WO2007108460A1

WO2007108460A1 - Shape retaining agent for permanent waves and method of retaining the shape of permanent waves using the same

Info

Publication number: WO2007108460A1
Application number: PCT/JP2007/055614
Authority: WO
Inventors: Saburo Uchikuga
Original assignee: Cosmebrain Corporation
Priority date: 2006-03-20
Filing date: 2007-03-20
Publication date: 2007-09-27
Also published as: JPWO2007108460A1; JP5166867B2

Abstract

[PROBLEMS] A shape retaining agent for permanent waves which exerts an excellent waving effect, never damages the hair and is safe to the hair and skin, and a method of retaining the shape of permanent waves with the use of the agent. [MEANS FOR SOLVING PROBLEMS] Using a thiol sulfonate compound as the active ingredient.

Description

Specification

Permanent wave retention and forming agent, and method for retention and formation of permanent vein using the same

Technical field

[0001] The present invention relates to a permanent wave retention and formation agent, and more particularly, to effectively effect wave action, not to cause oxidative damage to hair, and to be safe for scalp and skin. The present invention relates to a permanent wave holding and forming agent and a method for forming a permanent wave using the same.

Background art

[0002] Permanent wave preparations are required to have a wave forming or hair straightening effect as a basic function. The effect expression theory of permanent waving agents is generally defined as "the cleavage of cystine bond in hair by one agent and the recombination by two agents", so that the first agent is a reducing agent and the second agent is a second agent. Is blended with an oxidizing agent as an active ingredient.

[0003] As a permanent waving agent first agent (sometimes simply referred to as the first agent), thioglycolic acid, cystine, cysteamine, thiolactic acid, sulfite and the like are used, and at least one of these reducing agents is hair. Reduces the disulfide bond of keratin and breaks the S-S bond.

[0004] A brominated acid salt, hydrogen peroxide or the like is used as a permanent waving agent second agent (simply referred to as the second agent), and at least one of these oxidizing agents is a permanent waving agent. The hair keratin thiol group SH reduced and produced by the first agent is recombined in a form different from the original to reform the disulfide group.

[0005] On the other hand, since the second agent currently used is a strong oxidizing agent, only care must be taken in its handling, decoloring the hair, or using it for eyelash perms, etc. Trabl has been reported, and there is a need in the field to develop permanent wave holding and forming agents with less of these problems!

Non-Patent Document 1: Science of Wave, Japan Permanent Wave Liquid Industry Association, p. 26-27 (2003) New Beauty Publishing Co., Ltd.

Patent Document 1: EP 0 448 185 A2

Patent Document 2: Special Feature 2002- 529488

Disclosure of the invention

Problem that invention tries to solve

[0006] As described above, the inorganic bromate and hydrogen peroxide which are generally used as the second agent at present are also strong oxidizing agents, and therefore have their own toxicity. The thiol group of the hair keratin formed by the reduction of the first agent is excessively oxidized to cystic acid (one SO 2 H), which is the main cause of hair damage. Also because of its strong oxidizing power,

3

The melanin is destroyed and the so-called "fading Z decoloring" t occurs in a desirable manner.

[0007] Furthermore, these oxidizing agents adhere to the scalp and skin, causing various problems, and in the case of "eyelash perms", in particular, careful attention and advanced techniques are required.

[0008] In view of these points, the present invention provides a permanent wave holding and forming agent excellent in wave effect, causing no hair damage, safe for hair and skin and permanent wave holding formation using the same. It was made for the purpose of developing a new method. Means to solve the problem

The constitution of the permanent-wave holding formation of the present invention made for the purpose of solving the above-mentioned problems is characterized in that a thiol sulfonate compound is used as an active ingredient.

[0010] Further, the constitution of the permanent wave holding and forming method of the present invention made for the purpose of solving the above-mentioned problems is that the permanent wave treating agent was reductively cut by the first agent permanent agent. A hair keratin is reacted with the retention and formation agent according to any one of claims 1 to 3 to retain and form a permanent wave.

[0011] Furthermore, another configuration of the permanent wave holding and forming method of the present invention made for the purpose of solving the above-mentioned problems is a hair reductively cut by the permanene tave agent first agent in the permanent wave treatment step. The keratin is reacted with the retention forming agent according to any one of claims 1 to 3 as a pretreatment to pre-fix the permanent wave. After that, it is characterized by holding and forming the wave using a low concentration of hydrogen peroxide or bromate.

If attention is paid to the fact that the conventional second agent bromate, hydrogen peroxide, etc. requires the interposition of oxygen, the wave formation of hair can be achieved by the system without the interposition of oxygen. We have constructed a new permanent wave system that does not involve oxygen, as it may prevent hair damage, that is, generation of cysteic acid by peroxyacid of thiol group and “fading Z decolorization” by destruction of melanin pigment. The screening of compounds suitable for it was carried out intensively.

As a result, a water-soluble thiol sulfonate complex (a compound having a single S—SO— structure

2

For the first time found that the object fits this purpose.

Until now, prior art made for the same purpose includes disulfide compounds such as cystamine.

However, it is not enough in terms of the stability and effect of the compound.

Further, as a result of further researches, it is possible to use a compound having a thiolsulfonate group represented by the general formula (1) shown in the following chemical formula 1, for example, from the viewpoint of availability and price.

In contrast to conventional second agents, it forms a wave of hair that is safe without intercalating oxygen in the reaction system, and does not damage conventional hair and skin, and as a fixing agent. It confirmed that it could be used and came to this invention.

[Formula 1]

3⁄4——NH-CH-CH ₂ -S0 ₂

I · nHX (1)

Rl one NH- † H-CH ₂ -S

R ₂

Note: H, CH ₃ CO, NH ₂ (NH =)-C

R2: H, COOH

n: 0, 1, 2

X: CI, Br, HSO4

In the present invention, all compounds having a thiol sulfonate group can be suitably used, as long as the compounds of the general formula (1) can be used. Compounds are useful It is illustrated as a compound.

(I) 2-Aminoethyl 2-Aminoethanethiolsulfonate Dihydrochloride Z Sulfate [Formula 2]

R, = H, R ₂ = H, n 2 2/1, X = CI / HS 0 ₄ NH ₂ -CH ₂ -CH ₂ -S 0 ₂

I ■ 2HGI ZH ₂ S0 ₄

NH ₂ -CH ₂ -CH ₂ -S

(II) 2 guardinoethyl 2 guardinoethane thiol sulfonate dibromate [Chemical formula 3]

R] = NH ₂ (NH =) -C-, R ₂ = H, n = 2, X = Br

NH ₂ (NH =) -C-NH-CH ₂ -CH ₂ -S 0 ₂

I ■ 2HBr

_{NH 2 (NH =) -C-} NH-CH 2 -CH 2 -S

(III) 2-acetamidoethyl 2-acetamidoethanethiol sulfonate,

[Formula 4]

R〗 = CH3CO-, R ₂ = H, n = 0,

CH ₃ C 0 -NH-CH ₂ -CH ₂ -S 0 ₂

I

CH ₃ C 0 -NH-CH ₂ -CH ₂ -S

(iv) cystine thiol sulfonate R, = H, R ₂ = C00H, n = 0

NH ₂ -CH (C00H) -CH ₂ -S0 ₂

NH ₂ -CH (COOH) -CH ₂ -S

(v) Guar cystine thiol sulfonate

[Chemical 6]

R, = NH ₂ (NH =) -C-, R ₂ = COOH, n = 0

_{NH 2 (NH =) -C-} NH-CH (COOH) - CH 2 - S0 2

_{NH 2 (NH =) -C-} NH-CH (COOH) - CH 2 - S

(VI) N-acetyl cystine thiol sulfonate

[Chem. 7]

CH ₃ C 0-NH-GH (COOH) 1 CH _2- S 0 ₂

CH3CO-NH-CH (COOH) - Effect of CH ₂ -S invention

The present invention is characterized in that a compound having a thiol sulfonate group is newly used as a permanent wave holding and forming agent. Unlike the conventional strong oxidants, this compound has the property that it does not require the intervention of oxygen at the time of wave fixation of the hair, so damage to the scalp, skin and hair, which is highly safe, and troubles The effect of this method is significantly reduced, and the destruction of the melanin pigment in the hair is also suppressed, so that the decoloring of the hair does not occur, and a remarkable effect is exerted, and the force and the wave effect are excellent.

[0018] The compound is highly safe, so it can be used as a completely new second agent, thereby causing serious problems as in the conventional second agent even if it adheres to the hair and skin. about Because of their strength, the burden on practitioners such as cosmetologists can be greatly reduced.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is characterized in that a thiol sulfonate complex is used as an effective component of a permanent wave retention forming agent. In the present invention, unlike the conventional inorganic oxidizing agents which cause oxygen in the reaction system to acidify the thiol group of reduced hair keratin and form a disulfide bond, the property of the mechanism is completely different. It is an organic compound permanent fiber retention and forming agent. Although the reaction mechanism is unknown, it is possible to fix effectively formed waves of reduced hair keratin.

FIG. 1 is a plan view showing the results of treatment with a perm agent, and the left side of FIG. 1 shows those treated with a commercially available perm first agent (thiodaryl acid) to a second agent (hydrogen peroxide), The right side of FIG. 1 shows the same commercially available perma first agent (thiodaryl acid) to the second agent treated with a 5% aqueous solution of the hydrochloride salt of compound [I].

[0021] When the thiol sulfonate compound of the present invention is used as a permanent wave retention and formation agent. It is a 0.1 to 50% solution, preferably a 3 to 10% solution. In addition, the action time of this agent is 1 to 45 minutes, preferably 15 to 30 minutes, depending on the properties of the hair and the temperature of use. The pH during use is preferably neutral or less. The temperature at the time of use is 5 to 60 ° C, preferably 20 to 50 ° C.

When the thiol sulfonate complex is a mineral acid salt, it is preferable to neutralize and wash with a dilute alkaline agent such as ammonia, monoethanolamine, caustic soda or carbonate after treatment.

When the compound of the present invention is used as a second wave fixing agent, the first agent and existing ones may be used depending on the properties of the hair, the temperature of use, the degree of wave, etc., in addition to using the present agent alone. Depending on the combination with the second agent, V, 、, ろ can be adopted.

After using the thiol sulfonate compound as a prefix, conventional bromate or hydrogen peroxide can also be used as a postfix. In this method, after treating with a hair keratin first agent for a certain period of time, it is rinsed off and subsequently treated with thiol sulfonate mixture as a pre-fixing agent, and then further treated with bromate or hydrogen peroxide. Fix the cube using. In this case, the oxidizing agent is preferably 0.1 to 1% for hydrogen peroxide, preferably 1 to 5% for bromate, and preferably for low concentrations. [0024] The advantage of this method is that the thiol sulfonate complex is susceptible to damage, that is, the portion of the hair keratin where the cystine group of the hair keratin is prone to become cystic acid is immobilized by the peroxyacid, and so on. This is a method to complete fixation afterward with the conventional second agent. By using this method, even if the second agent which is a conventional oxidizing agent is used, damage to the hair can be reduced and wave fixation can be effectively performed.

[0025] First, as the present inventor, "less damaged, safe permanent wave first agent".

N guaninoless has been developed. (WO 2006/103860 A1)

When used as a permanent waving agent first agent and using a thiol sulfonate alone or in combination with a conventional second agent as an immobilizing agent, a completely new, safe, permanent system that does not damage the hair can be obtained. It is an ideal permanent wave system that minimizes hair damage during the hair reduction and wave retention stages.

The above examples are illustrated in the following examples, but the present invention is not limited only to these examples.

(Example 1: Synthesis of thiol sulfonate compound)

(1) Synthesis of 2-aminoethyl 2-aminoethanethiol sulfonate dihydrochloride Z sulfate

A solution of 114 g (1.0 mol) of aminoethanethiol. Hydrochloride and 1.0 g of potassium iodide is dissolved in 200 ml of water in a 2-liter reaction vessel, and a 1.5 molar solution of a 30% hydrogen peroxide solution with cooling and stirring (approximately Add 140 ml) dropwise below 25 ° C and leave to stir overnight. The reaction solution is concentrated under reduced pressure, acetic acid is added for crystallization, and the crystals are collected by filtration.

[0027] The collected crystals are dissolved in a small amount of water, covered with 95% ethanol, and recrystallized. The obtained crystals were filtered and dried to obtain 110 g of 2 aminoethyl-2 aminoethane thiol sulfonate dihydrochloride. Yield: 85.5%

Elemental analysis was as follows.

C (%) H (%) N (%)

(Measured site) 18.58 5.65 10.93

(Theoretical value) 18.67 5.49 10.89

Using aminoethanethiol sulfate instead of aminoethanethiol hydrochloride The compound was synthesized by the same method as described above to obtain 2-aminoethyl mono-aminoethanethiol sulfonate sulfate.

(II) 2 Guadinoethyl-2 Guadinoethanethiolsulfonate Dibromate

S (aminoethyl) isourea · 2-bromate (AET · 2HBr) 11.24 g (40.0 mmol) is quickly added to a solution of 12.6 g (40.0 mmol) of hydroxide barium octahydrate Z water, 200 ml, 10 After a minute, add 4.0 g of concentrated sulfuric acid under ice cooling. A small amount of iodine and about 6.2 ml equivalent to 60 mmol of 30% hydrogen peroxide are added. After standing for 2 days at 30 ° C., the precipitate (BaSO 4) is filtered off. The filtrate is concentrated under reduced pressure,

Four

Crystals were crystallized from an acetic acid solution to obtain 5.5 g (72%) of 2-glydinoethyl 2-glydinoethanethiolsulfonate dibromate of 5.5 g (72%) m.p.

(III) 2 acetamidoethyl-2 acetamido ethane thiol sulfonate,

2. Dissolve acetamidoethanethiol (122 g) and potassium iodide (1 g) in water (375 ml) and add 150 ml of 30% hydrogen peroxide at 25 ° C or less while stirring under cooling, and stir overnight put. Evaporation and crystallization, the crystals were recrystallized from 1-butanol to obtain 116.5 g (yield: 87%), 2-acetamidoethyl 2-acetamidoethanethiolsulfonate, m.p. 95-96 ° C.

[0030] (IV) Cystine thiol sulfonate

9.6 g (0.04 mol) of L-cystine is dissolved in 222 ml of 88% formic acid by stirring in 500 ml of reaction Kolbene, and the following operations are carried out at 20 ° C. by cooling. Add 8 ml of 30% concentrated hydrochloric acid, and then add 10 ml of 30% hydrogen peroxide dropwise. Stirring is continued for 2.5 hours, the solution is concentrated under reduced pressure until it becomes syrupy, 100 ml of water is added, and about 10 ml of concentrated aqueous ammonia is added until the pH is 3-4. The mixture was allowed to stand overnight at 4 ° C., and the precipitated crystals were filtered and dried under reduced pressure to obtain a cystine thiolsulfonate of 9.3 g (yield 85%), m.p. 172-175 ° C.

(V) Guar cystine thiol sulfonate

Guar cystin thiol sulfonate was obtained in the same manner as in the synthesis of compound (IV), using N-gua L-L cystine instead of L-cystine.

(VI) N-Acetyl cystine thiol sulfonate

N-acetyl cystine thiolsulfonate was obtained in the same manner as in the synthesis of compound (IV), using N-acetyl-L-cystin in place of L-cystin.

Example 2 When a thiol sulfonate compound is used alone as a wave retention forming agent <Permanent Wave Test Method>

Using commercially available test hair, it was washed with dilute neutral detergent, sufficiently rinsed and air dried hair tress (20) was set in the Kirby method measuring instrument and subjected to a wave test. First liquid treatment (30 minutes, 25 ° C) to second liquid treatment (30 ° C, 25 minutes) to water washing (10 minutes) However, in the case of sodium hydrogen sulfite and sodium sulfite, 40 ° C, 30 minutes It was processed.

After treatment, carefully remove the hair bundle from the appliance and measure the distance (bcm) of the five ridges of the formed web on the filter paper, and the wave efficiency (%) (WE%) according to the following equation ) Was calculated.

[Equation 1]

W. E. (%) = 100 100 X (b-a) / (c-a)

a: The distance from the first to the sixth of the rod of the device (30 mm)

b: distance between 5 mountains of formed wave (mm)

c: Distance when straightening b (90 mm)

The experimental results are shown below.

The reducing agent of the first agent was a commercially available thioglycolic acid preparation, and the fixative was treated with a 6% aqueous solution of thiol sulfonate compound (1).

[Table 1]

*): Benezelve's Wave Perm First Solution (Thioglycolic Acid Preparation), Dariya Co., Ltd. **): Benezel Wave Perm Second Solution (Hydrogen Peroxide Preparation), Dariya Co., Ltd.

***) After use, it was neutralized and washed with 2% sodium bicarbonate.

The figures in the table are the average of the W.E. (%) of three tests under the same conditions.

(+): Fading of the treated hair is slightly recognized.

(1): No discoloration of the treated hair is observed.

[0037] Rather than using a commercially available oxidizing agent (hydrogen peroxide), the thiol sulfonate compound is more The wave effect is good when used as a fixing agent for the Eve, and no hair discoloration is observed.

(Example 3)

A method of pre-fixing with a thiol sulfonate complex as a second agent and then treating with an existing second agent.

The reduced hair treated with the first agent was treated with a 7% aqueous solution of each thiol sulfonate compound as a pre-fix (25 min Z30 ° C) and subsequently acidified with dilute 1% hydrogen peroxide. . (25 minutes Z30 ° C)

[Table 2]

*): Benezel wave perm liquid first drug (glycolic acid formulation), Dariya Co., Ltd.

**): Benezel wave perm liquid second agent (hydrogen peroxide preparation), Dariya Co., Ltd.

(+): Fading of the treated hair is slightly recognized.

(-): No fading of the treated hair is observed.

[0040] As a result, using a thiol sulfonate complex as a pre-fixing agent, and subsequently using a dilute oxidizing agent, it is effective to use a wave that does not damage the hair. It can be fixed to

Example 4

Combination of first agent N-guanyl cysteine and first agent.

A 0.22 molar aqueous solution of the first agent reducing agent is adjusted to pH 9 with ammonia and treated with a 7% aqueous solution of the hydrochloride salt of compound (1) as the pre-fixing agent, followed by the second agent of the oxidizing agent. Was treated with 3% sodium bromate (PH 6.5).

[Table 3] First agent 7% aqueous solution of compound (1) (+) 3% sodium bromate solution thioglycolic acid 19.3 (-) 21.3 (-)

Cystein 15.6 (-) 17.3 (one)

N-guancist 23.1 (1) 26.8 (-)

(1) no discoloration of the treated hair is observed.

[0043] The results of the comprehensive sensory test were obtained in the order of N-guercystin> cystine> thioglycolic acid.

As above. The combination of N-guarstein and thiol sulfonate as a first agent produces a permanent system with extremely high wave damage and less hair damage.

Industrial applicability

As is apparent from the above, according to the present invention, as in the conventional oxidizing agents such as hydrogen peroxide and bromate, since the reaction system does not intervene in oxygen, peroxidation and fading Z decolorization Because it does not damage the hair due to acid, it is also safe for the scalp and skin, so it forms a wave of hair that is more efficient than the conventional product and immobilizes it with a mechanism that is completely different from conventional products. It is intended to provide a permanent wave retention and formation agent of an organic compound. Brief description of the drawings

FIG. 1 is a plan view showing the results of treatment with a perm agent.

Claims

[Claim 1] A permanent disk retention-forming agent characterized by comprising a thiol sulfonate compound as an active ingredient o A thiol sulfonate compound is represented by the following formula 1 and is represented by the general formula (1) It is a compound represented by these, The retention formation agent of Claim 1 characterized by the above-mentioned.

[Formula 1]

R]-H-CH-CH _2- S0 ₂

NH- † H-CH ₂ -SR,

Note: H, CH ₃ CO, NH ₂ (NH =)-C

R2: H, COOH

n: 0, 1,

2

X: CI, Br, HSO4

[3] Thiolsulfonate compound is 2-aminoethyl 2-aminoethanethiolsulfonate mineral acid salt, 2 guardoinoethyl 2-grazinoethanethiol sulfone monocarbonate mineral acid salt, 2-acetamide ethoxide The compound according to claim 1 or 2, which is a 2-acetamidoethanethiol sulfonate, cystine thiol sulfonate, guar cystine thiol sulfonate, or N-acetyl cystine thiol sulfonate. Retention forming agent.

[4] In the permanent wave treatment step, hair keratin reduced by permanent wave first agent is reacted with the retention forming agent according to any one of claims 1 to 3 to hold and form permanent waves. A permanent wave holding and forming method characterized by

[5] In the permanent wave treatment step, hair keratin reduced by permanent wave first agent is reacted with the retention agent according to any one of claims 1 to 3 as a pre-treatment agent to obtain permanent wave. A permanent wave characterized by holding and forming the wave using hydrogen peroxide or bromate after pre-fixing. Holding formation method.

[6] The holding and forming method according to claim 4 or 5, wherein the permanent waving agent first agent is N-guarantine.

[7] With or without oxygen in the reaction system, it is possible to safely and effectively improve the permanent wave effect without causing oxidative damage such as peroxidation or decolorization to the hair. The holding formation method in any one of Claims 4-6.