JP2008143998A - Method for producing anionic surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a high-purity anionic surfactant by stripping off impurities from a crude anionic surfactant efficiently within a short time. <P>SOLUTION: The method for producing the anionic surfactant comprises the step of stripping off impurities from a crude anionic surfactant of a water content of 0.01-5 wt.% in a granulator or dryer having an agitation blade by introducing a carrier gas thereto. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an anionic surfactant. More specifically, for example, high-purity anions that can be suitably used for clothes detergents, kitchen detergents, toothpaste foaming agents, shampoo powders, emulsion polymerization emulsifiers, pharmaceutical emulsifiers, cosmetic emulsifiers, cement foaming agents, etc. The present invention relates to a method for producing a surfactant.

  Anionic surfactants, when mixed with other surfactants or builders, are used in laundry detergents, kitchen detergents, toothpaste foaming agents, pharmaceutical emulsifiers, cosmetic emulsifiers, and other detergents. ing.

Conventionally, as a method for producing a relatively high-purity anionic surfactant powder or granular material, a method of spraying an anionic surfactant solution in a fluidized bed dryer and drying (Patent Document 1), or rotating thin film evaporation A method of drying with a machine so that the water concentration is less than 1% by weight (Patent Document 2), a method of removing at least part of the solvent by irradiating microwaves (Patent Document 3), and the like are known.
US Pat. No. 6,455,488 Japanese Patent Laid-Open No. 11-5999 JP 2002-129197 A

In the method described in Patent Document 1, since the anionic surfactant solution is sprayed and supplied into the fluidized bed dryer, it is necessary to keep the viscosity low. Therefore, the concentration of the active agent in the anionic surfactant solution had to be relatively low, about 44% by weight. Therefore, a very large amount of heated air of 17,000 to 20,000 Nm ³ / h is required to dry the moisture or fluidize the material to be dried because it is a fluidized bed dryer. The temperature of the heated air had to be as high as 170 ° C. For this reason, there is a problem that a great amount of heat energy is required, thermal deterioration of the anionic surfactant is promoted, and a large amount of exhaust gas is released to the atmosphere.

  Moreover, in the method of patent document 2, heating steam or warm water is introduce | transduced into the heating jacket of a rotary thin film evaporator, and it heats from the heat-transfer inner wall surface. Therefore, in order to dry until the water concentration becomes less than 1% by weight, the temperature of the inner wall surface of the heat transfer needs to be 110 ° C. or higher, and the water concentration of the anionic surfactant aqueous solution or the anionic surfactant slurry When an anionic surfactant is heated in contact with the inner wall surface of the heat transfer at a high temperature, or when the dry raw material is renewed locally on the inner wall surface of the heat transfer and heated locally, There was a problem that deterioration was accelerated and stable operation was difficult.

  In addition, anionic surfactants cause side reactions and hydrolysis by receiving a thermal history, and there is an increased concern that impurities will be generated, and the stability of quality during long-term storage is reduced, resulting in an unpleasant smell and taste. There is also a problem of manifestation.

  Furthermore, in the method described in Patent Document 3, since microwaves are irradiated, it is necessary to satisfy notifications and installation standards as high-frequency equipment based on the Radio Law, and the convenience and versatility are low. Although the heating by is effective in the high moisture region due to its principle, there is a problem that the effect on the region having little moisture and the substance not acting on the microwave is low.

  An object of the present invention is to provide a method for producing a high-purity anionic surfactant, which can solve the disadvantages of the conventional methods and can efficiently remove impurities contained in the anionic surfactant in a short time. is there.

  The present invention relates to an anionic surfactant having a step of introducing a carrier gas into a crude anionic surfactant having a water content of 0.01 to 5% by weight in a granulator or dryer having a stirring blade to distill off impurities. A manufacturing method is provided.

  According to the production method of the present invention, regardless of the quality in the sulfation or sulfonation step or the neutralization / drying step, the dried crude anionic surfactant is heated by stirring and heating by a carrier gas. Makes it possible to heat evenly and suppresses thermal decomposition due to local heating while efficiently distilling out impurities contained in the crude anionic surfactant in a short period of time to obtain a high purity anionic surfactant. Can be obtained stably.

  The anionic surfactant used in the present invention is not particularly limited, but alkyl or alkenyl sulfate, polyoxyalkylene alkyl or alkenyl ether sulfate, 痾 -olefin sulfonate, alkyl benzene sulfonate, 痾 -sulfo fatty acid salt Alternatively, 痾 -sulfo fatty acid ester salt, alkyl or alkenyl ether carboxylate and the like can be mentioned. Among these, alkyl or alkenyl sulfates, polyoxyalkylene alkyl or alkenyl ether sulfates are preferable, alkyl or alkenyl sulfates are more preferable, and alkyl sulfates are particularly preferable from the viewpoints of foamability and cleaning performance. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, alkanolamine salts and the like. Among these salts, alkali metal salts are preferable, and sodium salts, potassium salts, and mixtures of these salts are more preferable.

  Among these anionic surfactants, at least selected from the group consisting of alkyl or alkenyl sulfates represented by the following formula (I) and polyoxyalkylene alkyl or alkenyl ether sulfates represented by the following formula (II): One is more preferred.

(R ¹ O—SO ₃ ) _p M ¹ (I)
(Wherein R ¹ is a linear or branched alkyl or alkenyl group having 8 to 24 carbon atoms, M ¹ is a cation, and p is the valence of M ¹ and represents 1 or 2)
(R ² O— (AO) _m SO ₃ ) _q M ² (II)
(Wherein R ² represents a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and m A's may be the same or different. even better .m is the number of from 0.05 to 20 showing an average addition mole number of alkylene oxide .M ² cation, q is 1 or 2 a valence of M ^2.)
In the general formulas (I) and (II), the number of carbon atoms of R ¹ and R ² is preferably 8 to 20, more preferably 10 to 18, from the viewpoint of the caking resistance and solubility of the granular material. A is preferably an alkylene group having 2 to 4 carbon atoms, particularly 2 carbon atoms. m is preferably from 0.05 to 2, more preferably from 0.1 to 1, and particularly preferably from 0.2 to 0, from the viewpoint of obtaining excellent powder characteristics and improving the caking resistance of the granular material. .8. M ¹ and M ² are preferably an alkali metal atom such as Na or K, an alkaline earth metal atom such as Ca or Mg, or an alkanol-substituted or unsubstituted ammonium group, and more preferably an alkali metal atom, particularly Na.

  The alkyl or alkenyl sulfate represented by the above formula (I) is obtained, for example, by sulfating and neutralizing an alcohol having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms (hereinafter referred to as higher alcohol). The polyoxyalkylene alkyl or alkenyl ether sulfate represented by the formula (II) is, for example, an alkylene oxide added to a higher alcohol having an average addition mole number of 0.05 to 20, preferably 0.05 to 2. It is obtained by sulfating and neutralizing the alkylene oxide adduct of the added higher alcohol.

  Sulfation and neutralization can be performed by known methods. The sulfating agent used for sulfation is preferably sulfur trioxide or chlorosulfonic acid. When using sulfur trioxide gas, it is usually diluted with an inert gas, preferably dry air or nitrogen, and a sulfur trioxide gas concentration of 1 to 8% by volume, preferably 1.5 to 5% by volume of gas. Used as a mixture. Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, sodium carbonate and the like.

  The water content of the neutralized anionic surfactant is not particularly limited, but is preferably 20 to 40% by weight from the viewpoint of reducing fluidity and energy load during drying. The anionic surfactant may contain a water-soluble inorganic salt, but in the production of a high-purity anionic surfactant, it is preferable that the amount be as small as possible from the viewpoint of improving its purity. Representative examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like.

  After neutralization, drying is performed to obtain a crude anionic surfactant. The drying method is not particularly limited, and can be performed by a known method. Examples thereof include a method using a rotary thin film evaporator and a spray drying tower, a method of granulating and drying using a granulator having a stirring blade or a dryer.

  In the present invention, the water content of the crude anionic surfactant is 5% by weight or less, preferably 3.0% by weight or less from the viewpoint of impurity removal efficiency. From the viewpoint of productivity, it is 0.01% by weight or more, preferably 0.3% by weight or more. The amount of water in the crude anionic surfactant can be measured by a method such as heat loss method, distillation method, Karl Fischer method (JIS K 0068), etc., but the amount of water in this specification is determined by the Karl Fischer method (JIS K). K 0068).

  Moreover, the impurity contained in the crude anionic surfactant of the present invention means petroleum ether soluble matter. Here, the petroleum ether-soluble component includes alcohols, alkoxylates that have not been sulfated during the production of an anionic surfactant, and trace amounts of hydrocarbons, waxes, etc. produced as a by-product from the reaction. To dissolve petroleum ether soluble matter, 100 g of a sample was dissolved in 200 ml of a mixture of water and ethanol, extracted into a sufficient amount of petroleum ether, and then retained in a 60 ° C. water bath until there was almost no petroleum ether. After leaving, air is blown in to completely expel petroleum ether, and the weight of the petroleum ether extract obtained by drying in an oven at 85 ° C. for 15 minutes is divided by the sample weight.

In the present invention, the impurity removal rate is derived from the following equation, and the larger the value, the faster the removal rate. Log _e means the natural logarithm.

Removal rate [1 / h] = (− log _e (A / B)) / C
Further, the impurity removal rate is derived from the following equation.

Removal rate [%] = (1-A / B) × 100
Here, A, B, and C have the following meanings.

A: Petroleum ether soluble component contained in the treated anionic surfactant [%]
B: Petroleum ether soluble component contained in crude anionic surfactant before treatment [%]
C: Processing time [h].

The average particle size of the crude anionic surfactant in the machine of the present invention is preferably 0.01 mm or more, more preferably 0.03 mm or more, from the viewpoint of improving fluidity in the machine and suppressing adhesion to walls and filter cloths. More preferably, it is 0.05 mm or more. Moreover, from a viewpoint of the removal efficiency of an impurity, 3.0 mm or less is preferable, 2.0 mm or less is more preferable, and 1.2 mm or less is still more preferable. The average particle diameter in the present invention is 10 g for a sample using an air jet sheave (Hosokawa Micron Corporation 200LS-N type), a differential pressure ΔP = 3000 mmH ₂ O above and below the sieve, and a treatment time of 3 minutes. Calculated from the weight fraction that passed through the eye.

  In the present invention, the crude anionic surfactant may be pulverized in advance. Examples of the pulverizer used at that time include an atomizer (manufactured by Fuji Paudal Co., Ltd.), Fitzmill (manufactured by Dalton Co., Ltd.), Pulverizer (manufactured by Dalton Co., Ltd.), and a power mill (manufactured by POWREC Co., Ltd.). , Comil (manufactured by Quadro) and the like.

  The granulator or dryer used in the present invention is preferably equipped with a stirring blade, a jacket for adjusting the internal temperature (article temperature), and a nozzle for introducing a carrier gas. It is. Specific examples of such a more preferred granulator include the granulators described in JP-A-10-296064, JP-A-10-296065, and Japanese Patent No. 3165700.

  Further, a crushing blade may be provided, and the crushing blade appropriately crushes the crude anionic surfactant and increases the specific surface area, thereby increasing the contact efficiency with the carrier gas and effectively removing impurities. it can.

  The average particle diameter of the crude anionic surfactant after pulverization is preferably 0.01 mm or more, more preferably 0.03 mm or more, from the viewpoint of improving fluidity in the machine and suppressing adhesion to the wall or filter cloth. .05 mm or more is more preferable. Moreover, from a viewpoint of the removal efficiency of an impurity, 0.50 mm or less is preferable, 0.30 mm or less is more preferable, and 0.20 mm or less is still more preferable.

  Examples of the granulator or dryer preferably used in the present invention include, for example, a Henschel mixer [Mitsui Miike Chemical Co., Ltd.], a high-speed mixer [Fukae Powtech Co., Ltd.], a vertical granulator as a batch type. [Powrec Co., Ltd.], Redige mixer [Matsuzaka Giken Co., Ltd.], Pro-share mixer [Pacific Kiko Co., Ltd.] and the like, particularly preferred Redige mixer [Matsuzaka Giken Co., Ltd.] ], High-speed mixer [Fukae Powtech Co., Ltd.], professional share mixer [Pacific Kiko Co., Ltd.]. Continuous-type readyge mixer (medium speed mixer: relatively long residence time) as a continuous type, CB recycler (manufactured by Loedige) as a high speed mixer (relatively short residence time), turbulizer (Hosokawa Micron Co., Ltd.) Product), Shugi mixer (manufactured by POWREC Co., Ltd.), flow jet mixer (manufactured by Powder Research), and the like.

In the present invention, a carrier gas is introduced mainly for the purpose of promoting the evaporation of impurities. The amount of carrier gas introduced is preferably 0.2 m ³ / Hr or more, more preferably 0.5 m ³ / Hr or more, preferably 1.0 m ³ from the viewpoint of promoting the evaporation of impurities per kg of anionic surfactant in the machine. / Hr or more is particularly preferable. Moreover, from a viewpoint of reducing an equipment load, 20.0 m < ³ > / Hr or less is preferable, 10.0 m < ³ > / Hr or less is more preferable, 5.0 m < ³ > / Hr or less is especially preferable.

  The carrier gas is introduced into the machine by a nozzle provided in the granulator or the dryer. Further, the carrier gas may be introduced so as to generate a swirling flow for the purpose of increasing the contact efficiency with the crude anionic surfactant and / or introduced from a nozzle inserted inside the crude anionic surfactant. You may do it.

  Examples of the carrier gas include inert gas such as nitrogen gas, air, and / or water vapor. In particular, the effect of distilling off impurities is the same regardless of the type of gas used, but condensable gas is preferred from the viewpoint of gas exhaustion and equipment scale, and water vapor is particularly preferred. The carrier gas may be used by heating, and the water vapor may be introduced as superheated steam.

  It is possible to uniformly heat the crude anionic surfactant charged in the granulator or dryer using the heat of the carrier gas. The introduced carrier gas temperature is preferably 20 to 120 ° C. In addition, 40 degreeC or more is more preferable from a viewpoint as a heat source, and 60 degreeC or more is still more preferable. Moreover, from a viewpoint of suppressing the thermal deterioration of a crude anionic surfactant, 110 degrees C or less is more preferable, and 100 degrees C or less is still more preferable. In addition, examples of a method for controlling the temperature of the crude anionic surfactant in the granulator or the dryer include a method of appropriately adjusting the jacket temperature in the granulator, the fluid number of the stirring blades of the granulator, and the like.

  Examples of the heat source of the granulator include a hot water jacket and electric tracing, but a hot water jacket is preferable, and the jacket temperature is preferably 100 ° C. or less, and is 90% from the viewpoint of applying to a heat sensitive raw material. More preferably, it is 70 ° C. or less. Moreover, from a viewpoint as a heat source, 30 degreeC or more is preferable, 40 degreeC or more is more preferable, and 50 degreeC or more is the most preferable.

  From the viewpoint of increasing the volume of the carrier gas, the internal pressure of the granulator or dryer in the present invention is preferably 130 kPa or less, more preferably 101 kPa or less, still more preferably 50 kPa or less, and particularly preferably 20 kPa or less. On the other hand, from the viewpoint of the burden on the vacuum pump and the airtightness of the granulator, 0.5 kPa or more is preferable, 1.5 kPa or more is more preferable, 4.0 kPa or more is further preferable, and 5.3 kPa or more is particularly preferable.

  In the present invention, the treatment temperature of the crude anionic surfactant in the machine is preferably 100 ° C. or less, more preferably 95 ° C. or less, and particularly preferably 90 ° C. or less, from the viewpoint of suppressing thermal degradation. On the other hand, from the viewpoint of improving the distillation rate of impurities, 20 ° C. or higher is preferable, 40 ° C. or higher is more preferable, and 60 ° C. or higher is particularly preferable.

  As the high purity anionic surfactant obtained by the method of the present invention, the anionic surfactant is 80% by weight or more, preferably 90% by weight or more, more preferably from the viewpoint of effectively exhibiting the function of the anionic surfactant itself. Is 95% by weight or more, most preferably 100% by weight.

  The high-purity anionic surfactant obtained by the method of the present invention may further contain a water-soluble inorganic salt in addition to the anionic surfactant. Examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. The content of the water-soluble inorganic salt in the high-purity anionic surfactant obtained by the method of the present invention is not particularly limited, but from the viewpoint of keeping the effective amount of the anionic surfactant high, the anionic surfactant is added in 100 parts by weight. On the other hand, it is 5 parts by weight or less, preferably 2 parts by weight or less, more preferably 1 part by weight or less, and particularly preferably 0.5 parts by weight or less.

  The high-purity anionic surfactant obtained by the method of the present invention can contain a surfactant other than the anionic surfactant. Examples of the surfactant other than the anionic surfactant include a cationic surfactant and a nonionic surfactant.

  The high-purity anionic surfactant obtained by the method of the present invention can contain other additives as necessary. Other additives include, for example, alkali agents such as silicates and carbonates, divalent metal ion scavengers such as citrates and zeolites, anti-contamination agents such as polyvinylpyrrolidone and carboxymethylcellulose, anti-caking agents, and oxidation. An inhibitor etc. are mentioned. Such other additives can be used as long as the object of the present invention is not impaired.

  In the examples, “%” means “% by weight” unless otherwise specified.

Synthesis example 1
A higher alcohol having 12 carbon atoms in the alkyl group (molecular weight 189) was continuously charged at 60 ° C. and reacted with 2.0 vol% sulfur trioxide gas in the thin film flow reactor. The flow rate was adjusted so that the reaction molar ratio of sulfur trioxide gas to higher alcohol was 0.96. The obtained sulfate is neutralized with a 23% aqueous sodium hydroxide solution, and 30% phosphoric acid (buffer) is added to make a fine adjustment to pH = 8. Further, the effective amount of the anionic surfactant becomes 30%. As described above, an aqueous solution of sodium alkylsulfate (hereinafter referred to as an aqueous solution of sodium alkylsulfate 1) was obtained by adjusting with water. The obtained sodium alkylsulfate aqueous salt solution 1 contained 0.9% of petroleum ether-soluble component.

  Next, using a vacuum dryer having a capacity of 2500 L [FMD-1200JE, manufactured by Fukae Pautech Co., Ltd.], jacket temperature 65 ° C., internal pressure 4.0 kPa, stirring blade rotation speed: 70 r / min, crushing blade rotation speed: 2000 r Drying and granulation were performed simultaneously by supplying the sodium alkylsulfate aqueous salt solution 1 so as to adjust the temperature of the dried product to 36.2 ° C. under a dry granulation condition of / min. Thereafter, the dry granulation was completed when the total amount of the aqueous solution supplied reached 1810 kg. Subsequently, the mixture was treated for 60 minutes under the conditions of a stirring blade rotation speed: 15 r / min, a crushing blade rotation speed: 0 r / min, a jacket temperature of 65 ° C., and an in-machine pressure of 4.0 kPa to obtain sodium alkylsulfate salt granules. The obtained sodium alkylsulfate salt granules had an average particle size of 1.05 mm, a water content of 0.99%, and a crude anionic surfactant containing 2.3% petroleum ether soluble matter (hereinafter referred to as crude sodium alkylsulfate salt granules). Body 1).

Synthesis example 2
An anionic surfactant [EMAL 10PT: manufactured by Kao Corporation, average particle size 0.36 mm] was pulverized with an atomizer (Fuji Paudal Co., Ltd., FIIS-5 type), average particle diameter 0.15 mm, moisture 0 A crude anionic surfactant (hereinafter referred to as crude sodium alkylsulfate salt granules 2) having .92% and petroleum ether-soluble content of 0.80% was obtained.

Example 1
540 kg of crude sodium alkylsulfate salt powder 1 was put in a vacuum dryer with a capacity of 2500 L [Fukae Powtech Co., Ltd., trade name: High Speed Mixer FMD-1200JE type], jacket temperature 80 ° C., machine pressure 4.0 kPa, Stirring blade rotation speed: 55 r / min, crushing blade rotation speed: 2000 r / min, superheated steam is introduced as a carrier gas at a rate of 3.2 m ³ / Hr / kg-powder for 5 hours. A pure sodium salt of alkyl sulfate was obtained.

Example 2
40 kg of crude sodium alkylsulfate salt powder [EMAL 10PT: manufactured by Kao Corporation, average particle size 0.36 mm] is charged into a 100 L capacity Nauter mixer [made by Hosokawa Micron Corporation, NX-1 type], jacket Treated for 5 hours while introducing nitrogen gas as a carrier gas at a rate of 1.4 m ³ / Hr / kg-powder under conditions of a temperature of 95 ° C., an internal pressure of 5.3 kPa, and a rotating speed of a stirring blade of 90 r / min A pure sodium salt of alkyl sulfate was obtained.

Example 3
A 65-liter vacuum dryer (Fukae Powtech Co., Ltd., trade name: High Speed Mixer FMD-65JE type) was charged with 20 kg of crude sodium alkylsulfate salt granulate 2, jacket temperature 85 ° C, granulator pressure 4 2 hours while introducing superheated steam as a carrier gas at a rate of 9.6 m ³ / Hr / kg-powder under the conditions of 0.0 kPa, stirring blade speed: 200 r / min, and crushing blade speed: 0 r / min Treatment gave high purity alkyl sulfate sodium salt.

Example 4
A 65-liter vacuum dryer [Fukae Powtech Co., Ltd., trade name: High Speed Mixer FMD-65JE type], 20 kg of crude alkyl sulfate sodium salt [EMAL 10P-HD: Kao Co., Ltd., average particle size 0 .15 mm], a jacket temperature of 95 ° C., a pressure in the granulator of 10.7 kPa, a rotating speed of the stirring blade: 200 r / min, and a rotating speed of the crushing blade: 3000 r / min. The mixture was treated for 1.5 hours while being introduced at a rate of 7 m ³ / Hr / kg-powder to obtain a high-purity sodium alkylsulfate salt.

Comparative Example 1
A 65-liter vacuum dryer [Fukae Powtech Co., Ltd., trade name: High Speed Mixer FMD-65JE type], 20 kg of crude alkyl sulfate sodium salt [EMAL 10P-HD: Kao Co., Ltd., average particle size 0 .15 mm], jacket temperature 95 ° C., granulator pressure 5.3 kPa, stirring blade rotation speed: 200 r / min, crushing blade rotation speed: 0 r / min, without introducing carrier gas As a result, it took 20 hours to obtain high-purity sodium alkylsulfate.

Comparative Example 2
A 65-liter vacuum dryer [Fukae Powtech Co., Ltd., trade name: High Speed Mixer FMD-65JE type], 20 kg of crude alkyl sulfate sodium salt [EMAL 10P-HD: Kao Co., Ltd., average particle size 0 .15 mm], 1.8 kg of water was added under the conditions of a jacket temperature of 20 ° C., a pressure in the granulator of 101.3 kPa, a rotating speed of the stirring blade: 200 r / min, and a rotating speed of the crushing blade: 3000 r / min. After mixing for 5 minutes, it was held for 5 hours. Then, when it processed on the same conditions as Example 4, the removal rate fell compared with Example 4. FIG.

  Table 1 summarizes the processing conditions and processing results of Examples 1 to 4 and Comparative Examples 1 and 2.

Claims (8)

  A method for producing an anionic surfactant, comprising a step of introducing a carrier gas into a crude anionic surfactant having a water content of 0.01 to 5% by weight in a granulator or a dryer having a stirring blade to distill off impurities.   The manufacturing method of the anionic surfactant of Claim 1 which performs the process of distilling off an impurity under the pressure of 0.5-130 kPa. The method for producing an anionic surfactant according to claim 1 or 2, wherein an introduction amount of the carrier gas is 0.2 to 20.0 m ³ / Hr per 1 kg of the anionic surfactant in the machine.   The method for producing an anionic surfactant according to any one of claims 1 to 3, wherein the carrier gas is water vapor.   The manufacturing method of the anionic surfactant in any one of Claims 1-4 whose temperature of the anionic surfactant in a machine is 20-100 degreeC.   The manufacturing method of the anionic surfactant in any one of Claims 1-5 whose anionic surfactant is an alkyl sulfate.   The method for producing an anionic surfactant according to any one of claims 1 to 6, wherein the in-machine anionic surfactant has an average particle size of 0.01 to 0.50 mm.   The manufacturing method of the anionic surfactant in any one of Claims 1-7 in which the granulator or dryer which has a stirring blade further has a crushing blade.