JP2883453B2 - Novel cationic compound, method for producing the same, and surfactant comprising the compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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 having a mild action on the skin and having excellent flexibility, which is useful as a hair rinse base and a method for producing the same.

[0002]

2. Description of the Related Art In recent years,
Surfactants used for rinsing bases and the like are required to be excellent in various properties such as safety and low irritation to eyes and skin in addition to surface active ability. As the rinse base currently used, the following cationic activators are well known.

<Monoalkyltrimethylammonium salt>

[0004]

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<Dialkyldimethylammonium salt>

[0006]

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[0007] However, when these cationic activators are used as a rinse, they often have a problem in irritation to the skin, although the safety is good. For this reason, there is a strong demand for an active agent having excellent flexibility, high safety, and low irritation.

[0008]

Means for Solving the Problems In view of the above-mentioned circumstances, the present inventors have conducted intensive studies on compounds having excellent flexibility, high safety and low irritation as a hair rinse agent. The present inventors have found that the novel cation compound represented by the general formula (1) meets the object of the present invention, and have completed the present invention.

That is, the present invention provides a compound represented by the general formula (1)

[0010]

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[Wherein R ¹ and R ² are linear or branched carbon atoms having 8 carbon atoms.
An alkyl or alkenyl group of 22 to 22, R ³ and R ⁴ are the same or different alkyl groups of 1 to 3 carbon atoms, Y is H or hydroxy group, A is OH, a halogen atom or an alkyl sulfate group of 1 to 4 carbon atoms Represents n represents 0 or an integer of 1 to 5, and n =
1 represents Y = H or a hydroxy group, and n = 0,
In the case of 2,3,4,5, Y = H. And a method for producing the same, and a surfactant comprising the compound.

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

[0013]Manufacturing method <1>  "Cationization" General formula (2) R¹NH_Two (2) (where R¹Is a linear or branched alkyl group having 8 to 22 carbon atoms
Or an alkenyl group. Represented by the following formula:
Min and general formula (3)

[0014]

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[Wherein, R ² represents a straight-chain or branched carbon number of 8 to
22 alkyl groups or alkenyl groups, R ³ and R ⁴ 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 sulfate group having 1 to 4 carbon atoms. Represent. n represents 0 or an integer of 1 to 5, and n = 1
Represents Y = H or a hydroxy group, and n = 0, 2,
3, 4, and 5 represent Y = H. Z represents a halogen atom. To the aliphatic primary amine (2) using the cationizing agent (3) in an amount of 1 to 3 moles per mole.

The present manufacturing method is specifically shown by the following formula.

[0017]

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[Wherein, R ¹ , R ² , R ³ , R ⁴ , Y, Z, A, and n have the same meaning as described above. The reaction between an aliphatic primary amine (2) and a cationizing agent (3) is usually carried out by an aliphatic primary amine.
After the aqueous solution of the cationizing agent (3) is added dropwise to the alcohol solution of (2), the pH is preferably maintained at 8 to 12, and for this purpose, an alkali solution such as sodium hydroxide or potassium hydroxide is optionally added. It is charged into the reaction solution. During the reaction, the pH of the reaction system is maintained in the above range in order to react the aliphatic primary amine (2) with the cationizing agent (3). It is preferably on the alkaline side with a pH of 8 or higher in terms of reaction rate, and when the pH exceeds 12, a cationizing agent is used.
(3) is not preferable because it causes hydrolysis. The reaction proceeds at room temperature, but the higher the temperature, the faster the reaction. However, when the temperature and pH are high, the hydrolysis of the cationizing agent (3) is promoted, so that the temperature is 100 ° C. or lower, preferably 90 ° C. or lower.

In the present production method, the molar ratio of the cationizing agent (3) to the aliphatic primary amine (2) is usually from 1/1 to 3
/ 1, more preferably 1.1 / 1 to 1.5 / 1. When the amount of the cationizing agent (3) is less than this range, the reaction rate decreases.When the amount of the cationizing agent (3) is larger than this range, the cationizing agent (3) or the hydrolyzate of the cationizing agent (3) is used. Is undesirably left in the reaction mixture. The end point of the reaction between the aliphatic primary amine (2) and the cationizing agent (3) is confirmed by analyzing the remaining amount of the aliphatic primary amine (2) during the reaction using high performance liquid chromatography. can do.

The reaction solution in the 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.

[0021]Manufacturing method <2>  [Cationization] Aliphatic primary amine (2) and general formula (4)

[0022]

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Wherein R ² , R ³ , R ⁴ and A have the above-mentioned meaning. With a cationizing agent (glycidyltrialkylammonium salt) represented by the general formula (1 ′)

[0024]

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[Wherein, R ¹ , R ² , R ³ , R ⁴ , and A have the above-mentioned meanings. Is obtained.

The present manufacturing method is specifically shown by the following formula.

[0027]

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[Wherein R ¹ , R ² , R ³ , R ⁴ and A have the same meaning as described above. In the reaction of the glycidyltrialkylammonium salt (4) with the aliphatic primary amine (2), the glycidyltrialkylammonium salt (4) is reacted with the aliphatic primary amine.
The molar ratio with the secondary amine (2) is 1/1 to 3/1. If the molar ratio is below this range, the reactivity is reduced, and if the molar ratio is beyond this range, a large amount of hydrolyzate of glycidyltrialkylammonium salt (4) remains in the reaction mixture, which is not preferable. . The reaction temperature is 30-120
° C, preferably 50-90 ° C. If the reaction temperature is lower than this range, the reaction rate is low, and if it exceeds this range, coloring and the like occur, which is not preferable. In the reaction between the aliphatic primary amine (2) and the glycidyltrialkylammonium salt (4), in order to secure the reactivity and promote a certain reaction, an appropriate amount of an aqueous alkali solution is charged and the pH is adjusted to 8
Preferably, it is maintained at ~ 12. If the pH is below this range, the reaction rate will be low, and if it is outside this range, a large amount of by-products will be produced and the yield will decrease.

The reaction of the present invention may be all carried out in air or in an inert gas atmosphere, but is preferably carried out in an inert gas atmosphere from the viewpoint of coloring and the like.

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

[0031]

The compound obtained by the method of the present invention has surface activity, and a surfactant containing such a compound as a main component has excellent flexibility and low irritation, so that it can be used as a hair rinse base. Can be offered.

[0032]

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.

Embodiment 1Cationization (synthesis of compound (1))  3 liters with stirrer, condenser, thermometer, dropping funnel
185 g of laurylamine (1 m
), 185g of ethanol, 70-80 ° C with stirring
Until heated. Then, while stirring the mixture,
Insert the electrode into the solution and drop a 40% aqueous sodium hydroxide solution.
The pH was lowered to 10. Next, 3-chloro-2-hydroxy
Propyl-N-stearyl-N, N-dimethylammonium
1846 g (1.3 mol) of 30% aqueous solution of muchloride (MW426)
It was dropped in 2 hours. During this time, to maintain pH10, 40% water
Sodium oxide was added dropwise as appropriate. 3-chloro-2-hydride
Roxypropyl-N-stearyl-N, N-dimethylan
After completion of the dropping of monium chloride, maintain pH 10
While continuing heating and stirring, high-speed liquid chromatography is performed every hour.
The remaining amount of laurylamine was confirmed by chromatography.

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

After purifying the reaction solution using an electrodialysis apparatus, a part of the reaction solution was evaporated to dryness, and the above-mentioned formula (1) was analyzed by mass spectrometry.
And N-lauryl-N- [3- (N'-stearyl-N ', N'-dimethylammonio) -2-hydroxypropyl] amine chloride (having the following structural formula) was obtained.

[0036]

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<Mass Spectrometry>Apparatus; SX-102 type mass spectrometer manufactured by JEOL Ltd. Measurement conditions; introduction method directly; ionization method FAB (Fast Atom Bomberdment) analysis result; fragment ion molecular weight 540, 186 main peak 2 A book was observed, and 540 was the (M ⁺ -Cl) ion peak, confirming that it was a cationic compound having the above structure.

Example 2 Stearylamine was used in place of laurylamine as a raw material amine, and 3-chloro-2-hydroxypropyl-N-lauryl-N, N-dimethylammonium chloride was used as a cationizing agent in 3-chloro-2- A method similar to that of Example 1 was carried out in the same manner as in Example 1, except that hydroxypropyl-N-stearyl-N, N-dimethylammonium chloride was used instead of the obtained compound, and that the obtained compound had the following structure: Confirmed.

[0039]

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<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

Analysis results; fragment ion molecular weight 540, 270 Two main peaks were observed, and 540 was the (M ⁺ -Cl) ion peak, confirming that it was a cationic compound having the above structure.

Example 3 3-Chloro-2-hydroxypropyl-N-lauryl-N, N-dimethylammonium chloride was converted to 3-chloro-2-hydroxypropyl-N-stearyl-N, N-dimethylammonium as a cationizing agent. The same procedure as in Example 1 was carried out to confirm that the obtained compound had the following structure, except that chloride was used instead of chloride.

[0043]

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<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

Analysis result: fragment ion molecular weight 456, 270 Example 4 The same procedure as in Example 1 was carried out except that stearylamine was used instead of laurylamine as the starting amine, and the obtained compound had the following structure: This was confirmed in the same manner as in Example 1.

[0046]

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<Mass Spectrometry> The analysis was performed under the same conditions as in Example 1.

Analysis results; fragment ion molecular weight 624, 270 Example 5 As a cationizing agent, instead of 3-chloro-2-hydroxypropyl-N-stearyl-N, N-dimethylammonium chloride, 2,3-oxypropyl- A method similar to that of Example 1 was carried out under the same conditions as in Example 1 except that N-stearyl-N, N-dimethylammonium chloride was used, and the obtained compound was 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 evaluated for skin irritation and flexibility by the methods described below. Was evaluated. Table 1 shows the results.

<Control Compound 1> Cotamine manufactured by Kao Corporation
86P (stearyltrimethylammonium chloride)-Skin irritation test A 24-hour closed patch test on humans was performed. That is, a patch test adhesive bandage impregnated with 0.1 ml of an aqueous solution containing 0.2% of a surfactant as an effective component was applied to 20 subjects for 24 hours, and the irritation was evaluated 24 hours after removing the application. As a result of determination, those showing clear erythema were defined as positive, and the positive rate was shown.

Flexibility evaluation test An alcohol emulsion adjusted to be 1% of various surfactants, 3% of higher alcohol, and 3% of propylene glycol was washed with a shampoo without a treatment agent, and then washed with a squeezer. % By weight and left for 1 minute. afterwards
It was rinsed with warm water at 40 ° C for a certain period of time, dried with a towel, and evaluated for WET. After that, dry uru with a drier and dry
The time was evaluated. The evaluation results were evaluated as ○ when good, × when unfavorable, and Δ when intermediate.

[0052]

[Table 1]

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 213/00 C07C 213/00 215/18 215/18 305/06 305/06 C11D 1/62 C11D 1/62 (56) Reference Document JP-A-61-207362 (JP, A) JP-B-51-12646 (JP, B1) Chem. Abstr. , (1963) vol. 58 abstract No. 10030f (58) Fields investigated (Int.Cl. ⁶ , DB name) C07C 211/63 A61K 7/08 B01F 17/18 C07C 209/68 C07C 209/74 C07C 213/00 C07C 215/18 C07C 305/06 C11D 1/62 CAOLD (STN) CAPLUS (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] [Claim 1] General formula (1) Wherein R ¹ and R ² are linear or branched alkyl or alkenyl groups having 8 to 22 carbon atoms, R ³ and R ⁴ are the same or different alkyl groups having 1 to 3 carbon atoms, and Y is H or hydroxy. Group, A is O
H represents a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms. n represents 0 or an integer of 1 to 5, and when n = 1,
Y represents H or a hydroxy group, and n = 0, 2, 3, 4,
In the case of 5, Y = H. ] The cation compound represented by these. 2. A compound of the general formula (2) R ¹ NH ₂ (2) wherein R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms. And an aliphatic primary amine represented by the general formula (3): Wherein R ² is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ³ and R ⁴ are the same or different carbon atoms having 1 to 2 carbon atoms.
3, an alkyl group, Y represents H 2 or a hydroxy group, A represents OH, a halogen atom or an alkyl sulfate group having 1 to 4 carbon atoms.
n represents 0 or an integer of 1 to 5, and when n = 1, Y = H
Or a hydroxy group, and when n = 0, 2, 3, 4, 5 represents Y = H. Z represents a halogen atom. The method for producing a cation compound represented by the general formula (1) according to claim 1, wherein the cation compound is reacted with a cationization agent represented by the following formula: 3. General formula (2) R ¹ NH ₂ (2) wherein R ¹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms. And an aliphatic primary amine represented by the general formula (4): Wherein R ² is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and R ³ and R ⁴ are the same or different carbon atoms having 1 to 2 carbon atoms.
3 alkyl groups, A is OH, a halogen atom or a carbon atom
4 represents an alkyl sulfate group. And a cationizing agent represented by the following general formula (1 ′): [Wherein R ¹ , R ² , R ³ , R ⁴ and A have the above-mentioned meaning. ]
A method for producing a cationic compound represented by the formula: 4. A surfactant comprising the cationic compound represented by the general formula (1) according to claim 1.