JP2006347970A - Permanent waving agent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a permanent waving agent composition having excellent waving effects and curly hair straightening effects and holding waving effects imparting curls with excellent elasticity or the curly hair straightening effects over a long period. <P>SOLUTION: The permanent waving agent composition is characterized as comprising the following copolymer (A) in the permanent waving agent composition using a first agent containing a reducing agent and an alkaline agent and a second agent containing an oxidizing agent. (A) a copolymer composed of dimethyldiallylammonium chloride and acrylamide and having 2,000-40,000 average molecular weight. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a permanent wave agent composition. More specifically, the present invention relates to a permanent wave agent composition that has an excellent wave effect or curly hair straightening effect, imparts an excellent wave of elasticity, and can maintain the wave effect or curly hair straightening effect for a long period of time.

  Permanent wave treatment of hair is for permanent waves containing a reducing agent such as thioglycolic acid or its salt, thiolactic acid or its salt, cysteine or its salt, and an alkaline agent such as aqueous ammonia, monoethanolamine or ammonium bicarbonate. By applying the first agent to the hair, the disulfide bonds present in the constituent proteins in the hair are reductively cleaved to make the hair into the desired shape, and then an oxidizing agent such as sodium bromate or hydrogen peroxide as the main component. The disulfide group is reformed at a new position by the treatment with the second agent, and the wave effect or the hair straightening effect is expressed.

In general, depending on the permanent wave processing, the strength of the wave is weak and it is not possible to give a sufficiently elastic wave. Moreover, the wave effect and the hair straightening effect cannot be maintained for a long time. Therefore, attempts have been made to blend various substances into the permanent wave agent composition for the purpose of sustaining the effect of imparting elastic waves and the effect of straightening hair for a long time. For example, it is known that a water-dispersible polyester resin is blended with a permanent wave agent composition (Patent Document 1) or a silk fiber protein hydrolyzate is blended (Patent Document 2).
JP 7-223929 A JP 2003-55172 A

  However, even if these substances are blended, it is difficult to impart sufficient elasticity to the wave, and the wave effect and the hair straightening effect cannot be maintained for a long time.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by blending a permanent wave agent composition with a copolymer having a specific molecular weight, and the present invention has been completed. It was.

  The object of the present invention is to provide a permanent wave agent composition having excellent wave effect and curly hair straightening effect as expected, capable of obtaining a satisfactory elastic wave, and capable of maintaining the wave effect and hair straightening effect for a long period of time. Is to provide.

That is, the present invention is characterized in that a permanent wave agent composition using a first agent containing a reducing agent and an alkali agent and a second agent containing an oxidizing agent contains the following copolymer (A). A permanent wave agent composition is provided.
(A): A copolymer having an average molecular weight of 2000 to 40000 consisting of dimethyldiallylammonium chloride and acrylamide.

Moreover, this invention provides the 1st agent for permanent waves characterized by containing the following copolymer (A), a reducing agent, and an alkaline agent.
(A): A copolymer having an average molecular weight of 2000 to 40000 consisting of dimethyldiallylammonium chloride and acrylamide.

(1) The present invention is a permanent wave composition having an excellent wave effect or curly hair straightening effect.
(2) The present invention is a permanent wave composition capable of imparting a wave having excellent elasticity.
(3) The present invention is a permanent wave composition that can maintain the wave effect and the hair straightening effect for a long period of time.
(4) The said effect of this invention can be achieved by mix | blending the copolymer (A) with a specific low molecular weight. Therefore, in addition to the copolymer (A), it is not necessary to substantially blend other compounding components conventionally used for the above purpose (for example, the polymer compounds of Patent Document 1 and Patent Document 2). It does not matter if they are used together.

  Hereinafter, the present invention will be described in detail.

共重合体（Ａ）の平均分子量は、ゲルパーミエーションクロマトグラフィー（以下ＧＰＣと略す）による重量平均分子量（以下、Ｍｗと略す）で、その平均分子量が２０００〜４００００である。好ましくは、３０００〜３３０００程度である。なお、分子量が小さくなるほど、本発明のパーマネントウエーブ剤組成物で処理したときに、毛髪の弾力が強くなる傾向があり、最も好ましい分子量範囲は３０００〜７０００である。以下にＧＰＣの測定条件を示す。
＜ＧＰＣの測定条件＞
カラム ＯＨｐａｋ ＳＢ−８０４ＨＱ
ＯＨｐａｋ ＳＢ−８０３ＨＱ
ＯＨｐａｋ ＳＢ−８０２ＨＱ
（いずれも昭和電工株式会社製）
カラム温度 ：４０℃
検出器 ：ＲＩ
溶媒 ：０．２５Ｍ酢酸＋０．０５Ｍ食塩（ｐＨ＝３．５）
流速 ：０．７ｍｌ／分
試料濃度 ：０．５％
注入量 ：５０μｌ
標準 ：プルラン
（昭和電工株式会社製；Ｓｈｏｄｅｘ ＳＴＡＮＤＡＲＤ Ｐ−８２）
なお、従来から配合されている、ＤＡＤＭＡＣとＡＡｍの共重合体の重量平均分子量は、数１０万のオーダーを有する分子量の大きいものである。例えば、ＭＥポリマー０９Ｗ（東邦化学工業社製）の重量平均分子量は約４５万であり、本発明に使用する平均分子量２０００〜４００００の共重合体（Ａ）とは、極めて大きく異なる高分子量の共重合体である。 “(A): Copolymer having an average molecular weight of 2000 to 40,000 consisting of dimethyldiallylammonium chloride and acrylamide”
The copolymer (A) used in the present invention comprises dimethyldiallylammonium chloride (hereinafter sometimes abbreviated as DADMAC), acrylamide (hereinafter sometimes abbreviated as AAm), water and isopropyl alcohol (hereinafter referred to as IPA). A copolymer obtained by copolymerization by a conventional method using a polymerization initiator in a mixed solvent, which is a cationic copolymer having an average molecular weight of 2000 to 40000. The monomer composition ratio of the copolymer is preferably DADMAC: AAm of 20:80 to 60:40, and is a random copolymer composed of the following structural units. A specific production method is shown in the synthesis example of the examples. The purified copolymer (A) may be used as an aqueous solution in which it is dissolved at an appropriate concentration, or may be used after being dried until the pure content becomes 100%.

The average molecular weight of the copolymer (A) is a weight average molecular weight (hereinafter abbreviated as Mw) by gel permeation chromatography (hereinafter abbreviated as GPC), and the average molecular weight is 2000 to 40000. Preferably, it is about 3000-33000. In addition, there exists a tendency for the elasticity of hair to become strong when it processes with the permanent wave agent composition of this invention, so that molecular weight becomes small, and the most preferable molecular weight range is 3000-7000. The measurement conditions for GPC are shown below.
<GPC measurement conditions>
Column OHpak SB-804HQ
OHpak SB-803HQ
OHpak SB-802HQ
(Both made by Showa Denko KK)
Column temperature: 40 ° C
Detector: RI
Solvent: 0.25M acetic acid + 0.05M sodium chloride (pH = 3.5)
Flow rate: 0.7 ml / min Sample concentration: 0.5%
Injection volume: 50 μl
Standard: Pull Run
(Made by Showa Denko; Shodex STANDARD P-82)
In addition, the weight average molecular weight of the copolymer of DADMAC and AAm blended conventionally has a large molecular weight having an order of several hundred thousand. For example, ME polymer 09W (manufactured by Toho Chemical Co., Ltd.) has a weight average molecular weight of about 450,000, and is a copolymer having a very high molecular weight that is significantly different from the copolymer (A) having an average molecular weight of 2000 to 40000 used in the present invention. It is a polymer.

  The 1st agent containing the reducing agent and alkali agent used for this invention is not specifically limited. At least a reducing agent such as thioglycolic acid or a salt thereof, thiolactic acid or a salt thereof, cysteine or a salt thereof, and an alkaline agent such as aqueous ammonia, monoethanolamine, or ammonium bicarbonate, which are usually used for the first agent As long as it can be used as a two-component permanent wave agent. The blending amounts of the reducing agent and the alkali agent are not limited, and are appropriately determined according to the reducing agent and the alkali agent to be used.

  The 2nd agent containing the oxidizing agent used for this invention is not specifically limited. At least a compound usually used in the second agent, for example, a peroxide-containing compound such as hydrogen peroxide, sodium peroxide, urea peroxide; sodium perborate, sodium persulfate, potassium monopersulfate, etc. Alkali metal persalt; it may contain an oxidizing agent such as alkali metal bromate such as sodium bromate and potassium bromate, and may be used as a two-component permanent wave agent. The blending amount of the oxidizing agent is not limited, and is appropriately determined according to the oxidizing agent used.

  In the permanent wave agent composition of the present invention, the copolymer (A) may be added to either the first agent or the second agent, or may be added to both. The blending amount of the copolymer (A) is preferably about 0.001 to 5% by mass, particularly 0.01 to 1.0% by mass as the pure content of the first agent relative to the total amount of the second agent. % Is preferred. Usually, it is preferable to mix with the first agent.

  In addition to the above essential components, the first and second agents used in the present invention are usually added with any compounding ingredients used in permanent wave agents within a range that does not affect the effects of the present invention. Can do. Specifically, it can be produced by a conventional method by blending the above essential components and one or more of the following optional blending components.

  Examples of optional components include humectants (eg, propylene glycol, dipropylene glycol, glycerin, etc.); water-soluble polymer compounds (eg, methyl cellulose, hydroxyethyl cellulose, etc.); cationic polymer compounds (eg, cationic cellulose, methacryloxyethyl) Copolymer of trimethylammonium salt and polyvinylpyrrolidone, etc.); water-soluble silicone; nonionic surfactant (eg, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, etc.); amphoteric surfactant (eg, 2-alkyl- N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, trialkylaminoacetic acid betaine, etc.); penetrants (eg urea, alkylurea, benzyl alcohol, monoethylene oxide benzyl ether, etc.); Natural extracts of plants; amino acids; organic acids (eg, citric acid, lactic acid, etc.); inorganic salts (eg, sodium chloride, potassium chloride, etc.); fragrances; preservatives (eg, parabens); sequestering agents (eg, EDTA-3Na) ); UV absorber (for example, oxybenzone, etc.);

  The permanent wave agent composition in the present invention is a concept including both a permanent wave agent and a hair straightener used for so-called straight permanents.

  Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited to this. The blending amount is mass% unless otherwise specified.

"Synthesis example 1 of copolymer (A)"
A glass flask having a capacity of 3 liters equipped with a thermometer, a reflux condenser and a stirrer was charged with 834 g of water and 1172 g of IPA and heated to 60 ° C. Next, a mixed solution of AAm 173 g (2.4 mol), 65% DADMAC aqueous solution 233 g (0.9 mol) and water 92 g, 20% sodium persulfate aqueous solution 97 g, and 20% sodium bisulfite aqueous solution 211 g were separately added. It was dripped at the reactor under stirring from the dropping funnel over 6 hours. After completion of the dropping, the reaction solution was kept at 60 ° C. for 6 hours to complete the polymerization. After completion of the polymerization, stirring was stopped, the lower phase solution separated into two phases was separated, washed with 1400 g of 50% IPA aqueous solution, allowed to stand, and then phase-separated to separate the lower phase solution. This washing operation was performed once more to obtain a polymer solution containing the lower phase.
An equal amount of water was added thereto, and IPA was distilled off under reduced pressure at 80 ° C. under reduced pressure. It was Mw 3,000 as a result of measuring GPC of the obtained polymer aqueous solution.
<GPC measurement conditions>
Column OHpak SB-804HQ
OHpak SB-803HQ
OHpak SB-802HQ
(Both made by Showa Denko KK)
Column temperature: 40 ° C
Detector: RI
Solvent: 0.25M acetic acid + 0.05M sodium chloride (pH = 3.5)
Flow rate: 0.7 ml / min Sample concentration: 0.5%
Injection volume: 50 μl
Standard: Pull Run
(Made by Showa Denko; Shodex STANDARD P-82)

"Synthesis example 2 of copolymer (A)"
A glass flask having a capacity of 3 liters equipped with a thermometer, a reflux condenser and a stirrer was charged with 173 g (2.4 mol) of AAm, 631 g of water and 1172 g of IPA, and heated to 60 ° C. Next, 325 g (0.9 mol) of 47% DADMAC aqueous solution, 47 g of 20% sodium persulfate aqueous solution, and 211 g of 20% sodium bisulfite aqueous solution were respectively added dropwise to the reactor with stirring over 6 hours. . All subsequent operations were performed in the same manner as in Synthesis Example 1 to obtain an aqueous polymer solution having a Mw of 7,000.

“Synthesis Example 3 of Copolymer (A)”
A 3-liter glass flask equipped with a thermometer, a reflux condenser and a stirrer was charged with 173 g (2.4 mol) of AAm, 233 g (0.9 mol) of 65% DADMAC aqueous solution, 698 g of water and 698 g of IPA, and heated to 60 ° C. . Subsequently, 49 g of a 20% aqueous sodium persulfate solution and 211 g of a 20% aqueous sodium bisulfite solution were added dropwise from a separate dropping funnel to the reactor over 6 hours with stirring. All subsequent operations were performed in the same manner as in Example 1 to obtain a polymer aqueous solution having a Mw of 33,000.

"Examples 1-2, Comparative Examples 1-3"
A permanent wave agent composition having the composition shown in Table 1 was prepared and evaluated for wave strength, elasticity, and wave holding power. In addition, each evaluation was implemented with the following method.
<Wave strength>
Using non-chemically treated hair, a hair bundle (12 hairs, length 114 mm) was uniformly wound around a glass rod (Φ = 7 mm), and the first agent was uniformly applied by 80 μl. After 2 minutes at room temperature, 5 rods were placed in a 50 ml glass container, which was closed and treated in a 37 ° C. constant temperature bath for 20 minutes. Then, after washing with water for 1 minute and sprinkling 5 ml of the second agent on the entire rod, the excess liquid was removed, and the mixture was treated in a constant temperature bath at 37 ° C. for 10 minutes. Thereafter, it was washed with water and carefully removed from the rod to obtain a hair coil. The created hair coil was placed on a glass plate in a wet state, and the diameter was measured (mm) to obtain the hair coil diameter. The smaller the value of the hair coil diameter, the stronger the wave. The evaluation criteria were ◎ when the hair coil system was 8 mm or less, ◯ when 8 mm to 8.5 mm, Δ when 8.5 mm to 9 mm, and × when 9 mm or more.
<Resistance>
Using non-chemically treated hair, a hair bundle (12 hairs, length 114 mm) was uniformly wound around a glass rod (Φ = 7 mm), and the first agent was uniformly applied by 80 μl. After 2 minutes at room temperature, 5 rods were placed in a 50 ml glass container, which was closed and treated in a 37 ° C. constant temperature bath for 20 minutes. Then, after washing with water for 1 minute and sprinkling 5 ml of the second agent on the entire rod, the excess liquid was removed, and the mixture was treated in a constant temperature bath at 37 ° C. for 10 minutes. Thereafter, it was washed with water and carefully removed from the rod to obtain a hair coil. The created hair coil was fixed at one end and hung vertically in the air, and the length to the other end was measured (mm) to obtain the hair coil length. It was judged that the smaller the value of the hair coil length, the more elastic. The evaluation criteria are ◎ when the hair coil length is 40 mm or less, ◯ when 40 mm to 50 mm, Δ when 50 mm to 60 mm, and × when 60 mm or more.
<Wave holding power>
The hair coil used for the evaluation of elasticity was left to stand for 1 week at room temperature while hanging vertically in the air. One week later, the hair coil length was measured again to determine the wave retention. Evaluation criteria are as follows: hair coil length before being left as 100%, hair coil length from 100% to 110% ◎, 110% to 120% ○, 120% to 130% △, 130% or more X.

＊１：共重合体（Ａ）：合成例１にて得られたＭｗ３，０００の共重合体を精製して使用した。
＊２：Eastman AQ 38S（イーストマン・ケミカルプロダクツ社製）

* 1: Copolymer (A): The copolymer of Mw 3,000 obtained in Synthesis Example 1 was used after purification.
* 2: Eastman AQ 38S (Eastman Chemical Products)

As shown in “Table 1”, the permanent wave agent compositions of Examples 1 and 2 are stronger in wave, elastic and superior in wave holding power than Comparative Examples 1 to 3. Admitted.

“Examples 3 to 5, Comparative Examples 4 to 5: Relationship between Molecular Weight and Elasticity of Copolymer (A)”
A permanent wave agent composition having the composition shown in “Table 2” was prepared, and the relationship between the molecular weight and elasticity of the copolymer (A) was evaluated. The elasticity was evaluated by the hair coil length in accordance with the above-described experimental method.
Synthesis example 1, synthesis example 2, and synthesis example 3 having different molecular weights of the copolymer (A) were blended, the copolymer pure content was fixed at 1.0% by mass, and the elasticity was compared. The average molecular weight of Synthesis Example 1 is 3000 (Example 3), the average molecular weight of Synthesis Example 2 is 7000 (Example 4), and the average molecular weight of Synthesis Example 3 is 33000 (Example 5). Comparative Example 4 is a comparison in which the copolymer (A) is not blended, and Comparative Example 5 is a comparison in which Marcote 550 (manufactured by CALGON) having an average molecular weight of several hundred thousand is blended.

The results are shown in “FIG. 1”. Compared with the comparative example 4 which does not mix | blend a copolymer (A), all of Examples 3-5 are improving the elasticity of a wave clearly. Further, the smaller the molecular weight of the copolymer (A), the better the elasticity, and Synthesis Example 1 had the highest elasticity improvement effect. On the other hand, the elasticity of the wave was not improved in the comparative example 5 which mix | blended the marcoat 550 whose structure is similar to a copolymer (A).
From the above, when the copolymer (A) is blended in the permanent wave agent composition, the smaller the average molecular weight, the higher the effect of improving wave elasticity, and the lower the molecular weight, the effect is somewhat reduced. In addition, the effect of improving the wave elasticity is not recognized in the case of MERCOAT 550 having an average molecular weight of several hundred thousand.

マーコート５５０（ＣＡＬＧＯＮ社製）共重合体純分８〜９％

Marcote 550 (manufactured by CALGON) copolymer pure content 8-9%

  Next, the formulation example of the permanent wave agent composition by this invention is given.

Example 6
[First Agent] Blending amount (% by mass)
Ammonium thioglycolate solution (50%) 16.0
Diammonium dithioglycolate solution (40%) 3.8
28% ammonium water 1.5
Monoethanolamine 1.0
Ammonium bicarbonate 1.5
Copolymer (A) 0.5
Polydimethylsiloxane 1.0
Cationized hydrolyzed keratin 0.2
Edetate disodium 0.1
POE (20) lauryl ether 0.3
Fragrance 0.1
Purified water balance ――――――――――――――――――――――――――――――――――――
Total 100.0

[Second agent] Compounding amount (% by mass)
Sodium bromate 7.0
Potassium phosphate 0.5
Caustic soda 0.2
Sodium lauryl sulfate solution (40%) 1.5
Carboxyvinyl polymer 0.3
POE (20) oleyl ether 0.5
Purified water balance ――――――――――――――――――――――――――――――――――
Total 100.0

Example 7
[First Agent] Blending amount (% by mass)
Ammonium thiolactic acid solution (60%) 10.0
Thiolactic acid monoethanolamine solution (40%) 10.0
Dithiodilactic acid diammonium solution (40%) 2.5
L-Arginine 1.0
Monoethanolamine 2.0
Copolymer (A) 1.5
Amino-modified silicone 1.0
Oat extract 0.2
Edetate trisodium 0.1
POE (15) cetyl ether 0.3
Fragrance 0.2
Purified water balance ――――――――――――――――――――――――――――――――――――
Total 100.0

[Second agent] Compounding amount (% by mass)
Sodium bromate 8.0
Copolymer (A) 0.5
Potassium phosphate 0.1
Disodium phosphate 0.2
Palm oil fatty acid methyl tauride sodium solution (30%) 1.5
Purified water balance ――――――――――――――――――――――――――――――――――
Total 100.0

Example 8
[First Agent] Blending amount (% by mass)
DL-cysteine hydrochloride 6.5
N-acetyl-L-cysteine 1.5
Ammonium thioglycolate solution (50%) 2.0
Monoethanolamine 3.5
Soy protein 0.1
Edetate trisodium 0.1
Fragrance 0.2
Purified water balance ――――――――――――――――――――――――――――――――――――
Total 100.0

[Second agent] Compounding amount (% by mass)
Hydrogen peroxide solution (3.0%) 6.7
Copolymer (A) 5.0
Phosphoric acid 0.1
Diethylenetriaminepentaacetic acid 5 sodium solution (40%) 0.2
Cetanol 0.5
Myristyl alcohol 0.5
Stearyltrimethylammonium chloride 1.0
POE (8) cetyl ether 0.2
Acrylic acid / alkyl methacrylate copolymer 0.3
Purified water balance ――――――――――――――――――――――――――――――――――
Total 100.0

Example 9
[First Agent] Blending amount (% by mass)
Sodium pyrosulfite 3.0
Urea 3.0
Monoethanolamine 3.0
2-Amino-2-methylpropanol 1.0
Copolymer (A) 0.01
Hydrolyzed silk solution disodium edetate 0.1
Fragrance 0.2
Purified water balance ――――――――――――――――――――――――――――――――――――
Total 100.0

[Second agent] Compounding amount (% by mass)
Sodium bromate 1.0
Potassium phosphate 0.1
POE (3) sodium lauryl sulfate solution (30%) 0.5
Behenyl alcohol 0.3
Cetostearyl alcohol 1.5
POE (50) oleyl ether 0.2
Sodium polyacrylate 0.1
Purified water balance ――――――――――――――――――――――――――――――――――
Total 100.0

Example 10
[First Agent] Blending amount (% by mass)
Ammonium thioglycolate solution (50%) 4.0
Ammonium thiolactate solution (60%) 3.0
N, N′-Diacetylcystine 1.0
Monoethanolamine 1.3
Behenyl alcohol 3.0
Cetanol 3.0
Distearyldimethylammonium chloride (75%) 1.0
POE (15) oleyl ether 0.5
Cationized cellulose 1.0
Copolymer (A) 0.001
Edetate disodium 0.1
Fragrance 0.2
Purified water balance ――――――――――――――――――――――――――――――――――――
Total 100.0

[Second agent] Compounding amount (% by mass)
Hydrogen peroxide solution (30%) 6.8
Phenacetin 0.1
Phosphoric acid 0.2
Disodium phosphate 0.1
Methylparaben 0.1
Behenyl alcohol 3.0
Cetostearyl alcohol 3.0
N-myristoylmethyl-N-taurine sodium 1.0
POE (15) oleyl ether 0.2
Aminopropyl dimethicone 0.1
Purified water balance ――――――――――――――――――――――――――――――――――
Total 100.0

  According to the present invention, there is provided a permanent wave agent composition that has an excellent wave effect or curly hair straightening effect, imparts an excellent elastic curl, and can maintain the wave effect or curly hair straightening effect for a long period of time. it can.

It is the graph which showed the elasticity of the wave.

Claims (2)

A permanent wave composition comprising the following copolymer (A) in a permanent wave composition using a first agent containing a reducing agent and an alkaline agent and a second agent containing an oxidizing agent: object.
(A): A copolymer having an average molecular weight of 2000 to 40000 consisting of dimethyldiallylammonium chloride and acrylamide. 1st agent for permanent waves containing the following copolymer (A), a reducing agent, and an alkaline agent.
(A): A copolymer having an average molecular weight of 2000 to 40000 consisting of dimethyldiallylammonium chloride and acrylamide.

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