or acidic amino acids (e.g. daltamic acid, asparagine #1
) peptides synthesized from lfi or 2ff of , conglycinin, a hydrolyzate produced as a decomposed derivative of casein protein or soybean protein by the method described in JP-A No. 57-85308, etc.; ■ Naturally occurring hormones or physiological FB sex peptides, e.g. Examples include insulin and oxidized glutathione. Among these, polylysine with a molecular weight of 10,000 or less, preferably 5,000 or less; hydrolysates of keratin protein, large protein jX, etc.; and insulin are particularly preferred.

These peptides or derivatives thereof may be used alone or in combination of 2 or more to add 0.01 to 502 Jtf to the hair deforming treatment agent.
f1% (hereinafter simply referred to as love), preferably 0.1 to 1
Contains 0%.

(ii) General formula % formula % of divalent metal salt arrow (wherein A is Ba % Ca , Zn 1Ni and M
g is a cation distributed from the group υ, B is F-1
C/-1Br''', ■-1802'''', po3'''', O
represents an anion selected from the group consisting of H- and co2-, m represents the valence of B), or acetate, citrate, lactic acid of the divalent metal (A) above. Examples include organic acid salts such as salts, succinates, and tartrates. Among them, acetates and chlorides of calcium, zinc, nickel, magnesium, and barium are particularly preferred.

These divalent metal salts may be used alone or in combination of two or more, and in the final use form, the amount of metal ions is 10 to 5000 pp.
m, preferably 100 to 11,000 pp.

(iii) Cationic or amphoteric polymer JP-A-56-
The following may be mentioned which are water-soluble or soluble in water in the presence of an inorganic or organic salt as described in No. 92812.

■ Copolymer of acidic vinyl monomer and basic vinyl monomer Typical examples include acidic vinyl monomer or its salt 4
5 to 55 molti, basic vinyl monomer or its salt 45 to
Examples of amphoteric copolymers obtained by copolymerizing a monomer mixture of 55 molti at 150°C in the presence of a known radical polymerization initiator and in the presence or absence of a known accelerator are listed below. be able to. 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 adjusted to 114 so that the net charge is approximately O.

Acidic vinyl 4L-mer is a carboxyl group in one molecule,
A compound having an acidic group such as a sulfonic acid group or a phosphoric acid group and a polymerizable vinyl group, such as acrylic acid,
Methacrylic acid, crotonic acid, vinylbenzoic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrene sulfonic acid, vinyl sulfonic acid,
Unsaturated basic acids such as methacrylic acid, 3-methacrylpropanesulfonic acid, itaconic acid, maleic acid,
Examples include unsaturated dibasic acids such as 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 has a primary amino group, 2
A compound having a basic group such as a primary amino group or a tertiary amino group and a polymerizable vinyl group, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylamine, Noprobyl acrylate, dimethylamine propyl methacrylamide, dimethylaminopropylacrylamide, 2
Examples include -vinylpyridine, 4-vinylpyridine, dimethylallylamine, diallylmethylamine, and quaternized products thereof. Quaternary compounds include hydrides, methylated compounds, ethylated compounds, and compounds whose counter anions are chloride ions, bromide ions, halogen ions, hydroxyl ions, methyl sulfate groups, and the like.

■ Amphoteric polymers A typical amphoteric product is an amphoteric monomer obtained by polymerizing an amphoteric monomer represented by the general formula (n) in the presence of a radical polymerization initiator at a temperature range of 20 to 120°C. Examples include polymers.

OR,R.

(In formula (1), R4, R1, R1 are hydrogen atoms or methyl groups, islands, all are methyl groups or ethyl groups, A is 10- or -Ni (-1X is -CO, -8O9 or -P
HO, and υ, m, and n are integers of 1 to 3. ) The amphoteric monomer represented by the general formula (11) can be prepared by reacting an appropriate aminoalkyl ester or noalkylamide of acrylic acid or methacrylic acid with a 2-chton, a long-height phosphite or a hori-like phosphite. can be a threat.

Examples of these compounds include 3-dimethyl(methacroyloxyether) ammonium propanesulfonate and 3-dimethyl(methacroylamide furohil) ammonium propanesulfonate.

The polymerization reaction can be carried out by conventionally known methods, such as bulk polymerization, aqueous solution polymerization, reverse phase suspension polymerization, and precipitation polymerization, at a reaction temperature of 20 to 150°C and in the presence of a radical polymerization initiator. It is carried out smoothly at the bottom.

Examples of radical polymerization initiators include sodium persulfate, potassium persulfate, ammonium persulfate, 2゜2'-azobis(2-amidinopropane) dihydrochloride, benzoyl peroxide, hydrogen peroxide, sodium peracetate, and cumene hydroperoxide. ,
Azobisisobutylnitrile and the like are used. The amount of radical polymerization initiator to be used differs depending on the type a, but generally it is 0. Approximately 01 to 5 f- is suitable. These cationic or amphoteric polymers may be used alone or in combination of 28 [classes or more] to form a hair deforming treatment agent of 0.01 to 2
0% by weight (hereinafter simply indicated by -), preferably 0, 1 to 1
Contains 0%.

Furthermore, other conventionally known ingredients can be added to the hair deformation 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 and anionic surfactants, urea, silicone, aluminum stearate, aluminum compounds such as light bread, organic acids such as citric acid and malic acid, hydrochloric acid, etc. inorganic acids, ethylenediamine, mono-, di- or triethanolamine, basic amino acids such as morpholine, arginine, lysine, ammonia.

Alkaline agents such as caustic soda, hair nourishing agents, sterilizing agents, coloring agents,
Examples include fragrances and the like.

When the treatment agent for deforming raw wheat of the present invention is used as the first liquid of a cold double-bath type permanent waving agent, it is carried out in a conventional manner using a commonly used second liquid. When used as a heating-warming permanent waving agent, the following method is used. That is,
゛First, apply a treatment agent to the hair. Before applying the treatment agent, it is preferable to wrap the hair around a rod, curler, heatable hand-held setting device, etc. to form the desired waves. However, if you want gentle waves, You can use a hair dryer or a brush to create a curl using the usual blow finishing method. The amount of application varies depending on conditions such as heating temperature, but it is usually 910 ~
It is preferable to set it to 150 mj. Then, Mao'It-4
Warm to 0-160°C. The heating temperature and time depend on the degree of hair damage, the type of peptide used, the type of buffer,
It varies depending on the dosage form of the treatment agent, and for healthy hair that has not been permed, dyed, bleached, etc., treatment at high temperatures is advantageous, but considering the damage to the hair caused by heating, the treatment temperature is 40 to 160 degrees Celsius. , especially preferably between 40 and 80°C. Furthermore, it is effective to cover the hair with a cap and further humidify the hair to prevent moisture from evaporating from the hair during heating.

The heating time is preferably 30 minutes or less, and preferably 3 to 10 minutes, for the same reason, although the lower the temperature, the longer the heating time will result in complete recovery. On the other hand, when it comes to chemical treatments such as perms, hair dyes, and bleaching, it is desirable to choose milder treatment conditions.

〔Effect of the invention〕

By using the hair deformation treatment agent of the present invention, strong waves can be formed in hair in a relatively low temperature and short time by simple operations. In addition, each heating 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 explained with reference to synthesis examples and examples.
The present invention is not limited to these examples.

Synthesis Example 3 - Synthesis of mercapto-2-hydroxypropyltrimethylammonium chloride: Sodium hydrosulfide 25.
Add 9 to 301 ethanol and dissolve at 55°C.

A homogeneous solution consisting of 27 g of carbon monosulfide, 50.9 g of glycidyltrimethylammonium chloride, and 1081 g of ethanol is added dropwise to this. This is heated to about 1 at 25℃.
．． Allow to react for 5 hours. Next, 36% 33N hydrochloric acid is added dropwise to make the solution acidic, and then hydrogen sulfide is removed at 40° C. under a nitrogen stream. Next, add 100I of water, top it under reduced pressure, remove carbon disulfide, and reduce to 01I. When the SH group content in the obtained concentrate was analyzed by the iodo oxidation method, it was 2.2.
%, and 3-mercapto-2-hydroxyclovirtrimethylammonium was 12.%. ．． A 5% aqueous solution was obtained.

Example 1 No. 1 for cold and warm permanent wave shown in Table 1.
A liquid was prepared and its wave-forming effect was investigated.

No. 19: Table 1 Second liquid: Sodium bromate 5.0% water 95. O1%
Wrap a healthy hair tress around a rod, apply the first liquid for permanent waves, rinse after 30 minutes at 3, 5, 10, 20 degrees, apply the second liquid, remove the tress after another 10 minutes, and check the wave formation process. Hairdressers were asked to evaluate temporal changes. The evaluation was based on the following evaluation criteria and compared with wave formation in conventional permanent wave treatment. Table 2 shows the results.
Shown below.

Table 2 Evaluation Criteria 20 Strong 0 Slightly Strong Slightly Weak x Weak Example 2 Permanent waving agents of each type of heating shown in Table 3 were prepared and tested for wave formation and wave retention. The results are also shown in Table 3.

[Measurement method] Wave degree and wave retention force measurement test (f) 15c
+n 10 healthy Japanese hairs were used as Ichito, and a glass tube (
10mm diameter) and placed it in each treatment agent at 30°C and 50°C.
℃, 20 minutes each at 80℃? ! ! I crushed it. 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 using the following formula.

X: Total length of hair (15 cIIL) Y: Length of two hair coils an) (ii) After air-drying the hair used in (i) for one day with the hair down, a 0.5% aqueous solution of sodium lauryl sulfate was added at 40°C. The product was soaked in water 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.

Table 3 The basic level of nutrition 1 was set to be the same for all reducing agents.

4 pieces GLFI (7% thioglycolic acid, pF19.0
) for 10 minutes.

It is clear from Table 3 that the product of the present invention is immersed in the second liquid (4% sodium bromate) for 10 minutes, and when the SH temperature is the same, compared to the conventionally used thioglycolic acid and cysteine. , the wave degree and wave holding power are both extremely excellent. .

Example 3 A heating-slanting permanent waving agent having the following composition was prepared.

A, 3-merca 7° to 2-hydroxyglobil trimethylammonium chloride z, o
(%) B, keratin mortar negative hydrolyzate (M, W630) 1.0 C0 stearyltrimethylammonium chloride 1.0D, polyoxyethylene lauryl ether (E, 0.23 mol) 1.0 E, subcarbonate Ammonium 3.0
Arginine...adjusted to 8.5 G, fragrance 0.2 H, ion exchange water balance 100
．． 0 Add A, B, and E to ion-exchanged water, stir, and evenly dissolve.
Add the solution in which G was dissolved to C and D, and finally adjust the pH and pH with KF.
Perform 1st adjustment and manufacture.

Example 4 Eleven heating-slanting permanent waving agents having the following composition were prepared.

A, 3-mercapto-2- and dorogyu cyclovir trimethylammonium chloride 1.5 ('
J) B, Calcium chloride 1.
0C0 Cetyltrimethylammonium chloride
2.0D, ammonium chloride 2.5E,
Ammonia water (28%) pi (
9.0F, fragrance 0.1G, ion exchange water balance ioo.

A, B, and D are added to ion-exchanged water, stirred, and dissolved uniformly. Then, a solution in which F is dissolved in C is added, and any necessary adjustments are made in E for production.

Example 5 A heating type/slanting type permanent waving agent having the following composition was prepared.

A,: 3-Mercapto-2-hydroxychlorotrimethylammonium chloride (2.0 (%)) B, cationized cellulose 0.5 [Commercial product name, Polymer JR400 (Union Carbide grade)] C0 Stearyltrimethylammonium chloride Seid 2・OD, glycyl-glycine 3.52
, +Noji 7 pi
(9, Oi/(Preparation F, Fragrance 0.1 G, Ion Father Replacement Water Balance 100.0 Add A, B, 1) to Ion Father Replacement Water, stir, and toss evenly into the bath, then C ( Add Iζb゛, 9?, and finally E
Manufactured with complete pH adjustment.

that's all

Claims (1)

[Claims] 1. The following general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is an alkyl group having 1 to 12 carbon atoms, R_
2 and R_3 are lower alkyl groups, and X is a halogen atom.