JPH04257548A - Novel cationic compound, its production thereof and surfactant comprising the compound - Google Patents

Abstract

PURPOSE:To provide a novel cationic compound giving excellent flexibility to hair, having high safety, low irritation and surface activity and useful as a surfactant employed in a rinse base material for the hair. CONSTITUTION:A compound of formula I (R<1>, R<2> are 3-22C linear or branched alkyl or alkenyl; R<3>, R<4> are 1-3C alkyl; Y is H, OH; A is OH, halogen, 1-4C alkyl sulfuric acid group; (n) is 0-5; but when (n) is 1, Y is H or OH, and when (n) is not 1, Y is H), e.g. N-lauryl-N-[3-(N'-stearyl-N',N'-dimethylammonio)-2- hydroxypropyl ] amine chloride. The compound is obtained by reacting a compound of the formula R<1>NH2 with a cationizing agent of formula II or III (Z is halogen).

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 method for producing the same. More specifically, the present invention relates to a cationic compound useful as a hair rinse base that has a mild effect on the skin and excellent flexibility, and a method for producing the same.

0002

[Prior art and problems to be solved by the invention] In recent years,
Surfactants used in rinse bases and the like are required to have excellent properties, such as safety and low irritation to the eyes and skin, in addition to surfactant ability. Among the currently used rinse bases, the following cationic activators are well known.

<Monoalkyltrimethylammonium salt>

0004

[C5]

<Dialkyldimethylammonium salt>

[
0006

[C6]

However, when these cationic active agents are used as a rinse, although they are safe, they often have problems with skin irritation. Therefore, there is a strong desire for an active agent that has excellent flexibility, high safety, and low irritation.

[0008]

[Means for Solving the Problems] In view of the above-mentioned current situation, the present inventors conducted intensive studies on compounds that are highly flexible, highly safe, and hypoallergenic as a hair rinse agent, and as a result, the following results were found: The present inventors have discovered that a novel cationic compound represented by the general formula (1) meets the objectives of the present invention, and have completed the present invention.

That is, the present invention provides general formula (1)

0010
]

[C7]

[In the formula, R1 and R2 are linear or branched alkyl groups or alkenyl groups having 8 to 22 carbon atoms, R3,
R4 is the same or different alkyl group having 1 to 3 carbon atoms, Y
represents H or a hydroxy group, and A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms. n represents 0 or an integer from 1 to 5; when n=1, Y=H or a hydroxy group; when n=0, 2, 3, 4, 5, Y=H. The present invention provides a novel cationic compound represented by the following formula, a method for producing the same, and a surfactant comprising this compound.

The present invention will be explained in detail below. There are no reports regarding the cationic compound represented by the general formula (1) in conventional literature, patent publications, etc., and the cationic compound of the present invention is novel. The cationic compound of the present invention represented by the above general formula (1) can be produced by the following two methods.
1> or <2>.

Production method <1>"Cationation" General formula (2) R1NH2 (2) [In the formula, R1 represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. ] and the general formula (3)

[0014]

[Chemical formula 8]

[In the formula, R2 is a straight chain or branched chain having 8 to 8 carbon atoms]
22 alkyl or alkenyl groups, R3 and R4 are the same or different alkyl groups having 1 to 3 carbon atoms, Y is H or a hydroxy group, A is OH, a halogen atom or a carbon number 1
~4 alkyl sulfate group. n represents 0 or an integer from 1 to 5; when n = 1, Y = H or a hydroxy group; when n = 0, 2, 3, 4, 5, Y = H
represents. Z represents a halogen atom. ] can be produced by reacting the cationizing agent (3) with 1 to 3 times the mole of the aliphatic primary amine (2).

[0016] This manufacturing method can be concretely illustrated by the following formula.

[0017]

[Chemical formula 9]

[In the formula, R1, R2, R3, R4, Y
, Z, A, n have the same meanings as above. ] The reaction between the aliphatic primary amine (2) and the cationizing agent (3) is usually carried out by dropping an aqueous solution of the cationizing agent (3) into an alcoholic solution of the aliphatic primary amine (2), and then adding p
It is preferable to maintain H at 8 to 12, and for this purpose, an alkaline solution such as sodium hydroxide or potassium hydroxide is added to the reaction solution as necessary. The reason for maintaining the pH of the reaction system within the above range during the reaction is to allow the aliphatic primary amine (2) to react with the cationizing agent (3). From the viewpoint of reaction rate, it is preferable to use an alkaline pH of 8 or more, and a pH exceeding 12 is not preferable because the cationizing agent (3) will undergo hydrolysis. 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 cationizing agent (3)
The temperature is 100°C or lower, preferably 90°C or lower, since the hydrolysis of .

[0019] In this production method, the cationizing agent (3)
and aliphatic primary amine (2) is usually 1
/1 to 3/1 is preferable, more preferably 1.1/1
~1.5/1. From this range, the cationizing agent (3
) If the amount of the cationizing agent (3) is less than this range, the reaction rate will decrease, and if the amount of the cationizing agent (3) is greater than this range, a large amount of the cationizing agent (3) or the hydrolyzate of the cationizing agent (3) will remain in the reaction mixture. So I don't like it. Aliphatic primary amine (2
) and the cationizing agent (3) can be confirmed by analyzing the remaining amount of the aliphatic primary amine (2) during the reaction using high performance liquid chromatography.

[0020] The reaction solution in this production method is an aqueous solution,
Alternatively, a mixed solution of an aqueous solution and a lower alcohol such as ethanol or isopropyl alcohol, or a diol such as 1,3-propanediol or propylene glycol may be used.

Manufacturing method <2> "Cationization" Aliphatic primary amine (2) and general formula (4)

0022
]

[Chemical formula 10]

[In the formula, R2, R3, R4 and A have the above meanings. ] by reacting with a cationizing agent (glycidyl trialkylammonium salt),
General formula (1')

[0024]

[Chemical formula 11]

[In the formula, R1, R2, R3, R4,
A has the meaning given above. ] is obtained.

[0026] This manufacturing method can be concretely illustrated by the following formula.

[0027]

[Chemical formula 12]

[In the formula, R1, R2, R3, R4,
A has the same meaning as above. ] Glycidyl trialkylammonium salt (4) and aliphatic primary amine (
In the reaction with 2), the molar ratio of glycidyltrialkylammonium salt (4) and aliphatic primary amine (2) is 1/1 to 3/1. If the molar ratio is below this range, the reactivity will decrease, and if the molar ratio exceeds this range, a large amount of the hydrolyzate of the glycidyl trialkylammonium salt (4) will remain in the reaction mixture, which is undesirable. . The reaction temperature is 30 to 120°C, preferably 50 to 90°C. If the reaction temperature is lower than this range, the reaction rate will be slow, and if it exceeds this range, coloring etc. will occur, which is not preferable. Aliphatic primary amine (
2) and glycidyl trialkylammonium salt (4)
In the reaction with p.
It is preferred to maintain H between 8 and 12. If the pH is less than this range, the reaction rate will be slow, and if it exceeds this range, many by-products will be produced and the yield will be reduced.

All the reactions of the present invention may be carried out in air or in an inert gas atmosphere, but an inert gas atmosphere is preferable from the viewpoint of coloring and the like.

Examples of the aliphatic primary amines represented by the general formula (2) used in the present invention include caprylamine, decylamine, laurylamine, myristylamine, hexadecylamine, stearylamine, behenylamine, and coco. Examples include nutamine and oleylamine.

[0031]

[Effects of the Invention] The compound obtained by the method of the present invention has surface activity, and the surfactant containing such a compound as a main component has excellent flexibility and low irritation, so it can be used as a hair conditioner base. can be provided.

[0032]

EXAMPLES Next, the present invention will be explained in detail based on Examples, but the scope of the present invention is not limited by these.

Example 1 Cationization [Synthesis of Compound (1)] 185 g of laurylamine was placed in a 3-liter four-necked flask equipped with a stirrer, condenser, thermometer, and dropping funnel.
(1 mol) and 185 g of ethanol were added and heated to 70 to 80°C while stirring. Thereafter, a pH electrode was inserted into the mixture while stirring the mixture, and a 40% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 10. Next, 3-
Chloro-2-hydroxypropyl-N-stearyl-
N,N-dimethylammonium chloride (MW42
6) 1846g (1.3 mol) of a 30% aqueous solution of
It dripped in time. During this time, in order to maintain pH 10,
% sodium hydroxide was added dropwise accordingly. 3-chloro-2-
After completing the dropping of hydroxypropyl-N-stearyl-N,N-dimethylammonium chloride, p
Heating and stirring were continued while maintaining H10, and the remaining amount of laurylamine was checked every hour by high performance liquid chromatography.

3-chloro-2-hydroxypropyl-N
Six hours after the dropwise addition of -stearyl-N,N-dimethylammonium chloride was completed, the reaction was terminated after confirming that the concentration of laurylamine in the system had reached 1%.

After purifying this reaction solution using an electrodialyzer, it was partially evaporated to dryness, and mass spectrometry revealed that the general formula (1) was obtained by mass spectrometry.
) compound, N -lauryl-N -[3- (N'
-stearyl-N',N'-dimethylammonio)-
2-Hydroxypropyl]amine chloride (having the following structural formula) was obtained.

[0036]

[Chemical formula 13]

<Mass spectrometry> Equipment: SX-102 model mass spectrometry manufactured by JEOL Ltd. Measurement conditions: Introduction method: Direct; Ionization method: FAB (Fast Atom Bomb)
erdment) Analysis results: Fragment ion molecular weight: 540, 186 Two main peaks were observed, and 540 was the (M+-Cl) ion peak, confirming that it was a cationic compound with the above structure.

Example 2 Stearylamine was used instead of laurylamine as the raw amine, and 3-chloro-2-hydroxypropyl-N-lauryl-N,N-dimethylammonium chloride was used as the cationizing agent. Example 1 except that hydroxypropyl-N-stearyl-N,N-dimethylammonium chloride is used instead.
It was confirmed in the same manner as in Example 1 that the obtained compound had the following structure.

[0039]

[Chemical formula 14]

<Mass spectrometry> It was carried out under the same conditions as in Example 1.

Analysis result: Fragment ion molecular weight 54
0, 270 Two main peaks were observed, and 540 was the (M+-Cl) ion peak, confirming that it was a cationic compound with the above structure.

Example 3 3-chloro-2-hydroxypropyl-N-lauryl-N,N-dimethylammonium chloride was used as a cationizing agent.
-Producted in the same manner as in Example 1 except for using instead of -stearyl-N,N-dimethylammonium chloride,
It was confirmed in the same manner as in Example 1 that the obtained compound had the following structure.

[0043]

[Chemical formula 15]

<Mass spectrometry> It was carried out under the same conditions as in Example 1.

Analysis result: Fragment ion molecular weight 45
6,270 Example 4 The same procedure as Example 1 was carried out except that stearylamine was used instead of laurylamine as the raw material amine, and the obtained compound had the following structure. I confirmed it.

[0046]

[Chemical formula 16]

<Mass spectrometry> It was carried out under the same conditions as in Example 1.

Analysis result: Fragment ion molecular weight 62
4,270 Example 5 2,3-oxypropyl-N instead of 3-chloro-2-hydroxypropyl-N-stearyl-N,N-dimethylammonium chloride as a cationizing agent
-Stearyl-N,N-dimethylammonium chloride was used under the same conditions as in Example 1, and the obtained compound was confirmed to be the same as the compound shown in Example 1. confirmed.

Test Examples The surfactants obtained in Examples 1 to 4 and the control compound 1 shown below, which is conventionally known to have excellent flexibility, were tested for skin irritation and flexibility by the method shown below. was evaluated. The results are shown in Table 1.

<Control Compound 1> Cortamine 86P (stearyltrimethylammonium chloride) manufactured by Kao Corporation - Skin irritation test A 24-hour closed patch test on humans was conducted. That is, 2
A patch test plaster impregnated with 0.1 ml of an aqueous solution containing 0.2% active surfactant was applied to 0 subjects for 24 hours, and irritation was determined 24 hours after removal. . The test result was determined to be positive if it showed clear erythema, and was expressed as a positive rate.

・Flexibility evaluation test An alcohol emulsion adjusted to contain 1% of various surfactants, 3% of higher alcohols, and 3% of propylene glycol was applied to hair that had been washed with a shampoo containing no treatment agent. Apply % by weight and leave for 1 minute. After that, rinse with warm water at 40℃ for a certain period of time, towel dry and wash.
Evaluation was performed at T time. Thereafter, the hair was dried with a hair dryer, and a dry evaluation was performed. The evaluation results were evaluated as ◯ for good results, × for unfavorable results, and △ for intermediate results.

[0052]

[Table 1]

Claims (4)

[Claims] [Claim 1] General formula (1) [Formula 1] [In the formula, R1 and R2 are linear or branched carbon atoms of 8 to 22]
an alkyl group or an alkenyl group, R3 and R4 are the same or different alkyl groups having 1 to 3 carbon atoms, Y is H or a hydroxy group, A is OH, a halogen atom, or an alkyl group having 1 to 3 carbon atoms;
4 represents an alkyl sulfate group. n represents 0 or an integer from 1 to 5; when n = 1, Y = H or a hydroxy group; when n = 0, 2, 3, 4, 5, Y = H
represents. ] A cationic compound represented by 2. General formula (2) R1NH2 (2) [wherein R1 represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. [In the formula, R2 is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R3 and R4 are the same or a different alkyl group having 1 to 3 carbon atoms, Y represents H or a hydroxy group, and A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms. n represents 0 or an integer from 1 to 5, and if n=1
Y=H or represents a hydroxy group, n =0,2,3,
4 and 5 represent Y=H. Z represents a halogen atom. A method for producing a cationic compound represented by the general formula (1) according to claim 1, characterized in that the cationic compound is reacted with a cationizing agent represented by the following. 3. General formula (2) R1NH2 (2) [wherein R1 represents a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms. [In the formula, R2 is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R3 and R4 are the same or a different alkyl group having 1 to 3 carbon atoms; A represents OH, a halogen atom, or an alkyl sulfate group having 1 to 4 carbon atoms; ] The general formula (
1') [Formula, R1, R2, R3, R4, A have the above-mentioned meanings. ] A method for producing a cationic compound represented by 4. A surfactant comprising a cationic compound represented by the general formula (1) according to claim 1.