JPH05186484A - Particulate alkylphosphoric ester metal salt and its production - Google Patents

Abstract

PURPOSE:To produce a particulate alkylphosphoric ester metal salt without adopting a special drying or dehydrating process. CONSTITUTION:An acidic alkylphosphoric ester is neutralized with an alkali metal hydroxide aqueous solution having a concentration of >=40wt.% at a temperature of >= the melting point of the acidic alkylphosphoric ester, and the resultant solid product is ground.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a powdery granular metal alkylphosphate ester salt used for treating fibers and the like and a method for producing the same.

[0002]

2. Description of the Related Art Generally, an alkyl phosphoric acid ester metal salt is obtained by neutralizing an acidic alkyl phosphoric acid ester obtained by phosphoric acid conversion of a higher alcohol with phosphoric acid anhydride with an alkali metal hydroxide. Therefore, a large amount of water is added to neutralize the mixture to a concentration such that stirring, filling, and removal from the container are possible. For this reason, it is usually a viscous liquid or paste with an effective concentration of about 30-60% by weight. Since such an alkyl phosphate metal salt has a low effective concentration, it has a problem of high logistics cost such as container and transportation in terms of pure content, and also changes in product viscosity or separation depending on storage temperature or period. Is likely to occur.

To address this problem, the metal salt of an alkyl phosphoric acid ester obtained by neutralizing an acidic alkyl phosphoric acid ester with an alkali metal hydroxide is solidified by reducing water by various methods, and the form is powder or particles. There is a way to make it. For example, the powdery alkylphosphoric acid ester metal salt can be prepared by spray drying the liquid alkylphosphoric acid ester metal salt produced by the above method. However, this method has high energy cost, large thermal decomposition due to high temperature, there is a problem in performance, and further, since bulk specific gravity is low, logistics costs such as containers and transportation cannot be lowered so much So, in general, it is rarely used.

[0004]

DISCLOSURE OF THE INVENTION The present invention is intended to be used,
For example, when it is used as a fiber treatment agent, it does not contain components that are harmful to the purpose, the energy cost during production is low, the bulk specific gravity of the product is high, it has good flowability during handling, and good solubility. By providing a granular alkyl phosphoric acid ester metal salt and a process for producing the same,
It is intended to solve the problems of the conventional technology.

[0005]

According to the present invention, an acidic alkyl phosphate ester has a concentration of 40% by weight at a temperature above its melting point.
The present invention relates to a method for producing a granular alkylphosphoric acid ester metal salt characterized by being neutralized with the above alkali metal hydroxide aqueous solution and then pulverizing in a solid state, and a granular granular alkylphosphoric acid ester metal salt produced by this production method.

The inventors of the present invention have found that the neutralized product of an acidic alkyl phosphoric acid ester with an alkyl metal hydroxide becomes a sticky substance having a very high viscosity when the water content is low. According to the present invention, uniform neutralization was achieved, and further, by making this waxy reaction product to have a certain water content or less and a certain temperature or less, it was rapidly solidified and pulverized. Thus, the present invention has been achieved.

In the present invention, the acidic alkyl phosphate ester can be obtained by a conventional method, for example, by reacting an alcohol with phosphoric anhydride. Alcohol has 8 to 2 carbon atoms
Suitable are saturated or unsaturated aliphatic alcohols which may have 2, more preferably 12 to 22 side chains.
Any alcohol may be used as long as the finally obtained alkylphosphoric acid ester metal salt becomes solid at a water content of 10% or less. Therefore, a mixture may be used as long as it meets the conditions.

The acidic alkylphosphoric acid ester in the present invention is not particularly limited in its production conditions.
(Number of gram atom of phosphorus atom bonded to 1 mol of alcohol)
Phosphoric acid anhydride was added so as to be 0.6 to 1.2, and 60
Obtained by stirring at ~ 100 ° C.

The alkali metal used in the metal salt of an alkyl phosphoric acid ester in the present invention is lithium, sodium, potassium or the like, and potassium is particularly useful for fiber applications because it has excellent smoothness and antistatic property. is there.

The degree of neutralization of the metal salt of an alkyl phosphate ester which can be granulated by the method of the present invention is preferably 5-40 KOH mg / g in terms of acid value.

The concentration of the alkali metal hydroxide aqueous solution used for neutralizing the acidic alkyl phosphate ester in the present invention is preferably as high as possible. For example, potassium
It is preferable to use commercially available liquid potassium having a concentration of 50% as it is, and if necessary, solid potassium may be added to liquid potassium to make it a high concentration close to the saturated concentration. On the contrary, it is possible to add water to 50 wt% concentration of liquid potassium to make the concentration low and to react, but in order to solidify thereafter, it is preferable that the water content is less, so that the concentration of at least 40 wt% or more is required. It is necessary to stop at.

In the present invention, the neutralization of the acidic alkyl phosphoric acid ester with the aqueous solution of the alkali metal hydroxide is carried out by mixing the liquid with the aqueous solution of the alkaline metal hydroxide at a temperature not lower than the melting point of the acidic alkyl phosphoric acid ester, followed by sufficient stirring. It can be carried out by In this case, the heated acidic alkyl phosphate ester is added while stirring the heated aqueous alkali metal hydroxide solution, or conversely, the heated aqueous alkali metal hydroxide solution is stirred while stirring the heated aqueous alkali metal hydroxide solution. May be added.

In the present invention, the neutralized reaction product is 80
Since it has a sticky high viscosity even at a temperature of not less than 0 ° C., it is preferable to carry out the reaction under strong stirring conditions, particularly kneading and cutting conditions. Therefore, this reactor is preferably equipped with a stirring blade and a chopper.

In the present invention, the solidification of the neutralized reaction product is determined by the type of the reaction product such as the alkyl group, the degree of phosphorylation and the degree of neutralization, the water content and the temperature. Solidification typically occurs at higher temperatures with lower moisture content. However, economically, the moisture content is 1
It is preferable to set the temperature to 0% or less, preferably 8% or less, and reduce the temperature to 65 ° C or less, preferably 55 ° C or less.

Therefore, with respect to the water content, it is preferable to minimize the amount of water used for the neutralization reaction. Further, during the neutralization reaction, the heat of reaction positively evaporates the water content,
Furthermore, the water content can be reduced by blowing cooling air or reducing the pressure while stirring. Regarding the temperature, when the neutralization reactor is used as it is, the temperature of the reactor jacket can be lowered or the temperature can be lowered in a short time by blowing cooling air. Incidentally, this solidification can also be carried out by taking out from the neutralization reactor and using another device.

In the present invention, the pulverization can be carried out by a known method and is not particularly limited. However, when the above-mentioned reactor equipped with a stirring blade and a chopper is used, the neutralization reaction and the pulverization are continuous. It is preferable because it can be

The powdery granular alkylphosphoric acid ester metal salt in the present invention means a state in which crushed particles and powder are mixed, and the maximum particle size of the particles may be 5 mm in handling. Desirably, more preferably 2 mm or less. This can also be achieved by sieving and classifying.

It is necessary that the water content of the powdery granular alkyl phosphate metal salt is not more than the limit of water content at which the tackiness of each alkyl phosphate metal salt is generated, and usually 10% or less, preferably. Is 8% or less.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Example 1 Using a speed mixer FS-5 type manufactured by Fukae Kogyo Co., Ltd. equipped with a stirrer and a chopper, 0.7 Kg of 50% caustic potash aqueous solution was added, and the temperature was raised to 85 ° C.
Stirrer and chopper are 150 rpm and 1000 rpm respectively
2 kg of acidic stearyl phosphate ester having a phosphorylation degree of 0.8 at 90 ° C. was added while rotating at 90 ° C. and stirred for 15 minutes to carry out a neutralization reaction. During this time, the viscosity gradually increased and became sticky. Then, when the jacket temperature was lowered, the viscosity of the reaction product further increased, and solidification began at 75 ° C., but pulverization was difficult. When the temperature is further lowered, the reaction product becomes 6
Grinding became possible below 5 ° C. When the temperature of the reaction product is 50 ° C., the stirrer and the chopper are set to 300 rpm and 36
It was spun at 00 rpm and ground for 10 minutes.

As a result, a powdery granular stearyl phosphate ester K salt having a free-flowing property in which both particulate and powdery forms were mixed was obtained. The water content of the powdery, granular stearyl phosphate ester K salt was 6.8% by weight. Further, this powdery granular stearyl phosphate K salt was passed through a 2 mm sieve for classification. As a result, the powdery granular stearyl phosphate ester K salt (Invention-1) having a particle diameter of 2 mm or less was 95.6% by weight, and the particles exceeding 2 mm were 4.6% by weight. The bulk specific gravity of the present invention-1 was 0.78 g / cc.

Next, 2 kg of acidic stearyl phosphate having a phosphorylation degree of 0.7 was prepared by a conventionally used method under the conditions corresponding to 0.7 kg of a 50% by weight caustic potash aqueous solution, and the effective concentration was 40% by weight. % Paste-like stearyl phosphate ester K salt (Comparative Example-1) was prepared.

Table 1 shows the results of measuring the solubility and the degree of decomposition of the present invention example-1 and comparative example-1 after long-term storage. That is, the dissolution time of Inventive Example-1 was about the same as that of Comparative Example-1, and there was no problem at this time, and it was within a sufficiently practical range. In addition, the change in acid value due to storage for 6 months is shown in Comparative Example-
It was about 1/2 or less than 1. This indicates that the powdery granular stearyl phosphate ester K salt of the present invention has lower hydrolysis and can be stored for a long period of time as compared with the conventional pasty stearyl phosphate ester K salt.

[0023]

[Table 1]

Dissolution time : Take a sample in a 500 cc beaker so that the effective concentration is 1% by weight, add ion-exchanged water at 75 ° C to 400 g, and stir under a condition that the liquid level rises by 5 mm with a magnetic stirrer. Time (minutes) to dissolve all

Change in acid value after storage for 6 months : For the same sample, the acid value immediately after production (KOHmg / g) and the acid value after storage in a sealed container at 40 ° C. for 6 months were measured, The amount of change (KOHmg / g) per pure sample was calculated.

Next, these invention example-1 and comparative example-1
For, the difference in properties when treated with polyester cotton was evaluated. As a result, as shown in Table 2, there was almost no difference in the treated cotton characteristics between the two samples, and the results can be regarded as equivalent performance.

[0027]

[Table 2]

(1) Preparation of treated cotton : cotton; polyester cotton, semi-dal 1.25 denier × 38 mm treatment method; spray treatment liquid concentration; 0.26% by weight treatment liquid adhesion amount; 50% (to fiber weight) target adhesion Amount: 0.13% (vs. fiber weight) Drying; 80 ° C x 2 hours

(3) Specific resistance : measured at a temperature and humidity of 20 ° C. and 45% RH using a fiber surface conductivity measuring instrument manufactured by Denpa Kogyo Co., Ltd.

(4) Static electricity generated by the card : 20 ° C. × 45% R
At H, the static electricity on the web of the miniature card made by Daiwa Kiko Co., Ltd. was measured by the collector type electric potential measuring device made by Kasuga Electric Co., Ltd.

(5) Sliver draft force : 3 drawing steps
Measurement of the sliver that has passed through at 20 ° C x 45% RH using a draft force tester manufactured by Eiko Sokki Co., Ltd.

(6) Spinning with a spinning roller : 30 ° C x 65% R
At H, the roving of the sample was fed to 10 spindles of the spinning machine, and 3
The ratio of the number of weights wrapped around the roller (%) when running for 20 minutes while cutting the thread after running for 0 minutes and letting the newer suck it

Example 2 A speed mixer FS-5 type manufactured by Fukae Kogyo Co., Ltd. was used, and the number of carbon atoms of the alkyl group was 1 in the same manner as in Example 1.
The acidic alkyl phosphate ester of 2 was neutralized with an aqueous solution of caustic potash to produce a granular alkyl phosphate metal salt.
The conditions and results are shown in Table 3, but a powdery granular metal alkyl phosphate metal salt having a free-flowing property was obtained.

[0034]

[Table 3]

Example 3 A speed mixer FS-5 type manufactured by Fukae Kogyo Co., Ltd. was used, and the number of carbon atoms of the alkyl group was 1 in the same manner as in Example 1.
The weight ratio of 6 and 18 is 35/65 and the degree of phosphorylation is 0.7, and the degree of neutralization is changed to 3 levels with an aqueous solution of caustic potash having an effective concentration of 50%. The rotation speed was neutralized at 150 rpm and 900 rpm for 10 minutes, and the maximum crushable temperature of each was investigated. Next, a crushing temperature of 40 ° C. and a rotating speed of a stirrer and a chopper were crushed at 300 rpm and 3600 rpm, respectively, for 10 minutes to produce a granular alkylphosphoric acid potassium salt. The results show that, as shown in Table 4, the lower the water content, the higher the maximum crushable temperature. The pulverized powdery metal alkyl phosphate metal salts were in a free-flowing state.

[0036]

[Table 4]

[0037]

INDUSTRIAL APPLICABILITY The powdery granular alkylphosphoric acid ester metal salt of the present invention is more effective than the conventional alkylphosphoric acid ester metal salt in the form of a viscous liquid or paste having an effective concentration of about 30 to 60% by weight. When it is used for other purposes, it has exactly the same performance, and has the advantage that its handleability does not change even if it is stored at a low temperature of -10 ° C or lower. Further, it has an advantage that the water content can be greatly reduced and the physical distribution cost can be significantly reduced. In addition, the granular alkylphosphoric acid ester metal salt does not change in performance as compared with the powdery alkylphosphoric acid ester metal salt using a spray dryer or the like, since it does not have a step of drying at a high temperature and thus has very little hydrolysis. In addition, since the bulk specific gravity is high, there is an advantage that the distribution cost can be further reduced.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yoshiaki Tanaka 2-3-1 Shibukawa-cho, Yao-shi, Osaka Within Matsumoto Yushi-Seiyaku Co., Ltd. (72) Inventor Zenji Fujimoto 2-3-1 Shibukawa-cho, Yao-shi, Osaka No. Matsumoto Yushi-Seiyaku Co., Ltd. (72) Inventor Minamiichi 2-3-1, Shibukawa-cho, Yao-shi, Osaka Prefecture Matsumoto Yushi-Seiyaku Co., Ltd.

Claims (9)

[Claims] 1. A powdery granular alkylphosphoric acid ester metal salt, characterized in that an acidic alkylphosphoric acid ester is neutralized with an aqueous alkali metal hydroxide solution having a concentration of 40% by weight or more at a temperature equal to or higher than a melting point, and then ground into a solid state. Manufacturing method. 2. The method for producing a powdery granular alkyl phosphate metal salt according to claim 1, which has a water content of 10% or less when pulverized. 3. The method for producing a powdery granular alkyl phosphoric acid ester metal salt according to claim 1, wherein the pulverizing temperature is 65 ° C. or lower. 4. A powdery or granular alkyl phosphate metal salt obtained by the method according to claim 1. 5. The powdery or granular alkyl phosphate metal salt according to claim 4, wherein the alkyl group has 8 to 22 carbon atoms. 6. The powdery or granular alkyl phosphate metal salt according to claim 4, wherein the metal salt is a potassium salt. 7. The powdery or granular alkyl phosphate metal salt according to claim 4, wherein the acid alkyl phosphate has a neutralization degree of 5 to 40 KOH mg / g in terms of acid value. 8. The powdery granular alkylphosphoric acid ester metal salt according to claim 4, which contains particles having a maximum particle size of 5 mm or less. 9. The powdery granular alkylphosphoric acid ester metal salt according to claim 8, which contains particles having a maximum particle size of 2 mm or less.