JPH0551352A - Novel cationic compound and surfactant containing the same - Google Patents

Abstract

PURPOSE:To provide the title novel compound mild to the skin, and useful for surfactants for cleaning the hair or body having excellent foamability and detergency. CONSTITUTION:The objective cationic compound of formula I (R<1> is straight or branched chain 8-22C alkyl or hydroxyalkyl; X is H or hydroxyl; R<2>-R<4> are each 1-4C alkyl; Z is OH, halogen or 1-4C alkylsulfate), for example, a compound of formula II. The compound of the formula I can be obtained, e.g. by reaction of an aliphatic primary amine of formula R<1>NH2 with 2 to 3 molar times of a compound of formula III (Y is halogen). The compound of the formula I can be used as the other objective surfactant of high safety either singly or in the form of its mixture with at least one compound selected from among the compounds of formula IV (R<5> is 8-22C alkyl, alkenyl or hydroxyalkyl; n is 1-5), compounds of formula V (Y is of formula VI or of formula VII) and compounds of formula VIII.

Description

Detailed Description of the Invention

[0001]

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 having a mild action on the skin and having excellent foaming power and detergency, which is useful as a surfactant for washing hair or body.

[0002]

2. Description of the Related Art In recent years,
Surfactants used for detergents and the like are required to have excellent properties such as biodegradability, safety, and low irritation to eyes and skin in addition to the surfactant ability. As surfactants that meet these requirements, acylated amino acid type surfactants and imidazoline type surfactants have been widely used. However, while these surfactants are generally excellent in safety and the like, they are inferior in foaming power and detergency, which are particularly important as surfactant ability, so that they cannot be used alone as a component of shampoo or the like. However, it is generally used in combination with an anionic surfactant such as alkyl ether sulfate or alkyl sulfate.

Since such anionic surfactants are highly irritating to the skin, they may damage the skin. Therefore, the emergence of an active agent having excellent foaming power and cleaning power and high safety is strongly desired.

[0004]

In view of the above situation, the present inventors have excellent cleaning power and foaming power for cleaning hair and body,
As a result of intensive studies on a highly safe surfactant, it was found that a novel cationic compound represented by the following general formula (I) meets the purpose of the present invention, and the present invention has been completed. 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]

[Chemical 7]

[Wherein R ¹ is a linear or branched C _{8 to} C ₂₂
Is an alkyl group or a hydroxyalkyl group, X is H or a hydroxyl group, R ² , R ³ and R ⁴ are C _{1 to} C ₄ alkyl groups, Z
Represents OH, a halogen atom or a C ₁ -C ₄ alkylsulfate group. The present invention will be described in detail below. There is no report on the cationic compound represented by the general formula (I) in the conventional literatures, patents and the like, and the 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] For the aliphatic primary amine represented by R ¹ NH ₂ (R ¹ represents a linear or branched alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group), a general formula ( VII)

[0009]

[Chemical 8]

[Wherein Y is a halogen atom, X is H or a hydroxyl group, R ² , R ³ and R ⁴ are alkyl groups having 1 to 4 carbon atoms, Z is OH, a halogen atom or a carbon atom having 1 to 4 carbon atoms] Indicates an alkylsulfate group. ] The compound represented by general formula (I) is obtained by reacting the compound represented by the formula (2) in a molar amount of 2 to 3 times.

For 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 this compound on the primary amine. If necessary, an alkaline solution such as sodium or potassium hydroxide is charged into the reaction solution.
During the reaction, the pH of the reaction system is maintained within the above range in order to react the primary amine with the compound represented by the general formula (VII). For this purpose, it is preferable to set the pH to 6 or more, but if the pH exceeds 12, the compound represented by the general formula (VII) causes hydrolysis, which is not preferable. The reaction proceeds even at room temperature, but the higher the temperature, the faster the reaction. However, if the temperature and pH are high, the hydrolysis of the compound represented by the general formula (VII) is promoted, and therefore the reaction temperature is 100 ° C. or lower, preferably
90 ° C or lower.

In the production method [1], the molar ratio of the compound represented by the general formula (VII) to the primary amine is usually 2 /.
It is 1-3 / 1, preferably 2.1 / 1-3.0 / 1. When the molar ratio is less than 2/1, the reaction rate decreases, and when it exceeds 3/1, the reaction mixture contains the compound of the general formula (VII)
A large amount of the hydrolyzate of the compound represented by remains, which is not preferable. 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 residual amount of the primary amine in the reaction solution using high performance liquid chromatography.

The primary amine and the general formula (VI
The reaction time with the compound represented by I) varies depending on the applied temperature and pH, but it generally takes 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 the production method [1] and the following general formula (V
III)

[0015]

[Chemical 9]

[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 alkylsulfate group having 1 to 4 carbon atoms. ] By reacting with a glycidyltrialkylammonium salt represented by the general formula (IX)

[0017]

[Chemical 10]

[Wherein R ¹ is a linear or branched alkyl group having 8 to 22 carbon atoms or a hydroxyalkyl group, 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 alkylsulfate group having 1 to 4 carbon atoms. ] The compound shown by this is obtained.

In the reaction of the glycidyltrialkylammonium salt represented by the general formula (VIII) with the primary amine, the molar ratio of the compound represented by the general formula (VIII) and the primary amine is 2/1 to 3 It is / 1. If the molar ratio is less than this range, the reaction rate decreases, and if 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.
℃. When the reaction temperature is lower than this range, the reaction rate is slow, and when it exceeds this range, coloring or the like occurs, which is not preferable.

The reaction of the primary amine with the glycidyltrialkylammonium salt represented by the general formula (VIII) ensures the reactivity, and in order to proceed a certain reaction, an appropriate amount of an alkaline aqueous solution is charged, It is preferred to maintain the pH at 6-12. When the pH is less than this range, the reaction proceeds 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 be carried out in air or in an inert gas atmosphere, but an inert gas is used in view of coloration prevention. It is preferably carried out in an atmosphere. Primary amine used in the present invention
Examples of R ¹ NH ₂ (R ¹ has the above meaning) include, for example, octylamine, decylamine, dodecylamine, tetradecylamine, hexadecylamine, octadecylamine,
Examples thereof include behenylamine, isostearylamine, and coconut fatty amine.

The cation compound represented by the above general formula (I) of the present invention is the cation compound alone or the general formula (I).
I)

[0022]

[Chemical 11]

[Wherein, X, R ² , R ² , R ³ and R ⁴ are represented by the general formula (I)
Same meaning, R ⁵ is an alkyl group of C ₈ -C _22, alkenyl or hydroxyalkyl group, n represents an integer of 1-5. ] A compound represented by the general formula (III)

[0024]

[Chemical formula 12]

[Wherein R ⁵ , X, R ² , R ³ , R ⁴ and n are general formulas]
(I) has the same meaning, Y is a compound represented by general formula (IV), and general formula (VI)

[0026]

[Chemical 13]

In the formula, R ⁵ , X, R ² , R ³ , R ⁴ and Z are general formulas.
It has the same meaning as (I). ] It 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
[At least one compound selected from the group of compounds represented by compound (II), compound (III), and compound (VI)] / [compound
The cationic compound represented by (I)] is generally in the range of 0/100 to 95/5. The ratio of the compound (II), the compound (III), and the compound (VI) can be changed in any ratio depending on the purpose. Further, the compound (II) provided by the present invention,
(III) and (VI) may contain at least one selected from the group of compounds, the cationic compound of the present invention
(I) can be used in combination with a conventionally known surfactant.

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)
It can be obtained by reacting with a compound represented by

[0030]

[Chemical 14]

[In the formula, 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 general formula (III) can be obtained by the method described in JP-A-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]

[Chemical 15]

[In the formula, Q represents a halogen atom and M represents an alkali metal. ]

[0034]

[Chemical 16]

[In the formula, Q and M have the same meanings as in the general formula (XI). ]

[0036]

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

[0037]

EXAMPLES Next, the present invention will be described in detail based on examples, but the scope of the present invention is not limited by these examples. Example 1 [Synthesis of Compounds (XIII) and (XIV)] A 2-liter four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and a dropping funnel was charged with 185 g of dodecylamine (molecular weight 185), 200 g of ion-exchanged water, and ethanol. I put 100g. The above mixture was then heated to 75 ° C with stirring. Next, while maintaining the above temperature, a pH electrode was inserted into the solution, and a 40% sodium hydroxide aqueous solution was added dropwise 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 period, a 40% sodium hydroxide aqueous solution was appropriately added dropwise to maintain the pH at 10. After the dropwise addition 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 dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, the concentration of dodecylamine in the system became 0.1%.

After the reaction solution was purified by electrodialysis,
Part of it was evaporated to dryness, dissolved in ethanol, and analyzed by high performance liquid chromatography.
Two components, a compound represented by III) and a compound represented by formula (XIV), were obtained as main components.

[0039]

[Chemical 17]

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

[0041]

[Chemical 18]

* Yield of compound (XIV) 70% by weight based on evaporated dry solids Mass spectrometry results Mass spectrometry was carried out under the following conditions. Equipment: JEOL Ltd. SX-102 type mass spectrometric measurement conditions; Sample introduction method-Direct introduction (without sampler) Ionization method-FAB (Fast Atom Bomberdme)
nt) The analysis results are shown in terms of fragment ion molecular weight.

Mass spectrometry result of compound (XIII) Two major peaks were observed at two positions of 394,218. Mass spectrometric result of compound (XIV) Two major peaks were observed at two positions of 301,125.
It was a (M ⁺ -Cl) ion peak, and it was confirmed that the compound was a cation 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., sodium monochloroacetate (molecular weight 116.5) prepared in advance was used. 379 g of 40% aqueous solution was added dropwise over 2 hours. During this period, a 40% alkaline aqueous solution was appropriately added dropwise to maintain the pH at 10. Keeping pH at 10 and heating,
While continuing stirring, the reaction was carried out by high performance liquid chromatography until the in-system concentration of the compound represented by the formula (XIV) became 0.1%, and then the reaction was terminated. After the reaction solution was purified using an electrodialysis device, part of it was evaporated to dryness,
When it was dissolved in ethanol and analyzed by high performance liquid chromatography, N- represented by the following formula (XV)
It was confirmed that a mixture containing dodecyl-N- (3-trimethylammonio-2-hydroxypropyl) aminoacetate and compound (XIII) as main components was obtained.

[0045]

[Chemical 19]

* Yield of compound (XV) 71% by weight based on the dry solid evaporated

[0047]

[Chemical 20]

* Yield of compound (XIII) 29% by weight based on dryness by evaporation IR analysis and mass spectrometry results of compound (XV) [IR analysis] at a wave number of 1590 cm ^-1 (6.25 μm) Strong absorption was observed. [Mass Spectrometry] The measurement conditions are the same as above. Analytical results: Three major peaks were observed at three locations of 359, 102, and 58, and 359 was a parent ion peak of (M + 1), and it was confirmed that the compound had a structure of betaine compound.

Example 3 [Synthesis of Compound (XIII) and Compound (XVI)] The mixture obtained by the same operation as in Example 1 was heated to 80 ° C. and then adjusted in advance with 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 period, 40 to maintain the pH at 10.
% Aqueous alkali solution was added dropwise. While maintaining the pH at 10 and continuing heating and stirring, the in-system concentration of the compound represented by the formula (XIV) was determined to be 0.1 by high performance liquid chromatography.
After the reaction was carried out until the amount reached%, the reaction was terminated. After the reaction solution was purified using an electrodialysis device, a part thereof 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) A mixture containing -N- (3-trimethylammonio-2-hydroxypropylene) amino-2-hydroxypropylenesulfonate and compound (XIII) as a main component was obtained.

[0050]

[Chemical 21]

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

[0052]

[Chemical formula 22]

* Yield of compound (XVI) 25% by weight with respect to dryness by evaporation IR analysis and mass spectrometry results of compound (XVI) [IR analysis] at a wave number of 1200 cm ^-1 (8.33 μm), which is peculiar to sulfonate ion Strong absorption was observed. [Mass Spectrometry] The measurement conditions are the same as above. Analytical results: Three major peaks were observed at three locations of 439, 102, and 58, and 439 was a parent ion peak of (M + 1), which was confirmed to be a betaine compound having the above structure.

Example 4 [Synthesis of Compound (XIII)] A reactor similar to that in Example 1 was charged with 185 g of dodecylamine (molecular weight 185), 200 g of ion-exchanged water, and 100 g of ethanol. Then 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 added dropwise 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 period, a 40% aqueous sodium hydroxide solution was appropriately added dropwise to maintain the pH at 10. After the dropwise addition 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 every one hour by high performance liquid chromatography. . Three hours after the dropwise addition of 3-chloro-2-hydroxypropyltrimethylammonium chloride was completed, the concentration of dodecylamine in the system became 0.1%.

After the reaction solution was purified by electrodialysis,
The structure of the compound (XIII) was confirmed by the same procedure as in Example 1.
It was confirmed that was obtained.

Comparative Example 1 As a surfactant, N-cocoyl-N'-hydroxyethyl-N'-sodium carboxymethylethylenediamine [Kawaken Co., Ltd., trade name softazoline CH] was used. Comparative Example 2 As a surfactant, N-lauroyl-N-methyl-β-
Alanine sodium [Kawaken Co., Ltd., trade name Alanone AL
E] was used. Comparative Example 3 As a surfactant, lauryl sulfate triethanolamine [manufactured by Kao Corporation, trade name Emal TD] was used. As the compounds of Comparative Examples 1 and 2, those conventionally known to be extremely mild to skin irritation were selected as controls.

[Test Example] -Test method for skin irritation As a test method for skin irritation, a 24-hour closed patch test for humans was performed. That is, 20 test subjects were stuck with a patch for a batch test impregnated with 0.1 ml of a 0.2% aqueous solution containing a surfactant as an active ingredient for 24 hours, and the irritation was determined 24 hours after the sticking was removed. Judgment results were made positive by showing clear erythema, and indicated by the positive rate. -Foaming power Diluted with DH hard water 4 times so that the final concentration would be 0.2% as the active ingredient of the surfactant, and measured by the inversion stirring method. The measurement was carried out at 40 ° C. with addition of 0.3% lanolin, and the results are shown in terms of foam volume (ml).・Detergency test 5 cm x 5 cm wool muslin cloth with 2% carbon black
Stain with almost the same composition as scalp oil containing (paraffin 12%, wax ester 21%, triglyceride 26%, higher fatty acid
32%, cholesterol 5%, monoglyceride 2%) are evenly applied and dried. Use this contaminated cloth as an active ingredient
About 100 containing 500 ml of 0.6%, pH 7.0, 4 degree DH detergent solution
It is put in a 0 ml stainless steel cylinder, shaken for 6 minutes in a constant temperature bath of 40 ° C., the contaminated cloth is thoroughly rinsed in running water, dried, and then the reflectance is measured. The cleaning rate is calculated by the following formula.

[0058]

[Equation 1]

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

[0060]

[Table 1]

Note: The mixture obtained in each example. ** Compound obtained in Example 4. It can be seen from Table 1 that the present invention can provide a surfactant having excellent detergency and foamability for hair and body washing, and having high safety.

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[Procedure amendment]

[Submission date] November 28, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 3

[Correction method] Change

[Correction content]

[Chemical 2] [In the formula, X, R ² , R ³ and R ⁴ have the same meanings as in formula (I), R ⁵
The alkyl group of C ₈ -C _22, alkenyl or hydroxyalkyl group, n represents an integer of 1-5. ]

[Chemical 3] [Wherein R ⁵ , X, R ² , R ³ , R ⁴ and n have the same meanings as in the general formula (I), and Y represents the general formula (IV).

[Chemical 4] Or general formula (V)

[Chemical 5] Indicates. ]

[Chemical 6] [In the formula, R ⁵ , X, R ² , R ³ , R ⁴ and Z have the same meanings as in formula (I). ]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

[0022]

[Chemical 11]

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0023

[Correction method] Change

[Correction content]

[Wherein, X, R ² , R ³ and R ⁴ have the same meanings as in the general formula (I), R ⁵ is a C _{8 to} C ₂₂ alkyl group, alkenyl group or hydroxyalkyl group, and n is 1 Indicates an integer of ˜5. ] The compound represented by the general formula (III)

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Claims (3)

[Claims] 1. A cationic compound represented by the following general formula (I): [Chemical 1] [In the formula, R ¹ is a linear or branched C _{8 to} C ₂₂ alkyl group or hydroxyalkyl group, X is H or a hydroxyl group, and R ² , R ³ and R ⁴ are C _{1 to} C ₄ alkyl groups. , Z represents OH, a halogen atom or a C _{1 to} C ₄ alkylsulfate group. ] 2. A surfactant containing 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 general formula (V
The surfactant according to claim 2, further comprising at least one selected from the group of compounds represented by I). [Chemical 2] [In the formula, X, R ² , R ² , R ³ and R ⁴ have the same meanings as in the general formula (I), R ⁵ is a C _{8 to} C ₂₂ alkyl group, an alkenyl group or a hydroxyalkyl group, and n is 1 Indicates an integer of ˜5. ] [Chemical 3] [Wherein R ⁵ , X, R ² , R ³ , R ⁴ and n have the same meanings as in the general formula (I), and Y represents the general formula (IV) Or general formula (V) Indicates. ] [Chemical 6] [In the formula, R ⁵ , X, R ² , R ³ , R ⁴ and Z have the same meanings as in formula (I). ]