JP2001294561A - Quaternary ammonium salt composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a quaternary ammonium salt composition causing no deterioration of its smell even during preservation, and causing no pH drop thereof, thus good in preservation stability, and to provide a method for producing the above composition. SOLUTION: This quaternary ammonium slat composition comprises at lest two components, i.e., a trialkylamine of a general formula (I) and a quaternary ammonium salt of a general formula (II), and furthermore contains <=100 mg/kg of benzaldehyde based on the quaternary ammonium salt and <=1,000 mg/kg of benzyl alcohol based on the quaternary ammonium slag, wherein the content of the trialkylamine in the composition is 500-8,000 mg/kg based on the quaternary ammonium slat. The method for producing the above composition is provided. (in the general formulas (I) and (II), R1 is a 6-24C alkyl or alkenyl; R2 is a 1-24C alkyl or alkenyl or 2-3C hydroxyalkel; R3 is a 1-3C alkyl or 2-3C hydroxyalkyl; and X is a halogen atom).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quaternary ammonium salt composition having good pH and odor storage stability and a method for producing the same.

[0002]

2. Description of the Related Art Quaternary ammonium salts such as trialkylbenzylammonium chloride have been used for sterilizing and antibacterial agents for a long time. It is also used as a fabric softener, a hair rinse, a cosmetic emulsifier, and the like. This quaternary ammonium salt is obtained by quaternizing a trialkylamine with benzyl halide. The product immediately after the quaternization has a bad odor, and after the quaternization reaction, activated carbon treatment or vacuum deodorization purification may be performed to improve the odor. But,
Even if such a purification operation is performed, in addition to the target quaternary ammonium salt, trialkylamine, benzaldehyde,
Benzyl alcohol and the like are present and cause deterioration of the quality of the product, particularly the odor during storage of the product. Further, even if the purity of the quaternary ammonium salt is increased by repeating the purification operation, the deterioration of the odor during storage of the product can be prevented, but there is a problem that the pH decreases during storage.

It is an object of the present invention to provide a fourth storage material which is excellent in storage stability in which the odor does not deteriorate during storage and the pH does not decrease.
It is an object of the present invention to provide a quaternary ammonium salt composition and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have found that a quaternary ammonium salt composition containing a specific proportion of a trialkylamine can solve the above problems.

The present invention relates to a trialkylamine represented by the general formula (I) (hereinafter referred to as trialkylamine (I)).
And at least two components of a quaternary ammonium salt represented by the general formula (II) (hereinafter referred to as a quaternary ammonium salt (II)), and the content of the trialkylamine (I) is
500 to 8000 mg / kg for the quaternary ammonium salt (II), and 100 mg / k for the quaternary ammonium salt (II).
The present invention relates to a quaternary ammonium salt composition containing benzaldehyde of not more than g and benzyl alcohol of not more than 1000 mg / kg, and a method for producing the same.

[0006]

Embedded image

[0007]

Embedded image

(In the above formula, R ¹ is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, R ² is a linear or branched alkyl or alkenyl group having 1 to 24 carbon atoms, or A hydroxyalkyl group having 2 to ³ carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms or 2 to 3 carbon atoms;
X represents a halogen atom. )

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formulas (I) and (II),
R ¹ is preferably an alkyl group or alkenyl group having 6 to 24, particularly 8 to 18 carbon atoms, and R ² is a group having 1 to ² carbon atoms.
Is preferred, and R ³ is preferably an alkyl group having 1 to 2 carbon atoms. X includes a chlorine atom and a bromine atom, and a chlorine atom is preferable.

Specific examples of the trialkylamine (I) include dimethylhexylamine, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine,
Dimethyltetradecylamine, dimethylhexadecylamine, dimethyloctadecylamine, dimethyloctadecenylamine, dimethyldecenylamine, dimethyldodecenylamine, dimethyltetradecenylamine, dimethylhexadecenylamine, dimethyloleylamine, diethylhexylamine, diethyl octylamine, diethyldecylamine, diethyl dodecylamine, diethyl tetradecyl amine, diethyl hexadecylamine, diethyl octadecylamine, N- methyl -N- hexadecyl - but octadecylamine, and the like, R ¹ is a carbon number 6 to 24 A linear or branched alkyl group of R ² and R ³
Is preferably a methyl group.

The content of the trialkylamine (I) in the composition of the present invention is from 500 to 8000 mg / k with respect to the quaternary ammonium salt (II) from the viewpoint of pH and storage stability of the odor.
g, preferably 600-6000 mg / kg, and 600-4000 mg / k
g is more preferred.

The composition of the present invention has a benzaldehyde content of 100 mg / kg or less, preferably 40 mg / kg or less, based on the quaternary ammonium salt (II), from the viewpoint of pH and odor storage stability. , The content of benzyl alcohol is 10
It is at most 00 mg / kg, preferably at most 600 mg / kg.

The composition of the present invention comprises a trialkylamine (I) and a benzyl halide represented by the general formula (III) (hereinafter referred to as benzyl halide (III)) per 1 mol of the trialkylamine (I). Benzyl halide (III) 0.9
After the quaternization reaction at a rate of 6 to 1.01 mol, the reaction product is maintained at a temperature of 50 to 100 ° C. and a degree of vacuum of 1 to 100 kPa, and water and / or
Alternatively, it is obtained by adding a polyhydric alcohol to the quaternary ammonium salt (II) in an amount of 0.5 to 4 times by weight and distilling off low-boiling components.

[0014]

Embedded image

(Wherein, X has the above-mentioned meaning.) The quaternization reaction of the trialkylamine (I) with the benzyl halide (III) is carried out by reacting 1 mole of the trialkylamine (I) with the benzyl halide ( III) 0.96 to 1.01 mol, preferably 0.98 to 1.00 mol, is dropped and reacted. The reaction is carried out in water, the reaction temperature is preferably 50 to 100 ° C., and the dropping time of benzyl halide (III) is preferably 1 to 4 hours. After completion of the quaternization reaction, aging at 50-100 ° C. for 1-5 hours is preferred.

Next, the quaternized reaction product is heated at a temperature of 50 to 100 ° C.
Preferably 60 to 95 ° C., degree of vacuum 1 to 100 kPa, preferably 10
While maintaining the pressure at ~ 65 kPa, low boiling components are distilled off while adding water and / or a polyhydric alcohol to the quaternary ammonium salt (II) by 0.5 to 4 times, preferably 1 to 4 times by weight. Steam may be added instead of water. Polyhydric alcohols include ethylene glycol, propylene glycol,
Glycerin and the like.

[0017]

EXAMPLES In the following examples, the analysis of trialkylamine was carried out by liquid chromatography [column: L-column ODS (4.6 mmφ × 150 mm) manufactured by Chemicals Evaluation and Research Institute, column temperature: 4
0 ° C., eluent: 1 mL / min, 0.1% TFA methanol / water = 8/2 solution], analysis of benzaldehyde and benzyl alcohol by liquid chromatography [Column: Develosil C30-UG-5 (manufactured by Nomura Chemical Co., Ltd.) 4.6mmφ × 250mm), Column temperature: 40 ° C, Eluent: 0.1mol / L NaClO ₄ aqueous solution
Mixture with 0.1 mol / L NaClO ₄ acetonitrile solution].

The content of the quaternary ammonium salt is calculated by subtracting the content of the trialkylamine obtained by the above-mentioned analytical method from the value of the total content of the quaternary ammonium salt and the amine obtained by the following method. Desired. <Quantitative method for quaternary ammonium salts> 0.30 g of a sample was precisely weighed, dissolved in 75 mL of water, and diluted with dilute hydrochloric acid to adjust the pH to 2.6 to 3.4. Add 1 drop of test solution. 0.02 mol / separately adjusted
Titrate with a sodium L-tetraphenylboron solution until the solution turns red, and determine the total content (%) of the quaternary ammonium salt and the amine by the following formula.

[0019]

(Equation 1)

Example 1 In a 500 ml four-necked flask, 85.2 g (0.400 mol) of dimethyldodecylamine and 135.000 ion-exchanged water were added.
2 g was charged and the temperature was raised to 60 ° C. To this, 50.1 g (0.396 mol) of benzyl chloride was added dropwise over 3 hours while maintaining the temperature at 60 ° C., and then aging was performed at the same temperature for 3 hours.
Then, further, the degree of vacuum in the system is 18 to 22 kPa, and the temperature is 60.
While maintaining the temperature at ６５65 ° C., 541.2 g of ion-exchanged water was gradually added dropwise, and low-boiling components were distilled off together with the ion-exchanged water. The amount of ion-exchanged water used for distilling low boiling components is 4 times the weight of dimethyldodecylbenzylammonium chloride (hereinafter referred to as effective component). After the distillation of the low boiling components was completed, the inside of the system was returned to normal pressure to obtain a purified product. Then, 20% NaO
The pH was adjusted using an aqueous H solution (pH = 7.0 to 7.0).
8.0). The resulting purified product had a pH of 7.8. As a result of analyzing the composition of the purified product, dimethyldodecylamine 600 mg / kg and benzaldehyde 7 mg /
kg, benzyl alcohol 240 mg / kg.

Example 2 A quaternization reaction and aging were carried out in the same manner as in Example 1 to obtain a similar reaction product. Thereafter, the temperature was raised to 75 ° C., and while maintaining the degree of vacuum in the system at 30 to 40 kPa, ion-exchanged water 27
0.6 g was gradually added dropwise, and low-boiling components were distilled off together with ion-exchanged water. The amount of ion-exchanged water used for distilling out the low-boiling components is twice as much as that of dimethyldodecylbenzylammonium chloride (hereinafter referred to as an effective component). After the distillation of the low boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was adjusted in the same manner. The resulting purified product had a pH of 7.8. As a result of analyzing the composition of the purified product, dimethyldodecylamine 1000 mg / kg, benzaldehyde 30
mg / kg and 580 mg / kg of benzyl alcohol.

Example 3 A quaternization reaction and aging were carried out in the same manner as in Example 1 except that the amount of benzyl chloride was changed to 50.6 g (0.40 mol) to obtain a similar reaction product. Thereafter, the temperature was raised to 75 ° C., and while maintaining the degree of vacuum in the system at 30 to 40 kPa, 271.6 g of ion-exchanged water was gradually dropped, and low-boiling components were distilled off together with the ion-exchanged water. The amount of ion-exchanged water used for distilling out the low-boiling components is twice as much as that of dimethyldodecylbenzylammonium chloride (hereinafter referred to as an effective component). After the distillation of the low boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was adjusted in the same manner. The resulting purified product had a pH of 7.8. As a result of analyzing the composition of the purified product, 3400 mg / kg of dimethyldodecylamine, 36 mg / kg of benzaldehyde, and 560
mg / kg. Example 4 A quaternization reaction and aging were carried out in the same manner as in Example 3 to obtain a similar reaction product. Thereafter, the temperature was raised to 85 ° C, and while maintaining the degree of vacuum in the system at 55 to 65 kPa, ion-exchanged water 27
1.6 g was gradually added dropwise, and low-boiling components were distilled off together with ion-exchanged water. The amount of ion-exchanged water used for distilling out the low-boiling components is twice as much as that of dimethyldodecylbenzylammonium chloride (hereinafter referred to as an effective component). After the distillation of the low boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was adjusted in the same manner. The resulting purified product had a pH of 7.9. As a result of analyzing the composition of the purified product, 4200 mg / kg of dimethyl dodecylamine and 18
mg / kg and benzyl alcohol 600 mg / kg. Example 5 A quaternization reaction and aging were performed in the same manner as in Example 3 to obtain a similar reaction product. Thereafter, the temperature was raised to 85 ° C, and while maintaining the degree of vacuum in the system at 55 to 65 kPa, ion-exchanged water 47
5.3 g was gradually added dropwise, and low-boiling components were distilled off together with ion-exchanged water. The amount of ion-exchanged water used for distilling low boiling components is 3.5 times by weight based on dimethyldodecylbenzylammonium chloride (hereinafter referred to as effective component). After the distillation of the low-boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was similarly adjusted.
Adjustments were made. The resulting purified product had a pH of 7.8. As a result of analyzing the composition of the purified product, dimethyldodecylamine was found to be 6000 mg / kg, benzaldehyde 24 mg / kg, and benzyl alcohol 560 mg / kg based on the effective components.

Comparative Example 1 A quaternization reaction and aging were carried out in the same manner as in Example 1 to obtain a similar reaction product. Thereafter, the degree of vacuum in the system is 8 to 12 kPa,
While maintaining the temperature at 43 to 45 ° C., ion-exchanged water 541.
2 g was gradually added dropwise, and low-boiling components were distilled off together with ion-exchanged water. The amount of ion-exchanged water used for distilling low boiling components is 3.5 times by weight based on dimethyldodecylbenzylammonium chloride (hereinafter referred to as effective component). After the distillation of the low boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was adjusted in the same manner. The resulting purified product had a pH of 7.8. As a result of analyzing the composition of the purified product, 1660 mg / kg of dimethyl dodecylamine and 17
0 mg / kg and benzyl alcohol 1100 mg / kg.

Comparative Example 2 A quaternization reaction and aging were carried out in the same manner as in Example 3 to obtain a similar reaction product. Thereafter, the temperature was raised to 85 ° C., and while maintaining the degree of vacuum in the system at 55 to 65 kPa, ion-exchanged water 74
6.9 g was gradually added dropwise, and low-boiling components were distilled off together with ion-exchanged water. The amount of ion-exchanged water used for distilling low boiling components is 5.5 times the weight of dimethyl dodecylbenzylammonium chloride (hereinafter referred to as an effective component). After the distillation of the low-boiling components was completed, a purified product was obtained in the same manner as in Example 1, and the pH was similarly adjusted.
Adjustments were made. The pH of the resulting purified product was 7.7. As a result of analyzing the composition of the purified product, dimethyldodecylamine was 100 mg / kg, benzaldehyde was 6 mg / kg, and benzyl alcohol was 240 mg / kg based on the effective components.

The pH of the purified products obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was measured immediately after purification and after storage at 60 ° C. for one month, and the odor was evaluated by the following method. Table 1 shows the results. <Evaluation method of odor> 50 ml of the aqueous solution (effective concentration: 3%) of the purified product obtained in Examples 1 to 5 and Comparative Examples 1 and 2 was weighed in a 100 ml Erlenmeyer flask with a stopper and heated to 40 ° C. The evaluation was performed by five odor panelists. 1 point for no odor, 0 point for weak odor, and -1 point for strong odor. The total score of 5 people was 2 or more: ○ (usable), -2 to less than 2 points: Δ (unusable), -2 A mark below the point was evaluated as x (unusable).

[0026]

[Table 1]

As is clear from Table 1, the purified product obtained in the Examples shows odor deterioration and pH even after storage at 60 ° C. for one month.
Although the storage stability was excellent and storage stability was excellent, the purified product obtained in the comparative example showed odor deterioration or pH reduction.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C11D 3/26 C11D 3/26 3/48 3/48 F term (reference) 4H003 AE05 DA02 EB19 FA16 FA25 FA28 FA34 4H006 AA02 AC52 AD11 AD40 BB14 BB31 BC31 BC50 BC51 BC52 4H011 AA02 BA04 BB04 BC04 DA13 DF03 DG03

Claims (2)

[Claims] 1. A trialkylamine represented by the general formula (I) (hereinafter referred to as trialkylamine (I)) and a quaternary ammonium salt represented by the general formula (II) (hereinafter quaternary ammonium salt ( II)), the content of the trialkylamine (I) is 500 to 8000 mg / kg with respect to the quaternary ammonium salt (II), and the quaternary ammonium salt (II) A) a quaternary ammonium salt composition containing 100 mg / kg or less of benzaldehyde and 1000 mg / kg or less of benzyl alcohol; Embedded image Embedded image (In the above formula, R ¹ is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms, and R ² is a C 1 to 24 carbon atom.
A linear or branched alkyl or alkenyl group, or a hydroxyalkyl group having 2 to ³ carbon atoms, R ³ is an alkyl group having 1 to ³ carbon atoms or a hydroxyalkyl group having 2 to 3 carbon atoms, and X is a halogen atom. Show. ) 2. Trialkylamine (I) and a compound represented by the general formula (II)
The benzyl halide represented by I) is quaternized at a ratio of 0.96 to 1.01 mol of benzyl halide to 1 mol of trialkylamine (I), and the reaction product is heated to a temperature of 50 to 50 mol.
Keep the water and / or polyhydric alcohol at 0.5 to 4 with respect to the quaternary ammonium salt (II) at 100 ° C. and a degree of vacuum of 1 to 100 kPa.
The method for producing a composition according to claim 1, wherein the low-boiling components are distilled off while being added by weight. Embedded image (In the formula, X has the above-mentioned meaning.)