JP3174141B2 - Method for producing di-long chain tertiary amine salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a dilong-chain tertiary amine salt which is a softener base useful as a softening agent for clothing. More specifically, when producing the base, a neutralization reaction can be performed in a low viscosity state by performing a neutralization reaction while controlling the temperature. The present invention relates to a method for producing an aqueous dispersion of a tertiary amine salt.

[0002]

2. Description of the Related Art Soft finishes for clothing contain a softener base as a main component, but in order to increase the convenience of use and to efficiently impart performance.
It is known that the softener base needs to be a stable aqueous dispersion. Therefore, a stable aqueous dispersion has been conventionally obtained by dispersing the softener base in warm water having a melting point or higher in the presence of an emulsifier. For example, di (hardened tallowalkyl) dimethylammonium chloride, which is a quaternary ammonium salt widely used as a main base of currently available home softeners, is made into an aqueous dispersion by the above-described method. . Since this compound is a quaternary ammonium salt, it does not involve a chemical change when it is made into an aqueous dispersion, so that there is no sharp rise in liquid viscosity, etc. I didn't find it.

The present inventors have previously proposed a di-long chain tertiary amine salt as a softening agent capable of imparting sufficient flexibility and antistatic properties to various fibers and imparting excellent elasticity. (Japanese Patent Application No. 2-221742), and tried to obtain an aqueous dispersion in the same manner as in the above method. However, when an aqueous dispersion is to be obtained using a di-long-chain tertiary amine salt in which a di-long-chain tertiary amine compound has been previously neutralized with an acid, the resulting di-long-chain tertiary amine compound is obtained. It has been found that the aqueous dispersion of a tertiary amine salt has inferior stability during storage, and the above-described method used for the quaternary ammonium salt cannot be directly applied.

As a means for obtaining a stable aqueous dispersion of a di-long-chain tertiary amine salt, a di-long-chain tertiary amine compound which is a non-aqueous component is completely melted in the presence of an emulsifier. Then, neutralization may be performed in a so-called O / W emulsion state dispersed in a continuous aqueous phase. However, in this system, the viscosity significantly increases with the progress of the degree of neutralization and becomes a gel, so that it takes a long time to obtain a uniform degree of neutralization, and further strong stirring power is required. Such,
There was a disadvantage that the manufacturing equipment was large and heavy. Further, in the aqueous dispersion without an emulsifier, although a remarkable increase in viscosity is not observed, there are problems such as that the particle size distribution of the dispersion becomes uneven, and that oily components and aqueous components are easily separated during storage. . An object of the present invention is to solve these problems by neutralizing an aqueous dispersion of a dilong-chain tertiary amine compound while controlling the temperature, so as to have a uniform degree of neutralization and improve stability. An object of the present invention is to provide an excellent method for producing an aqueous dispersion of a long-chain tertiary amine salt.

[0005]

Means for Solving the Problems The present inventors carried out a neutralization reaction between a dilong-chain tertiary amine compound and an acid in the presence of an emulsifier or a solvent while controlling the acid at a predetermined temperature range. It was found that a stable aqueous dispersion of a long-chain tertiary amine salt could be obtained without causing a sudden increase in the viscosity of the liquid at the time of neutralization. Also conducted intensive research with a focus on energy saving and the like, and completed the present invention. That aspect of the present invention, one of the R- CO O-groups derived from fatty acids having 12 to 22 carbon atoms in the molecule (R denotes an alkyl or alkenyl group having 11 to 21 carbon atoms), -CONH A dilong-chain tertiary amine salt by neutralizing a di-long-chain tertiary amine compound having one group and one alkyl or alkenyl group having 11 to 22 carbon atoms with an acid To produce a di-long-chain tertiary amine salt in the presence of an emulsifier or a solvent at a melting point of the di-long-chain tertiary amine compound at a melting point or a temperature range 25 ° C. lower than the melting point. The present invention relates to a method for producing a dilong-chain tertiary amine salt, which comprises producing an aqueous dispersion having a concentration of about 30% by weight.

[0006] The production method of the present invention comprises the above-mentioned di-long chain type third
This is to produce an aqueous dispersion of a dilong-chain tertiary amine salt by neutralizing a secondary amine compound with an acid. Here, as the di-long chain tertiary amine compound, for example, a compound represented by the following (A-1), (A-2) or (A-3) can be used.

[0007]

Embedded image

[0008] (In the formula, R ¹ represents an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, the R ^2, R ³ are the same or different and each an alkyl or alkenyl group having 11 to 21 carbon atoms, R ⁴ Represents an alkyl group or an alkenyl group having 12 to 22 carbon atoms. M is 2 or 3.) In the production method of the present invention, these compounds may be used alone or as a mixture of two or more. it can.

The method of synthesizing the above compound is not particularly limited, and it can be synthesized according to the following method (Japanese Patent Application No. 2-221742). That is,
The compound represented by (A-1) is, for example, a compound represented by the following formula (AB-1) obtained by cyanoethylation and hydrogenation of a dialkanolamine such as N-lower alkylalkanolamine or diethanolamine. Carbon number 12
To 22 fatty acids.

[0010]

Embedded image (In the formula, R ¹ and m represent the same meaning as described above.)

The compound represented by (A-2) is, for example, a compound represented by the following formula (AB-2) obtained by an intramolecular dehydration cyclization reaction of N-lower alkyldiethanolamine with an aliphatic amine And a ring-opening amidation reaction, followed by a reaction with a fatty acid halide having 12 to 22 carbon atoms, and washing the obtained compound with an alkali solution such as sodium hydroxide.

[0012]

Embedded image (In the formula, R ¹ has the same meaning as described above.)

Further, the compound represented by (A-3) can be obtained by, for example, the following formula (AB-) obtained by intramolecular dehydration cyclization of N-higher alkyl or alkenyldiethanolamine.
After reacting the compound represented by 3) with a lower alkylamine, the compound is reacted with a fatty acid halide having 12 to 22 carbon atoms,
The compound can be obtained by washing the obtained compound with an alkaline solution such as sodium hydroxide.

[0014]

Embedded image (In the formula, R ⁴ represents the same meaning as described above.)

As the acid used in the present invention, either an inorganic acid or an organic acid can be used. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Lactic acid, glycolic acid, citric acid,
An organic acid having 1 to 6 carbon atoms such as maleic acid can be used. These acids can be used alone or as an aqueous solution. Further, it can be used with a single acid or a mixed acid of two or more. Among them, hydrochloric acid or sulfuric acid is preferred from the viewpoints of acid cost, stability of the obtained di-long chain tertiary amine salt, odor and the like. In the present invention, the di-long chain tertiary amine compound may not be completely neutralized, and the amount of the acid used is preferably 0.8 to 1.5 times the equivalent amount of the neutralization. Preferably it is 1.0 to 1.3 times. 0.
If it is less than 8 times, hydrolysis of the di-long-chain tertiary amine compound occurs, and the stability of the aqueous dispersion is undesirably reduced. If it exceeds 1.5 times, the pH of the aqueous dispersion becomes extremely low, and its stability is lowered, and it is not preferable as a softening agent for clothing.

In the production method of the present invention, an emulsifier or a solvent is used at the time of neutralization in order to obtain a stable aqueous dispersion of the di-long-chain tertiary amine salt. Here, the emulsifier is not particularly limited as long as it is a nonionic surfactant. For example, polyoxyethylene alkyl ether (ethylene oxide: 5 to 50 mol, carbon number of alkyl group: 12 to 12)
24), polyoxyethylene alkenyl ether (ethylene oxide: 5 to 50 mol, carbon number of alkenyl group: 12)
To 24), polyoxyethylene alkylamine (ethylene oxide: 5 to 50 mol, carbon number of alkyl group: 12 to 2)
4), polyoxyethylene alkenylamine (ethylene oxide: 5 to 50 mol, carbon number of alkenyl group: 12 to 2)
4) and the like. In addition, substances using propylene oxide instead of ethylene oxide of these compounds and substances using a mixture of ethylene oxide and propylene oxide can also be suitably used. Further, tri- to hexa-valent polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol, and lauric acid, oleic acid, stearic acid, and hardened tallow fatty acid having 8 to 8 carbon atoms.
An ester compound with a long-chain fatty acid of 22 or a compound in which 2-80 mol of ethylene oxide and / or propylene oxide is added to a hydroxyl group of the ester compound can be used. Examples of the solvent include alcohols such as ethanol, isopropanol, propylene glycol, and ethylene glycol. These can be used alone or in combination of two or more. The amount of the emulsifier or the solvent to be added is generally 2 to 30 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of the dilong-chain tertiary amine compound. If the amount is less than 2 parts by weight, the effect of emulsification and dispersion or the stability of the di-long-chain tertiary amine salt decreases, which is not preferred. On the other hand, even if it is added in an amount of more than 30 parts by weight, the effect is not improved, and conversely, there is a problem in liquid properties at the time of use such as an increase in the viscosity of the aqueous dispersion solution, which is not preferable. The method for adding the emulsifier or the solvent is not particularly limited, and specific examples include the methods described below. In the present invention, either an emulsifier or a solvent may be used, but both may be used in combination. Water such as ion-exchanged water is usually used as the dispersion medium used in the present invention.

In the production method of the present invention, a neutralization reaction is performed using the above-mentioned raw materials. The present invention is characterized in that the neutralization reaction is performed while controlling the temperature within a specific temperature range. here,
The temperature of the neutralization reaction is usually a melting point of the dilong-chain tertiary amine compound or a temperature range 25 ° C. lower than the melting point,
Preferably a temperature 3 ° C. below the melting point to 15 ° C. below the melting point
Low temperature range. If the melting point is exceeded, a sharp increase in viscosity occurs, causing gelation, making it impossible to obtain a uniform aqueous dispersion, making the degree of neutralization non-uniform, and requiring a heavy stirrer and excessive power. This is not preferred in terms of surface. On the other hand, when the temperature is lower than 25 ° C. lower than the melting point, the di-long-chain tertiary amine compound and / or the di-long-chain tertiary amine salt, which is a neutralized product, precipitates to obtain a stable aqueous dispersion. At the same time, there is a difference in the degree of neutralization between the surface and the inside of the dispersion particles themselves, and it becomes difficult to obtain a uniform degree of neutralization between the dispersions.

In the production method of the present invention, the concentration of the obtained di-long-chain tertiary amine salt in the aqueous dispersion is usually 5 to 5.
The amount of the raw material used is adjusted so as to be 30% by weight, preferably 10 to 25% by weight. If the concentration is less than 5% by weight, a rapid increase in viscosity during neutralization is eliminated, but productivity is reduced because the solution is a dilute solution. On the other hand, if it exceeds 30% by weight, gelation occurs at the time of neutralization and uniform neutralization is difficult,
Further, it is difficult to obtain a stable aqueous dispersion. Specifically, although the amount slightly varies depending on the amount of the emulsifier, the solvent, and the acid used, the amount of the dilong-chain tertiary amine compound is mainly
By adjusting the concentration to 5 to 70 parts by weight with respect to 0 parts by weight, the concentration can be adjusted. By performing the neutralization reaction in such a concentration range and in the above temperature range, a di-length having a uniform degree of neutralization and excellent storage stability without causing a sudden increase in the liquid viscosity during neutralization. An aqueous dispersion of a chain type tertiary amine salt can be easily and energy-savingly produced.

The neutralization reaction of the di-long-chain tertiary amine compound and the acid in the present invention is in accordance with a general amine / acid neutralization reaction, and the neutralization procedure is also a method of adding an acid. Or a method in which a previously prepared solution containing an acid and a solution containing a dilong-chain tertiary amine compound are simultaneously mixed, and the method is not particularly limited. Specifically, the following various methods can be adopted. An acid is added to and mixed with a dispersion obtained by dispersing the above-mentioned emulsifier or solvent and a di-long-chain tertiary amine compound in water. Both a dispersion in which the above-mentioned emulsifier or solvent and the di-long chain tertiary amine compound are dispersed in water and an acid are simultaneously charged into a container and mixed. A dilong-chain tertiary amine compound is added to and mixed with an aqueous solution in which the above-mentioned acid and emulsifier or solvent are mixed with water. An aqueous solution obtained by mixing the above-mentioned acid and emulsifier or solvent in water and both liquids of the di-long chain tertiary amine compound are simultaneously charged into a container and mixed. An aqueous solution in which the above-mentioned emulsifier or solvent is mixed with water, and three components of a dilong-chain tertiary amine compound and an acid are simultaneously charged into a container and mixed.

The method of the neutralization reaction may be any of a batch system using a stirring tank, a continuous system such as a continuous stirring tank or a tubular line mixing, or a combination of the batch system and the continuous system. Mixing at the time of neutralization can be performed with a stirrer, a static mixer, a high-shear mixer, or the like, but it is preferable to mix with a high-shear mixer in view of the stability of the resulting aqueous dispersion.

[0021]

EXAMPLES The present invention will be described below with reference to examples and the like.
The present invention is not limited by these examples.

Synthesis Example 1 A known method using an adduct of N-methylethanolamine and acrylonitrile [J. Org. Chem. , 26 , 3
409, (1960)], 66 g of N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine and 284 g of hardened tallow fatty acid were placed in a four-necked flask equipped with a stirrer, thermometer and dehydration tube. It was charged and heated to 180 ° C. The mixture is heated at that temperature for about 10 hours while distilling off generated water. In the general formula (A-1), R ¹ is methyl, R ² and R ³ are hardened tallow fatty acid residues, and m is 2. Reactant 3 mainly composed of a dilong-chain tertiary amine compound
00 g were obtained. The acid value, saponification value, hydroxyl value, total amine value, and tertiary amine value of the obtained reaction product were measured, and the composition of the reaction product was examined.
6% by weight, 10% by weight of a mono-long-chain tertiary amine, and 4% by weight of an unreacted fatty acid. The molecular weight of the di-long-chain tertiary amine compound was 644, and the melting point was 58 to 64 ° C.

Example 1 313 g of ion-exchanged water was added to a 500 ml tall beaker having an inner diameter of 73 mm having stirring blades with a blade diameter of 35 mm, and the temperature was raised to 70 ° C. in a water bath capable of controlling the temperature. Ethylene oxide:
19 mol addition) 12.0 g of lauryl ether and Synthesis Example 1
80.0 g of the di-long chain tertiary amine compound obtained in the above was added. The mixture was emulsified at 70 ° C. for 5 minutes at a rotating speed of a stirring blade of 500 rpm, cooled to 50 ° C., and 13.0 g of a 35% by weight hydrochloric acid aqueous solution equivalent to neutralization while maintaining the liquid temperature at 50 ° C. under the stirring. Was added for 1 minute to neutralize, and then stirring was continued for 2 minutes to obtain an aqueous dispersion of 20% by weight of a dilong-chain tertiary amine salt. The maximum viscosity at the time of neutralization, the average particle size of the resulting aqueous dispersion of the di-long-chain tertiary amine salt, and the degree of neutralization were measured, and further the storage stability was tested. These physical property measurements and quality evaluations were performed by the following methods.

(1) Maximum viscosity during neutralization (unit: CP) A load current value of a motor used for mixing and stirring is automatically measured, and a measured value of a B-type viscometer prepared using a standard solution prepared in advance is used. The maximum viscosity at the time of neutralization was determined from a calibration curve of the load current value of the mixing and stirring motor. (2) Average particle diameter of dispersion (unit: nm) Di-long-chain tertiary amine salt aqueous dispersion is diluted with ion-exchanged water to a concentration of about 1% by weight, and the average particle diameter of dispersion is obtained. Was measured using a Coulter submicron particle analyzer (Coulter model N4). (3) Degree of neutralization (unit:%) The degree of neutralization was calculated from the amine value of the aqueous dispersion of the di-long-chain tertiary amine salt by the following formula. Degree of neutralization (%) = (amine value before neutralization−amine value after neutralization) / amine value before neutralization × 100 (4) Storage stability Di long chain type tertiary in a 100 cc sealed glass bottle 50 g of an aqueous dispersion of an amine salt was added thereto, and stored at 50 ° C. for 20 days.
Furthermore, the appearance was evaluated for a sample obtained by repeating storage at −20 ° C. and room temperature five times (24 hours / time). : No change in appearance. ×: Changes in appearance and properties such as liquid phase separation, cloudiness and thickening are observed.

Examples 2 to 5 Dilong-chain tertiary amine compounds, acids, emulsifiers,
Example 1 using a solvent at the neutralization temperature also shown in Table 1.
Under the same operating conditions as described above, an aqueous dispersion of a dilong-chain tertiary amine salt was obtained. Next, physical properties and quality evaluation were performed in the same manner as in Example 1. The di-long chain tertiary amine compound used in Example 2 was a compound represented by the following formula (AB-
21)

Embedded image To monostearylamine (CH ₃ (CH ₂ ) ₁₇ NH ₂ )
And a ring-opening amidation reaction with lauric chloride (CH ₃ (CH ₂ ) ₁₀ COCl), and the obtained compound is washed with an aqueous sodium hydroxide solution. The di-long chain tertiary amine compound used in Example 3 was a compound represented by the following formula (AB-3).
1)

Embedded image Is subjected to a ring-opening amidation reaction with monomethylamine (CH ₃ NH ₂ ), and then stearic acid chloride (CH ₃ (C ₃
H ₂ ) ₁₆ COCl), and the resulting compound was washed with an aqueous sodium hydroxide solution. The di-long-chain tertiary amine compounds used in Examples 4 and 5 were those obtained in Synthesis Example 1.

[0026]

[Table 1]

Embodiment 6 Inside diameter 6 having three propeller blades with a blade diameter of 200 mm inside
After charging 157 kg of ion-exchanged water into a 300-L stirring tank having a 00 mm jacket and pouring warm water of 80 ° C. into the jacket and raising the temperature of the stirring tank to 70 ° C., 6 kg of polyoxyethylene (addition of 19 mol of ethylene oxide: lauryl ether) 6 kg as an emulsifier And 40 kg of the dilong-chain tertiary amine compound obtained in Synthesis Example 1 were added. Rotation speed of stirring blade 200
The O / W emulsion of the di-long-chain tertiary amine compound kept at 70 ° C. while stirring at rpm was passed through a 0.1 m ² spiral heat exchanger while being fed to a metering pump for 100.
kg / Hr at a constant flow rate, while 3
A 5% by weight aqueous hydrochloric acid solution is neutralized at an equivalent ratio of 16.2 kg / H.
r and quantitatively simultaneously sent it to a static mixer (CSM-12-5) manufactured by Noritake Co., Ltd. to cause a neutralization reaction continuously and while maintaining the temperature of the neutralized product at the outlet of the static mixer at 50 ° C. Type tertiary amine salt 2
An aqueous dispersion of 0% by weight was obtained. Next, liquid properties and quality evaluation were performed in the same manner as in Example 1.

Comparative Examples 1 and 2 Neutralization temperature of 70 ° C. (Comparative Example 1) or 30 ° C. (Comparative Example 2)
In the same manner as in Example 1 except that the above, an aqueous dispersion containing 20% by weight of a di-long-chain tertiary amine salt was obtained. Next, liquid properties and quality evaluation were performed in the same manner as in Example 1.

The results of evaluation of physical properties and quality obtained in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 1 together with operating conditions.

As shown by the results in Table 1, in the production method of the embodiment in which the neutralization temperature is appropriate, the maximum viscosity at the time of neutralization is small, no coarse particles are generated, and the resulting aqueous dispersion is neutralized. High degree of storage stability. On the other hand, in the production method of Comparative Example 1 in which the neutralization temperature is too high, the liquid viscosity increases to 4,000 CP with the addition amount of hydrochloric acid, some gelation occurs, and the whole cannot be mixed uniformly. No degree of neutralization was obtained. In the case of the production method of Comparative Example 2 in which the neutralization temperature is too low,
Although no increase in viscosity was observed, the di-long-chain tertiary amine compound or the di-long-chain tertiary amine salt precipitated on the beaker walls and the like, and the degree of neutralization was as low as 80%.

[0031]

According to the method for producing a di-long-chain type tertiary amine salt of the present invention, storage stability having a uniform degree of neutralization without causing a sudden increase in liquid viscosity during neutralization. A water-based dispersion of a di-long-chain tertiary amine salt excellent in water content can be easily and energy-savingly produced.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-108174 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 231/12 C07C 233/36 C07C 233 / 38 C07C 237/06

Claims (3)

(57) [Claims] 1. An R— CO 2 O— group (R represents an alkyl group or an alkenyl group having 11 to 21 carbon atoms) derived from a fatty acid having 12 to 22 carbon atoms in the molecule;
A dilong-chain tertiary amine salt by neutralizing a di-long-chain tertiary amine compound having one group and one alkyl or alkenyl group having 11 to 22 carbon atoms with an acid In the production of the di-long chain type third in the presence of an emulsifier or a solvent
The neutralization reaction is carried out at the melting point of the tertiary amine compound or at a temperature in the range of 25 ° C. lower than the melting point.
A method for producing a dilong-chain tertiary amine salt, comprising producing an aqueous dispersion having a concentration of 0% by weight. 2. The dilong-chain tertiary amine compound is at least one selected from the group consisting of compounds represented by the following formulas (A-1), (A-2) and (A-3). The method according to claim 1, wherein Embedded image (Wherein, R ¹ is an alkyl group or hydroxyalkyl group having 1 to 4 carbon atoms, R ² and R ³ are the same or different and represent an alkyl group or alkenyl group having 11 to 21 carbon atoms, and R ⁴ is Represents an alkyl group or an alkenyl group of 12 to 22. m is 2 or 3.) 3. The amount of the emulsifier or the solvent added to the di-long chain type third
The method according to claim 1, wherein the amount is 2 to 30 parts by weight based on 100 parts by weight of the secondary amine compound.