JP2908610B2 - Novel cationic compound and surfactant containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cationic compound and a surfactant containing the same. More specifically, the present invention relates to a cationic compound which has a mild action on the skin and has excellent foaming and detergency, and is useful as a surfactant for cleaning hair or body.

[0002]

2. Description of the Related Art In recent years,
Surfactants used in detergents and the like are required to be excellent in various properties such as biodegradability, safety, and low irritation to eyes and skin in addition to surface activity. As surfactants satisfying these requirements, acylated amino acid surfactants and imidazoline surfactants have been widely used. However, these surfactants are generally excellent in safety and the like, but are inferior in foaming power and detergency, which are particularly important as surfactant properties, so that they themselves can be used alone as a component such as shampoo. In general, a combination with an anionic surfactant such as an alkyl ether sulfate or an alkyl sulfate is generally used.

[0003] Since such anionic surfactants are highly irritating to the skin, they may damage the skin. For this reason, the appearance of an activator having excellent foaming power and detergency and high safety is strongly desired.

[0004]

Means for Solving the Problems In view of the above situation, the present inventors have excellent detergency and foaming power for hair and body washing,
As a result of intensive studies on surfactants having high safety, they have found that a novel cationic compound represented by the following general formula (I) meets the object of the present invention, and have completed the present invention. It is a thing.

That is, the present invention provides a cationic compound represented by the following general formula (I) and a surfactant containing the same.

[0006]

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Wherein R ¹ is a linear or branched C ₈ -C ₂₂
Alkyl group, X is H or a hydroxyl ^{group, R 2, R 3, R} 4 is an alkyl group of C ₁ ~C _4, Z represents OH, an alkyl sulfate group of a halogen atom or a C ₁ -C _4. Hereinafter, the present invention will be described in detail. There are no reports on the cationic compound represented by the general formula (I) in the conventional literature, patents, and the like, and such a cationic compound is novel.

The cationic compound of the present invention can be produced by the following production methods [1] and [2]. Production method [1] R ¹ NH ₂ (R ¹ is a linear or branched alkyl having 8 to 22 carbon atoms.
Represents a hydroxyl group . With respect to the aliphatic primary amine represented by the general formula (VII)

[0009]

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Wherein Y is a halogen atom, X is H or a hydroxyl group, R ² , R ³ and R ⁴ are an alkyl group having 1 to 4 carbon atoms, Z is OH, a halogen atom or a 1 to 4 carbon atoms. Shows an alkyl sulfate group. And the reaction is carried out using a 2- to 3-fold molar amount of the compound represented by the general formula (I) to obtain a cationic compound represented by the general formula (I).

In the reaction between the primary amine and the compound represented by the general formula (VII), it is usually preferable to maintain the pH at 6 to 12 after dropping an aqueous solution of the compound onto the primary amine. An alkali solution such as sodium or potassium hydroxide is charged into the reaction solution as needed.
During the reaction, the pH of the reaction system is maintained in the above range in order to react the primary amine with the compound represented by the general formula (VII). For this purpose, the pH is preferably adjusted to 6 or more. However, if the pH exceeds 12, the compound represented by the general formula (VII) is hydrolyzed. The reaction proceeds at room temperature, but the higher the temperature, the faster the reaction. However, when the temperature and the pH are high, the hydrolysis of the compound represented by the general formula (VII) is promoted, so that the reaction temperature is 100 ° C. or less, preferably
90 ° C or less.

In the production method [1], the molar ratio of the compound represented by the general formula (VII) to the primary amine is usually 2 /
1-3 / 1, preferably 2.1 / 1 to 3.0 / 1. When the molar ratio is less than 2/1, the conversion decreases, and when the molar ratio exceeds 3/1, the compound represented by the general formula (VII) is added to the reaction mixture.
Is undesirable because a large amount of the hydrolyzate of the compound represented by the formula (1) remains. The end point of the reaction between the primary amine and the compound represented by the general formula (VII) can be confirmed by analyzing the remaining amount of the primary amine in the reaction solution by using high performance liquid chromatography.

The primary amine and the compound represented by the general formula (VI)
The reaction time with the compound represented by I) varies depending on the applied temperature and pH, but generally requires 1 to 12 hours. The reaction solution in the method of the present invention may be an aqueous solution or a mixed solution of water and a lower alcohol such as ethanol or isopropyl alcohol, or a diol such as 1,3-propanediol or propylene glycol.

Production method [2] The primary amine used in production method [1] and the following general formula (V
III)

[0015]

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[In the formula, R ² , R ³ and R ⁴ represent an alkyl group having 1 to ⁴ carbon atoms, and Z represents OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. And a glycidyltrialkylammonium salt represented by the general formula (IX):

[0017]

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[In the formula, R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms, R ² , R ³ and R ⁴ are alkyl groups having 1 to ⁴ carbon atoms, Z is OH, a halogen atom or It represents an alkyl sulfate group having 1 to 4 carbon atoms. Is obtained.

In the reaction of the glycidyltrialkylammonium salt of the general formula (VIII) with a primary amine, the molar ratio of the compound of the general formula (VIII) to the primary amine is 2/1 to 3 / 1. When the molar ratio is below this range, the reaction rate decreases, and when the molar ratio exceeds this range, a large amount of the hydrolyzate of the compound represented by the general formula (VIII) remains in the reaction mixture. It is not preferable. The reaction temperature is 50 to 120 ° C, preferably 60 to 100 ° C.
° C. When the reaction temperature is lower than this range, the reaction rate is low, and when the reaction temperature is higher than this range, coloring or the like occurs, which is not preferable.

In the reaction between the primary amine and the glycidyltrialkylammonium salt represented by the general formula (VIII), an appropriate amount of an aqueous alkali solution is charged in order to secure the reactivity and promote a certain reaction. Preferably, the pH is maintained between 6 and 12. When the pH is below this range, the reaction progresses slowly, and when it exceeds this range, by-products are formed and the yield is reduced, as in the above production method [1]. The reactions of the present invention described as the above production methods [1] and [2] may all be performed in air or may be performed in an inert gas atmosphere. It is preferably performed in an atmosphere. Primary amine used in the present invention
R ¹ NH ₂ (R ¹ has the above meaning) includes, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
Examples include behenylamine, isostearylamine, and coconut aliphatic amine.

The cationic compound represented by the above general formula (I) of the present invention may be used alone or in the form of the general formula (I)
I)

[0022]

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Wherein X, R ² , R ³ and R ⁴ have the same meanings as in formula (I), R ⁵ is a C ₈ -C ₂₂ alkyl, alkenyl or hydroxyalkyl group, and n is 1 Represents an integer of from 5 to 5. A compound represented by the general formula (III)

[0024]

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[Wherein, X , R ² , R ³ and R ⁴ have the same meanings as in the general formula (I), R ⁵ has the same meaning as in the general formula (II), and Y denotes the general formula (I
V)

[0026]

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[Wherein , X, R ² , R ³ , R ⁴ and Z are the general formulas (I)
And R ⁵ has the same meaning as in formula (II) . ]
Is useful as a surfactant containing a mixture with at least one selected from the group of compounds represented by

In this case, the ratio (weight ratio) of at least one selected from the group consisting of the compound (II), the compound (III), and the compound (VI) to the cationic compound (I) is as follows:
[At least one selected from the group of compounds represented by compound (II), compound (III), and compound (VI)] / [compound
Cation compound represented by (I)] = 0/100 to 95/5 in general. The ratio of compound (II), compound (III), and compound (VI) can be changed at an arbitrary ratio according to the purpose. Further, the compound (II) provided by the present invention,
(III) and may contain at least one selected from the group of compounds represented by (VI), the cationic compound of the present invention
(I) can be used in combination with a conventionally known surfactant.

Here, the compound represented by the general formula (II) can be obtained by the method described in JP-A-3-2137 proposed by the present inventors. For example, a compound represented by the general formula (VI), which is a known compound, is represented by the following general formula (X)
Can be obtained by reacting with the compound represented by

[0030]

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Wherein Q is a halogen atom, n is an integer of 1 to 5, M is H, a lower alkyl group or an alkali metal. The compound represented by the formula (III) can be obtained by the method described in Japanese Patent Application Laid-Open No. 2-56140 proposed by the present inventors. For example, it can be obtained by reacting a compound represented by the general formula (VI) with a compound represented by the following general formula (XI) or a compound represented by the following general formula (XII).

[0032]

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Wherein Q represents a halogen atom and M represents an alkali metal. ]

[0034]

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Wherein Q and M have the same meanings as in formula (XI). ]

[0036]

The cationic compound represented by the general formula (I) according to the present invention has a surfactant activity, and a surfactant containing such a compound as a main component has excellent foaming power and detergency,
Since it is hypoallergenic, it can be used not only as a hair washing base but also as a body washing base.

[0037]

Next, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited by these examples. Example 1 [Synthesis of Compounds (XIII) and (XIV)] 185 g of dodecylamine (molecular weight: 185), 200 g of ion-exchanged water, and ethanol were placed in a 2 l four-necked flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel. 100g was charged. Thereafter, the above mixture was heated to 75 ° C. with stirring. Next, while maintaining the above temperature, a pH electrode was inserted into the solution, and a 40% aqueous sodium hydroxide solution was dropped to adjust the pH to 10. Next, 3-chloro-2-
489 g of a 50% aqueous solution of hydroxypropyltrimethylammonium chloride (molecular weight: 188) was added dropwise over 2 hours. During this time, a 40% aqueous sodium hydroxide solution was appropriately added dropwise to maintain the pH at 10. After dropping of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining the pH at 10, and the remaining amount of dodecylamine was confirmed by high performance liquid chromatography every hour. . Six hours after the completion of dropping of 3-chloro-2-hydroxypropyltrimethylammonium chloride, the concentration of dodecylamine in the system became 0.1%.

After purifying the reaction solution by electrodialysis,
Partly evaporated to dryness, dissolved in ethanol and analyzed by high performance liquid chromatography, the following formula (X
Two components, a compound represented by III) and a compound represented by formula (XIV), were obtained as main components.

[0039]

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* Yield of compound (XIII) 30% by weight based on evaporated solids

[0041]

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* Yield of compound (XIV) 70% by weight based on evaporated dry solid Mass spectrometry results All mass spectrometry was performed under the following conditions. Apparatus; Mass spectrometry type SX-102 manufactured by JEOL Ltd. Measurement conditions; Sample introduction method-Direct introduction (without using a sampler)-Ionization method-FAB (Fast Atom Bomberdme)
nt) The analysis results were expressed in terms of the fragment ion molecular weight.

As a result of mass spectrometry of the compound (XIII), two main peaks were observed at two places of 394,218. Mass spectrometry of compound (XIV) showed two major peaks at two places, 301 and 125.
It was a (M ⁺ -Cl) ion peak, and it was confirmed that the compound was a cationic compound having the above structure.

Example 2 [Synthesis of Compound (XIII) and Compound (XV)] After heating the mixture obtained in Example 1 to 80 ° C., a previously prepared sodium monochloroacetate (molecular weight: 116.5) was prepared. 379 g of a 40% aqueous solution was added dropwise over 2 hours. In order to maintain the pH at 10, a 40% aqueous alkaline solution was appropriately added dropwise. Maintain pH at 10, warm,
While continuing the stirring, the reaction was performed by high performance liquid chromatography until the concentration of the compound represented by the formula (XIV) in the system became 0.1%, and the reaction was terminated. After purifying the reaction solution using an electrodialysis device, a part thereof was evaporated to dryness,
When it was dissolved in ethanol and analyzed by high performance liquid chromatography, N- represented by the following formula (XV) was obtained.
It was confirmed that a mixture containing dodecyl-N- (3-trimethylammonio-2-hydroxypropyl) aminoacetate and compound (XIII) as main components was obtained.

[0045]

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* Yield of compound (XV) 71% by weight based on evaporated solids

[0047]

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* Yield of compound (XIII) 29% by weight based on evaporation to dryness Results of IR analysis and mass spectrometry of compound (XV) [IR analysis] At a wave number of 1590 cm ^-1 (6.25 μm), a characteristic of carboxylate ion is specified. Strong absorption was observed. [Mass spectrometry] The measurement conditions are the same as described above. Analysis results: three major peaks were observed at three places of 359, 102 and 58, and 359 was the parent ion peak of (M + 1), confirming that the compound had a betaine compound structure.

Example 3 [Synthesis of Compound (XIII) and Compound (XVI)] The mixture obtained in the same manner as in Example 1 was heated to 80 ° C., and the previously prepared 3-chloro- 665 g of a 30% aqueous solution of sodium 2-hydroxypropylene sulfonate (molecular weight 196.5)
Was added dropwise over 2 hours. During this time, to maintain the pH at 10, 40
% Alkali aqueous solution was dropped appropriately. While maintaining the pH at 10 and continuing the heating and stirring, the concentration of the compound represented by the formula (XIV) in the system was adjusted to 0.1 by high performance liquid chromatography.
%, And the reaction was terminated. After purifying the reaction solution using an electrodialyzer, a part of the solution was evaporated to dryness, dissolved in ethanol, and analyzed by high performance liquid chromatography to find that N-dodecyl represented by the following formula (XVI) was obtained. A mixture containing -N- (3-trimethylammonio-2-hydroxypropylene) amino-2-hydroxypropylenesulfonate and compound (XIII) as a main component was obtained.

[0050]

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* Yield of compound (XVI) 75% by weight based on the evaporated dry solid

[0052]

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* Yield of compound (XVI) 25% by weight based on evaporation to dryness IR analysis of compound (XVI), mass spectrometry [IR analysis] At a wave number of 1200 cm ^-1 (8.33 μm), a characteristic of sulfonate ion was obtained. Strong absorption was observed. [Mass spectrometry] The measurement conditions are the same as described above. Analysis results; three major peaks were observed at three positions of 439, 102 and 58, and 439 was the parent ion peak of (M + 1), confirming that it was a betaine compound having the above structure.

Example 4 [Synthesis of Compound (XIII)] The same reactor as in Example 1 was charged with 185 g of dodecylamine (molecular weight: 185), 200 g of ion-exchanged water, and 100 g of ethanol. Thereafter, the above mixture was heated to 75 ° C. with stirring. Next, while maintaining the above temperature, a pH electrode was inserted into the solution, and a 40% aqueous sodium hydroxide solution was dropped to adjust the pH to 10. Next, 3-chloro-2-
752 g of a 50% aqueous solution of hydroxypropyltrimethylammonium chloride (molecular weight: 188) was added dropwise over 2 hours. During this time, a 40% aqueous sodium hydroxide solution was appropriately added dropwise to maintain the pH at 10. After dropping of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, heating and stirring were continued while maintaining the pH at 10, and the remaining amount of dodecylamine was confirmed by high performance liquid chromatography every hour. . Three hours after the completion of dropping of 3-chloro-2-hydroxypropyltrimethylammonium chloride, the concentration of dodecylamine in the system became 0.1%.

After purifying the reaction solution by electrodialysis,
The structure was confirmed in the same manner as in Example 1, and compound (XIII)
Was obtained.

Comparative Example 1 As a surfactant, N-cocoyl-N'-hydroxyethyl-N'-sodium carboxymethylethylenediamine (trade name: Softazoline CH, manufactured by Kawaken Co., Ltd.) was used. Comparative Example 2 As a surfactant, N-lauroyl-N-methyl-β-
Alanine sodium [Alanon AL, manufactured by Kawaken Co., Ltd.
E] was used. Comparative Example 3 Triethanolamine lauryl sulfate [trade name: Emar TD, manufactured by Kao Corporation] was used as a surfactant. In addition, as a compound of Comparative Example 1 and Comparative Example 2, a compound which was conventionally known to have extremely mild skin irritation was selected as a control.

[Test Example] Test Method for Skin Irritation As a test method for skin irritation, a 24-hour closed sticking test was performed on humans. That is, a band test adhesive bandage impregnated with 0.1 ml of a 0.2% aqueous solution containing a surfactant as an effective component was applied to 20 subjects for 24 hours, and the irritation was evaluated 24 hours after the removal of the adhesive. As a result of determination, those showing clear erythema were defined as positive, and the positive rate was shown. -Foaming power Diluted with DH hard water 4 times so that the final concentration becomes 0.2% as a surfactant effective component, and measured by an inverted stirring method. The measurement was carried out at 40 ° C. with the addition of 0.3% lanolin, and the results were shown in terms of foam volume (ml). -Detergency test 5cm x 5cm wool muslin cloth with 2% carbon black
Soil of almost the same composition as scalp fat containing (paraffin 12%, wax ester 21%, triglyceride 26%, higher fatty acids
32%, cholesterol 5%, monoglyceride 2%) is applied uniformly and dried. Activator active ingredient
0.6%, pH 7.0, about 100 containing 500ml of 4 degree DH detergent solution
The sample is placed in a 0 ml stainless steel cylinder, shaken in a constant temperature bath at 40 ° C. for 6 minutes, the contaminated cloth is thoroughly rinsed in running water, and after drying, the reflectance is measured. The cleaning rate is determined by the following equation.

[0058]

(Equation 1)

Table 1 shows the test results of Examples 1 to 4 and Comparative Examples 1 to 3.

[0060]

[Table 1]

[Note] * The mixture obtained in each Example. ** Compound obtained in Example 4. Table 1 shows that according to the present invention, it is possible to provide a highly safe surfactant having excellent detergency and foaming properties for cleaning hair and body.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/62 C11D 1/62

Claims (3)

(57) [Claims] 1. A cationic compound represented by the following general formula (I). Embedded image [Wherein, R ¹ is a linear or branched C ₈ -C ₂₂ alkyl
Group, X is H or a hydroxyl ^{group, R 2, R 3, R} 4 is C ₁ -C ₄
And Z is OH, a halogen atom or C ₁ -C ₄
Represents an alkyl sulfate group. ] 2. A surfactant comprising the cationic compound represented by the general formula (I) according to claim 1. 3. A compound represented by the following general formula (II):
A compound represented by the following general formula (III), and a compound represented by the general formula (V
3. The surfactant according to claim 2, further comprising at least one selected from the group of compounds represented by I). Embedded image ^{Wherein, X, R 2, R 3} , R 4 are the same meaning as the general formula (I), R ⁵
The alkyl group of C ₈ -C _22, alkenyl or hydroxyalkyl group, n represents an integer of 1-5. [Chemical formula 3] ^{Wherein, X, R 2, R 3} , R 4 are the same meaning as the general formula (I), R ⁵
Represents the same meaning as in the general formula (II), and Y represents the general formula (IV). Or the general formula (V): Is shown. [Formula 6] [Wherein, X , R ² , R ³ , R ⁴ and Z have the same meanings as in the general formula (I), and R ⁵ has the same meaning as in the general formula (II) . ]