JP2005068413A - Method for producing granular anionic surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a granular anionic surfactant, capable of producing its granular material which has good color tones, external appearance and solubility, is decreased in a water content as a powdery material, scarcely causes caking, and has good handleability, in an optimal particle diameter range, by using a drying apparatus of a small scale having a decreased drying load, and without causing heat deterioration of the surfactant. <P>SOLUTION: This method for producing the granular anionic surfactant comprises simultaneously conducting drying and granulation in a granulating machine having an agitating blade and a crushing blade, while adding anionic surfactant paste to a powdery raw material under reduced pressure, so that the granular material containing the anionic surfactant in an amount of 80-99.5 wt% is obtained. The granular anionic surfactant is obtained by this method. A detergent composition and an additive for cement contain the granular anionic surfactant, respectively. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is a simple and easy-to-use granular anionic surfactant having good particle properties, which can be suitably used for clothes detergents, kitchen detergents, toothpaste foaming agents, shampoo powders, polymerization emulsifiers, cement foaming agents and the like. The present invention relates to a production method, and a detergent composition and a cement additive containing the particulate anionic surfactant.

  Conventionally, a granular anionic surfactant is produced by drying and granulating by removing water from a liquid or paste-like anionic surfactant as a starting material. For example, as a conventional method for producing a granular anionic surfactant, a low-concentration slurry having a water content of 60 to 70% by weight is spray-dried in consideration of viscosity (Patent Document 1, Patent Document 2), alkyl sulfuric acid There is a method by a spray drying method such as a method (Patent Document 3) in which a high concentration slurry having a solid content concentration of 60 to 80% by weight is sprayed using a minimum value of the viscosity of the salt slurry. However, for example, the production methods disclosed in Patent Documents 1 and 2 have a spray drying process, and thus have a drawback of requiring a large-scale drying apparatus and a large amount of drying energy. Also, with respect to the method of Patent Document 3, since a high-concentration slurry is used, a large amount of energy is not required, but a large-scale drying apparatus is required.

  Patent Document 4 discloses a method of drying a high-concentration detergent paste material having a moisture content of 20 to 35% by weight using a vacuum thin film dryer. This method is a continuous high-density detergent paste material. There is no sufficient technical solution for the drying method and the method for granulating the anionic surfactant itself.

  In Patent Document 5, a high-density detergent paste raw material is supplied into a cylindrical casing under vacuum, and a thin film of the high-density detergent paste raw material is formed on the inner wall surface at the tip of a rotatable plate blade. , A method of quickly drying and scraping with a plate-like blade to obtain a flaky dried product is disclosed, but since the degree of vacuum is low in this thin film dryer, the raw material is processed There is a risk of disassembly. Moreover, since only a flaky dried product can be obtained, it is necessary to post-process the flakes by an extrusion granulation method or the like.

  Patent Documents 6 and 7 disclose a method in which a paste is granulated at the same time as drying by a flash method or a flash dryer. However, since the pressure in the granulator is high and the drying temperature is high, thermal degradation is likely. It cannot be applied to an anionic surfactant, and it is also pulverized with respect to the granulated product, the particle size distribution becomes broad, the burden on the stirring shaft becomes large and the desired particle size cannot be obtained, Furthermore, there is a drawback that it is necessary to obtain a desired particle size using an extruder or the like in a subsequent process.

  Patent Document 8 discloses a method for producing a granulated product of alkyl sulfuric acid. An anionic surfactant powder can be obtained, but the appearance is good only by means such as extrusion granulation in the subsequent step. Particles are not obtained.

  As described above, the prior art has disadvantages such as a large drying apparatus, a high drying load, and a large thermal deterioration, and a granulated product having a satisfactory external shape has not been obtained. At present, secondary processing is performed.

  Accordingly, the scale of the drying device is small, the drying load is low, the drying can be performed at a low temperature, the thermal degradation is small, the hue is good, and the granule having a good appearance shape is simultaneously formed with the optimum granule. A manufacturing method that can be manufactured in a diameter range is desired.

In addition, by optimizing the particle size of the granular anionic surfactant, it is possible to increase not only the handleability of the particles themselves but also the product yield, and the quality (for example, solubility, etc.), conventional drying In addition, the commercial value is greatly improved as compared with the granulated product.
Japanese Patent Laid-Open No. 55-69698 JP-A-53-39037 JP 54-106428 A JP-A-2-222498 Japanese Patent Laid-Open No. 5-331496 US Pat. No. 5,646,107 Japanese translation of PCT publication No. 2002-508783 International Publication No. 95/01959 Pamphlet

  The problem of the present invention is that the drying apparatus has a small scale, has a low drying load, can be dried at a low temperature, has little thermal deterioration, has a good hue, and further has an appearance shape, solubility, and granular material. A good granulated product with low moisture content and almost no caking is produced at the same time in the optimum particle size range, and by optimizing the particle size of the granular anionic surfactant, the handleability of the particles themselves And providing a method for producing a granular anionic surfactant having good solubility.

  The present invention performs granulation simultaneously with drying while adding an anionic surfactant paste to a powder raw material under reduced pressure in a granulator having a stirring blade and a crushing blade, and an anionic interface of 80 to 99.5 wt% A method for producing a granular anionic surfactant, a granular anionic surfactant obtained by the production method, and a detergent composition and a cement additive containing the granular anionic surfactant provide.

  According to the production method of the present invention, it is possible to obtain a granular anionic surfactant having high particle properties and high basic anion surfactant content without requiring preliminary mixing and complicated steps.

[Anionic surfactant paste]
The anionic surfactant used in the present invention is not particularly limited, and examples thereof include alkyl sulfates, polyoxyalkylene alkyl ether sulfates, α-olefin sulfates, alkylbenzene sulfonates, α-sulfo fatty acid ester salts and the like. . Of these, alkyl sulfates and polyoxyalkylene alkyl ether sulfates are preferred. 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 also preferable.

  Alkyl sulfates and polyoxyalkylene alkyl ether sulfates are both neutralized by, for example, sulfating an addition product obtained by adding a higher alcohol or an alkylene oxide such as ethylene oxide or propylene oxide to a higher alcohol. Can be obtained. In the sulfation reaction, unreacted substances may be present in the range of 10% by weight or less, preferably 5% by weight or less.

  Examples of the alkyl sulfate include alkyl sulfates represented by the formula (I).

(R ¹ O—SO ₃ ) _p M ¹ (I)
Wherein R ¹ is a linear or branched alkyl group or alkenyl group having 8 to 24 carbon atoms, preferably 8 to 18 carbon atoms, M ¹ is an alkali metal atom, alkaline earth metal atom, alkanol substituted or unsubstituted. (Cation such as ammonium group, p is the valence of M ¹ and represents 1 or 2)
Examples of the polyoxyalkylene alkyl ether sulfate include polyoxyalkylene alkyl ether sulfate represented by the formula (II).

(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. M is a number of 0.05 to 20 indicating the average number of added moles of alkylene oxide, and M ² is a cation such as an alkali metal atom, an alkaline earth metal atom, an alkanol-substituted or unsubstituted ammonium group. , q is 1 or 2 a valence of M ^2.)
The average addition mole number m of the alkylene oxide of the polyoxyalkylene alkyl ether sulfate represented by the formula (II) is 0.05 to 2 from the viewpoint of obtaining excellent granular physical properties and suppressing the caking property in granular form. 0.0 is preferable, 0.1 to 1.0 is more preferable, and 0.2 to 0.8 is particularly preferable. R ² is preferably an alkyl group or an alkenyl group having 8 to 20 carbon atoms, more preferably 8 to 18 carbon atoms, particularly 10 to 18 carbon atoms, and more preferably an alkyl group, from the viewpoint of caking properties when powdered and particle solubility. . AO is preferably an oxyalkylene group having 2 to 3, particularly 2 carbon atoms. M ² is 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 inorganic-substituted ammonium group, and more preferably an alkali metal atom, particularly Na. q is preferably 1 or 2, and more preferably 1.

  Of the polyoxyalkylene alkyl ether sulfates represented by the formula (II), particularly preferred are compounds represented by the formula (III).

(R ³ O— (AO) _n SO ₃ ) _q M ² (III)
(In the formula, R ³ is a linear alkyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, and n is a number of 0.05 to 2 indicating the average number of added moles of alkylene oxide. A, q and M ² indicates the above meaning.)
In the polyoxyalkylene alkyl ether sulfate represented by the formula (II), the addition distribution of alkylene oxide is not particularly limited, and may be an addition distribution obtained by a known method such as a broad and narrow distribution.

  The anionic surfactant of the present invention is a mixture containing a polyoxyalkylene alkyl ether sulfate and an alkyl sulfate to which no alkylene oxide is added at a constant ratio from the viewpoint of satisfying both cleaning performance and caking property. Preferably there is. The content of the alkyl sulfate is preferably 30 to 95% by weight, more preferably 50 to 90% by weight in the anionic surfactant.

The anionic surfactant paste used in the present invention can be prepared by, for example, the following methods (1) to (3).
(1) A higher product in which alkylene oxide is added to an alcohol having 8 to 24 carbon atoms, preferably 8 to 20 carbon atoms (hereinafter referred to as higher alcohol) so as to have an average added mole number of 0.05 to 20, preferably 0.05 to 2. A method of sulfating and neutralizing an alkylene oxide adduct of alcohol.
(2) A higher alcohol and an alkylene oxide adduct of a higher alcohol are mixed so that the average number of moles of alkylene oxide added in the mixture is 0.05 to 20, preferably 0.05 to 2, and then sulfated and neutralized. how to.
(3) A higher alcohol and a higher alcohol alkylene oxide adduct separately sulfated separately and neutralized, and the mixture has an average alkylene oxide addition mole number of 0.05 to 20, preferably 0.05 to 2. How to mix.

  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 unreacted component contained in the anionic surfactant paste of the present invention is not preferable because it causes a decrease in purity and the caking properties of the powder, but is preferably not more than 5% by weight and more preferably. Is 2% by weight or less. Here, the unreacted component includes alcohol, alkoxylate that has not been sulfated, and a small amount of hydrocarbon and wax by-produced from the reaction.

  The active ingredient content of the anionic surfactant paste of the present invention is preferably 60 to 80% by weight from the viewpoint of fluidity and reducing the energy load during drying.

  The anionic surfactant paste of the present invention may contain a water-soluble inorganic salt. Representative examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. These water-soluble inorganic salts may be added as they are, but may be by-produced by reaction. For example, when NaClO (sodium hypochlorite) is added to the anionic surfactant paste for the purpose of improving the hue, NaCl (sodium chloride) is by-produced. Although use is limited, sodium hypochlorite can be added in this way, and sodium chloride can also be by-produced as an inorganic salt.

[Powder material]
The powder raw material used in the present invention preferably contains at least one selected from the group consisting of a surfactant, a water-soluble inorganic salt and a water-insoluble inorganic salt, and is obtained in the granular form obtained by the production method of the present invention. It is more preferable to use a part of the product as a powder raw material. Furthermore, you may grind | pulverize a granular material.

  Examples of the surfactant include the anionic surfactants as described above. Examples of the water-soluble inorganic salt include sodium chloride, sodium sulfate, sodium carbonate and the like. Examples of water-insoluble inorganic salts include alkali agents such as silicates and carbonates, and divalent metal ion scavengers such as citrates and zeolites.

  The particle size of the powder raw material is preferably 500 μm or less, more preferably 300 μm or less, and most preferably 200 μm or less from the viewpoints of drying speed, particle size control of the final granulated product, and handling properties.

  Examples of the pulverizer preferably used in the present invention include, for example, an atomizer (manufactured by Fuji Paudal Co., Ltd.), Fitzmill (manufactured by Dalton Co., Ltd.), Pulverizer (manufactured by Dalton Co., Ltd.), and power mill (Powrec Co., Ltd.). )), Comil (manufactured by Quadro) and the like.

[Production method of granular anionic surfactant]
The method for producing a granular anionic surfactant of the present invention is a method of granulating simultaneously with drying while adding an anionic surfactant paste to a powder raw material under reduced pressure in a granulator having a stirring blade and a crushing blade. is there.

  In the present invention, the temperature of the granular material is preferably in the range of 35 to 75 ° C, more preferably 40 to 75 ° C, particularly preferably 45 to 70 ° C, and the temperature change during drying is within ± 5 ° C. It is preferable to perform granulation simultaneously with drying while controlling the temperature to be preferably within ± 2 ° C., particularly preferably within ± 1 ° C. As a method of controlling the temperature change and the particle size of the granular anionic surfactant in this way, (1) the amount and rate of addition of the anionic surfactant paste, (2) pressure in the granulator, (3) granulation Examples include a method of appropriately adjusting the jacket temperature in the machine, (4) introduction of air and / or inert gas into the granulator, and (5) the number of fluids of the blades of the granulator. Hereinafter, each method will be described in detail.

(1) Addition amount and addition rate of anionic surfactant paste It is preferable to control the addition amount and addition rate of the anionic surfactant paste so that the temperature of the granular material is within the above range. The addition amount of the anionic surfactant paste is preferably such that the weight ratio of the anionic surfactant paste to the powder raw material is 1/10 to 10/1, and more preferably 4/4 to 7/1. In addition, regarding the addition speed, if the time from the start of dropping the paste to the operating temperature is long, it is difficult to obtain a granulated product, and if the dropping speed is too high, coarse particles may be formed and stable operation is not achieved. It may be easy. For this reason, the ratio of the time to reach the operating temperature and the paste addition time is preferably 1/50 to 1/3.

(2) Pressure in the granulator The pressure in the granulator is preferably 0.67 to 40 kPa from the viewpoint of lowering the operation product temperature and suppressing the decomposition of the paste and the granulated product, and further the burden on the vacuum pump. From the viewpoint of airtightness of the granulator and granulator, 2.7 to 40 kPa is preferable, and 4.0 to 8.0 kPa is particularly preferable.

(3) Jacket temperature in the granulator The heating source of the granulator includes a warm water jacket, electric tracing, etc., but a warm water jacket is preferred, and the jacket temperature is preferably 115 ° C. or less, more preferably 100. 90 ° C. or lower is particularly preferable from the viewpoint of application to a raw material sensitive to heat or lower, and more sensitive to heat.

(4) Introduction of air and / or inert gas into the granulator In the present invention, during the addition of the anionic surfactant paste, air and / or inert gas is supplied to the granulator in order to carry out drying more effectively. An active gas may be introduced. The introduction amount is preferably 2 to 30 L / min, more preferably 3 to 10 L / min.

(5) Froude number of granulator blades In the present invention, from the viewpoint of promoting consolidation and sufficiently forming an adhesion layer to narrow the particle size distribution, the blades of the granulator defined by the following formula The fluid number is preferably 1 to 5, more preferably 1.5 to 4.

Fr = V / [(R × g) ^0.5 ]
(Where Fr is the fluid number, V is the peripheral speed [m / sec] of the tip of the stirring blade, R is the rotation radius [m] of the stirring blade, and g is the acceleration of gravity [m / sec. ² ]. Show.)
The granulator used in the present invention is preferably equipped with a stirring blade and a crushing blade and forms a clearance between the stirring blade and the wall surface when the stirring blade rotates. The average clearance is preferably 1 to 30 mm, more preferably 3 to 10 mm. When the average clearance is 1 mm or more, the pressure density of the adhesion layer is moderate, and the granulator does not become overpowered. Further, when the average clearance is 30 mm or less, the consolidation efficiency is good, the particle size distribution is not broad, and the productivity is good.

  Examples of the granulator preferably used in the present invention include, for example, a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), a high speed mixer (manufactured by Fukae Powtech Co., Ltd.), and a vertical granulator [(stock) ) Powrec], Redige mixer [Matsuzaka Giken Co., Ltd.], Pro-share mixer [Pacific Kiko Co., Ltd.], etc., particularly preferred Redige mixer [Matsuzaka Giken Co., Ltd.], high Speed mixer [Fukae Powtech Co., Ltd.], Pro-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.) Manufactured), Shugi mixer (manufactured by POWREC Co., Ltd.), flow jet mixer (manufactured by Flokken Co., Ltd.), etc.

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

  In the present invention, by using a granulator having a stirring blade and a crushing blade, even if the anionic surfactant paste is granulated and adhered to the wall of the granulator, the overpower of the granulator (overload), A granulated product having a high density can be produced without causing a decrease in granulation properties (generation of coarse particles). This phenomenon is considered as follows. The anionic surfactant paste added to the granulator has deposits with high pressure density due to contact with the stirring blade on the side of the stirring blade, and the deposit becomes lower as the wall of the granulator becomes closer. ing. Therefore, the anionic surfactant paste can be taken into the adhesion layer due to the stirring effect, and the granulator is not overpowered. The anionic surfactant paste taken in the adhering layer and the stirring blade is consolidated and spheroidized by the rolling operation, and is released from the adhering layer. Further, the spheroidized spheroidizing proceeds by the rolling action in the granulating part or mixing part in the granulator. That is, in the granulator, it is considered that the compaction / rolling granulation can be favorably performed by the compaction effect in the adhesion layer portion and the rolling operation in the granulation portion or the mixing portion. In order to perform such compaction / rolling granulation, it is important that a clearance is formed between the wall of the granulator and the stirring blade when the stirring blade rotates.

  In the present invention, since granulation is performed simultaneously with drying, it is preferable to carry out while blowing gas. This is to suppress the particulate matter from becoming a large lump by evaporating moisture and cooling the obtained particulate matter using gas. Examples of such gas include nitrogen gas and air.

  Further, in the present invention, fine powder may remain after the addition of the anionic surfactant paste, and therefore, it is possible to have a step of rotating only the stirring blade without substantially rotating the crushing blade. It is preferable from the viewpoint of taking in.

  In addition, the granular anionic surfactant obtained by the production method of the present invention can be used as necessary, for example, in order to further improve the caking property, crystalline alumino such as A-type, P-type, X-type, and Y-type zeolite. In order to coat the particle surface with an inorganic powder such as silicate or sodium sulfate or an alkyl sulfate powder, these may be added.

  In addition, the granular anionic surfactant obtained by the production method of the present invention may be colored with a known colorant such as a pigment or dye in order to improve the aesthetics of the granulated product itself. The coloring method is not particularly limited. For example, a method of spraying an aqueous solution containing a dye or a pigment described in JP-A-2-258882 on the surface of the granular anionic surfactant, or JP-A-11-158493. A method of blending an appropriate amount of the dye or pigment described in the paste and coloring the particulate anionic surfactant may be used. The colorant to be used is not particularly limited, but those having high solubility or dispersibility are preferable. For example, Bengala, Ultramarine Blue, Lionol Green, Red 226, Red 405, Blue 1 and the like are preferable.

[Granular anionic surfactant]
The granular material obtained in the present invention contains 80 to 99.5% by weight, preferably 90 to 99.0% by weight of an anionic surfactant from the viewpoint of effectively exhibiting the function of the anionic surfactant itself.

  The granular anionic surface activity of the present invention may further contain a water-soluble inorganic salt. 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 granular anionic surfactant of the present invention is not particularly limited, but from the viewpoint of keeping the solid content of the anionic surfactant high, it is 10% with respect to 100 parts by weight of the anionic surfactant. Part or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less.

  The granular anionic surfactant of the present invention can contain other additives as required. Examples of other additives include alkali agents such as silicates and carbonates, divalent metal ion scavengers such as citrate and zeolite, anti-contamination agents such as polyvinylpyrrolidone and carboxymethylcellulose, and other anti-caking agents. And antioxidants. Such other additives can be used as long as the object of the present invention is not impaired.

  The granular anionic surfactant of the present invention may contain water, unreacted alcohol and the like. The preferred composition of the granular anionic surfactant of the present invention is 60 to 80% by weight of alkyl sulfate, 18 to 38% by weight of polyoxyalkylene alkyl ether sulfate, 0.5 to 2.5% by weight of water, 0.5% of alcohol. -2.0% by weight and inorganic salt 1.0-2.0% by weight.

  As the physical properties of the granular anionic surfactant of the present invention, the following are preferable.

  (A) The average particle size is preferably 500 to 2000 μm, more preferably 1000 to 1500 μm. In addition, the average particle diameter in this invention is measured from the weight fraction by the size of the sieve mesh after vibrating for 5 minutes using the standard sieve of JISZ8801.

(B) the bulk density is preferably from 300~1000kg / m ^3, still has 600~800kg / m ³ preferred. The bulk density in the present invention is a value determined by a method defined in JIS K 3362.

  (C) The water content of the granular material is preferably 0.3 to 2.5% by weight, more preferably 0.3 to 2.0% by weight from the viewpoint of caking property, and 1.0 to 1.0% from the viewpoint of reducing the amount of dust. 2.0% by weight is particularly preferred. The method for measuring the moisture content of the granular material is not particularly limited and is measured by a method such as a heat loss method, a distillation method, or a Karl Fischer method (JIS K 0068). It is a value measured according to (JIS K 0068).

  (D) The pH value of the 1% by weight aqueous solution is preferably 7.5 to 11.5, and more preferably 8.0 to 10.0. The pH value in the present invention can be determined by preparing an aqueous solution in which particulate matter is dissolved in water (25 ° C.) so as to have a concentration of 1% by weight and measuring the pH of the aqueous solution.

  (E) The fluidity is preferably 10 seconds or less, and more preferably 8 seconds or less. The fluidity in the present invention is the time required for 100 mL of particulate matter to flow out from the hopper for measuring bulk density specified in JIS K 3362.

(F) The sieve passing rate by the caking property test is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. In the method for measuring caking property of the present invention, 70 g of a granular anionic surfactant is enclosed in a plastic bag with a chuck of 0.04 × 70 × 100 mm, a load of 1000 kg / m ² is applied uniformly from above, and a storage temperature of 50 After storage at 30 ° C. for 30 days, the composition is allowed to stand on a 2000 μm sieve, and the caking property of the granulated product is evaluated based on the passing rate of a 2000 μm sieve after hitting 10 times.

  (G) The sphericity is preferably 0.85 or more, more preferably 0.90 or more, and particularly preferably 0.95 or more. The sphericity of the present invention is preferably measured by image analysis. Although the specific measuring method is not specifically limited, For example, the method of Unexamined-Japanese-Patent No. 2003-130785 etc. are mentioned. This method is a method of measuring the sphericity and the like of each particle image data extracted by image processing from the obtained image data by dispersing extruded images without overlapping on a flat surface. The sphericity of the particles of the present invention is measured using this method, and at least 4000 particles are measured from the viewpoint of the stability of the measured values.

  (H) The hue is preferably a Klett value of 1-20, and more preferably 1-15. The Klett value is measured using a 10 mm cell and a wavelength of 420 nm by dissolving a granular anionic surfactant to a concentration of 10% by weight and using the solution using an absorptiometer.

Among these granular anionic surfactants, those satisfying all of the following conditions (a) to (d) are particularly preferable.
(A) Average particle diameter: 500 to 2000 μm
(B) Bulk density: 300 to 1000 kg / m ³
(C) Moisture: 0.3 to 2.5% by weight
(D) pH value of 1% by weight aqueous solution: 7.5 to 11.5
In addition, although it does not specifically limit as a grinder for manufacturing a powder raw material, An atomizer, a com mill, a pin mill, a pulverizer, a Fitz mill, a nebulizer, etc. are mentioned. Among them, those that can be pulverized as finely and uniformly as possible are preferable.

[Detergent composition]
The granular anionic surfactant of the present invention is added to and mixed with other detergent raw materials to form a detergent composition, and if necessary, it is formulated with a high resistance to hard water, foaming well in hard water, and dissolved at low temperature. Since a detergent having excellent properties can be obtained, it is very useful as a detergent base.

  In the present invention, among the detergent raw materials, as the surfactant, in addition to the granular anionic surfactant of the present invention, a nonionic surfactant and, if necessary, a cationic surfactant and an amphoteric surfactant may be used. it can.

  From the viewpoint of detergency, the content of the particulate anionic surfactant in the detergent composition of the present invention is preferably 1 to 50% by weight, more preferably 5 to 30% by weight. As the counter ion of the anionic surfactant, an alkali metal ion is preferable in terms of improving detergency.

  Nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene fatty acid ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, Examples thereof include alkyl glycosides, alkyl glucose amides, and alkyl amine oxides. From the viewpoint of detergency, an ethylene oxide adduct of an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon, or a mixed adduct of ethylene oxide and propylene oxide, having an alkylene oxide average addition mole number of 5 to 30, 6-15 polyoxyalkylene alkyl ethers are preferred. Moreover, polyoxyethylene polyoxypropylene alkyl ether is preferable in terms of detergency and solubility. The compound can be obtained by reacting propylene oxide and further ethylene oxide with an ethylene oxide adduct of an alcohol having 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms. From the viewpoint of detergency, the content of the nonionic surfactant in the detergent composition of the present invention is preferably 1 to 50% by weight, and more preferably 5 to 30% by weight.

  Examples of cationic surfactants include alkyltrimethylammonium salts, and examples of amphoteric surfactants include carbobetaine type and sulfobetaine type surfactants.

  The total content of the surfactant in the detergent composition of the present invention is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, from the viewpoints of detergency and the detergent composition obtaining desired powder properties. Preferably, 27 to 45% by weight is particularly preferable.

  In addition, the detergent composition of the present invention contains water-soluble inorganic salts such as carbonates, bicarbonates, silicates, sulfates, sulfites, or phosphates from the viewpoint of increasing the ionic strength in the washing liquid. can do. Here, the blending amount of the carbonate in the detergent composition is preferably 25% by weight or less, more preferably in terms of anhydride, from the viewpoint of detergency and low-temperature dispersibility under long-term standing conditions in cold water. It is 5 to 20% by weight, particularly preferably 7 to 15% by weight. Moreover, the total of carbonate and sulfate in the detergent composition is preferably 5 to 35% by weight, more preferably 10 to 35% by weight, and particularly preferably 12 to 25% by weight in terms of anhydride.

Furthermore, alkali metal silicate can be mix | blended with the detergent composition of this invention. As the alkali metal silicate, either crystalline or amorphous can be used, but it is preferable to contain a crystalline one because it has a cation exchange ability. In the alkali metal silicate, the ratio of SiO ₂ / M ³ ₂ O (wherein M ³ represents an alkali metal) is preferably 2.6 or less, more preferably 2.4 or less, particularly preferably from the viewpoint of alkalinity. Is 2.2 or less, and from the viewpoint of storage stability, it is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 1.5 or more, and particularly preferably 1.7 or more. Examples of the amorphous alkali metal silicate, for example, JIS 1 No. a granule of No. 2 sodium silicate and water glass dry matter _{Britesil C20, Britesil H 2 0,} Britesil C24, Britesil H24 ( both registered trademarks, The PQ Corporation). Alternatively, NABION15 (registered trademark, manufactured by RHONE-BOULENC), which is a composite of sodium carbonate and amorphous alkali metal silicate, may be used.

  Alkali metal silicate has excellent alkali ability by crystallization and cation exchange ability comparable to 4A-type zeolite, and is a very preferable base from the viewpoint of low-temperature dispersibility. Therefore, the detergent composition of the present invention preferably contains one or more crystalline alkali metal silicates selected from compounds represented by the following formula (IV) or (V).

x (M ⁴ ₂ O) · y (SiO ₂ ) · z (M ⁵ _u O _v ) · w (H ₂ O) (IV)
[Wherein, M ⁴ represents a group Ia element (preferably K and / or Na) of the periodic table, and M ⁵ represents a group IIa element, a group IIb element, a group IIIa element, a group IVa element or VIII of the periodic table. 1 or more selected from group elements (preferably Mg, Ca), y / x = 0.5 to 2.6, z / x = 0.001 to 1.0, w = 0 to 20, v / u = 0.5 to 2.0. ]
M ⁴ ₂ O · x ′ (SiO ₂ ) · y ′ (H ₂ O) (V)
[Wherein, M ⁴ has the same meaning as described above, and x ′ = 1.5 to 2.6 and y ′ = 0 to 20 (preferably substantially 0). ]
These crystalline alkali metal silicates are preferably 0.5 to 40% by weight, more preferably 1 to 25% by weight, particularly preferably 3 to 20% by weight and most preferably 5% in the detergent composition of the present invention. -15 wt% is blended. Here, the crystalline material is preferably 20% by weight or more of the total amount of the alkali metal silicate, more preferably 30% by weight or more, and particularly preferably 40% by weight or more. This crystalline alkali metal silicate can be obtained, for example, from Tokuyama Siltech Co., Ltd. under the trade name “Pre-Feed” (δ-Na ₂ O.2SiO ₂ ). good. In particular, the combined use with sodium carbonate is preferred.

  In addition, the detergent composition of the present invention includes citrate, hydroxyiminodisuccinate, methylglycine diacetate, glutamate diacetate, asparagine diacetate, serine diacetate from the viewpoint of improving the sequestering ability. Organic acid salts such as salts, ethylenediamine disuccinate and ethylenediaminetetraacetate can be blended. Further, from the viewpoint of improving the sequestering ability of metal ions and the dispersibility of solid particle dirt, it is preferable to blend a cation exchange type polymer having a carboxylic acid group and / or a sulfonic acid group. Polyacetal carboxylic acids such as polyacrylic acid such as polyacrylic acid having a molecular weight of 8 to 1,000,000, preferably 5,000 to 200,000 described in JP-A-54-52196 Acid salts are desirable. The cation exchange polymer and / or organic acid salt is preferably 0.5 to 12% by weight, more preferably 1 to 10% by weight, and still more preferably 1 to 7% in the detergent composition from the viewpoint of detergency. % By weight, particularly preferably 2 to 5% by weight.

  The detergent composition of the present invention can contain crystalline aluminosilicates such as A-type, P-type, X-type, Y-type, and faujasite-type zeolite. The average primary particle size of the crystalline aluminosilicate is preferably 0.1 to 10 μm. Further, for the purpose of preventing exudation of liquid components such as nonionic surfactants, an amorphous aluminosilicate having an oil absorption capacity of 80 mL / 100 g or more according to JIS K 5101 method can be blended. Examples of the amorphous aluminosilicate include those described in JP-A Nos. 62-191417 and 62-191419. The amorphous aluminosilicate is preferably blended in an amount of 0.1 to 20% by weight in the detergent composition of the present invention.

  The detergent composition of the present invention includes a dispersant such as carboxymethyl cellulose, polyethylene glycol, polyvinyl pyrrolidone and polyvinyl alcohol, a bleaching agent such as percarbonate, a bleach activator, an enzyme, a biphenyl type and a stilbene type. Fluorescent dyes, antifoaming agents, antioxidants, bluing agents, fragrances and the like can also be blended. In addition, you may after-blend separately granulated particle groups, such as an enzyme, a bleach activator, an antifoamer, and antioxidant.

  Examples of the bleach activator used in the present invention include tetraacetylethylenediamine, glucose pentaacetate, tetraacetylglycoluril, general formula (I), (II), (III) or (IV) of JP-A-8-3593. [For example, sodium p-phenolsulfonate ester (sodium acetoxybenzenesulfonate, sodium benzoyloxybenzenesulfonate, linear or branched octanoyl / nonanoyl / decanoyl / dodecanoylphenolsulfonate, etc.) Or p-hydroxybenzoic acid ester (acetoxybenzenecarboxylic acid, octanoyloxybenzenecarboxylic acid, decanoyloxybenzenecarboxylic acid, dodecanoyloxybenzenecarboxylic acid, etc.)] and the like.

  The enzyme used in the present invention is not particularly limited, and examples thereof include hydrolases, oxidoreductases, lyases, transferases, and isomerases. Particularly preferred are cellulase, protease, lipase, amylase, pullulanase, Examples include esterase, hemicellulase, peroxidase, phenol oxidase, protopectinase, and pectinase. Two or more of these may be used. Considering the dispersibility of the colorant during enzyme granulation and the dyeing property to clothing, a combination of protease and cellulase is particularly preferable. The reason for this is not clear, but coupled with the effect of removing stains and keratin on the fiber surface by protease, the effect of removing the cortex inside the fiber by cellulase is improved, thereby preventing the dye from remaining in sebum components. Guessed.

  The enzyme may be produced by any method and is not particularly limited. Usually, an enzyme obtained by filtering and further drying a culture containing the enzyme produced by a microorganism is used. Further, stabilizers, saccharides, inorganic salts such as sodium sulfate, polyethylene glycol, impurities, water and the like may be contained depending on the culture conditions, separation conditions, and the like.

  As a method of adding these bases in the production process, sodium carbonate is blended into an aqueous slurry and spray-dried, or powdered by an average particle size of about 1 to 40 μm. There are a method of adding to the reforming step, a method of after-blending dense ash, light ash and the like. Examples of the amorphous alkali metal silicate include a method of blending in an aqueous slurry and spray drying, a method of after-blending the granulated product, and the like. The crystalline alkali metal silicate has an average particle size of about 1 to 40 μm, preferably about 1 to 30 μm, more preferably about 1 to 20 μm, and even more preferably about 1 to 10 μm. There is a method of adding to the process. At this time, it is preferable to use a mixture of a crystalline and / or amorphous base such as an aluminosilicate in view of storage stability. Moreover, the method of after-blending the granule prepared by the method using the roller compactor etc. of Unexamined-Japanese-Patent No. 3-16442 is mentioned.

  The production method and shape of the detergent composition of the present invention are not particularly limited, and the granular anionic surfactant of the present invention and other detergent raw materials are mixed with a V-type blender, Nauter mixer (manufactured by Hosokawa Micron Corporation), etc. May be simply dry blended or granulated.

  When granulating, a binder can be mix | blended as needed. As the binder, the above-mentioned various surfactant aqueous solutions or pastes can be used. In addition, a cation exchange polymer having a carboxylic acid group and / or a sulfonic acid group having a sequestering ability and a solid particle soil dispersibility, or a polymer compound such as polyethylene glycol can also be used as an effective binder. The granulation method is also not particularly limited. (1) Stirring rolling granulation method, (2) Fluidized bed granulation method, (3) Extrusion granulation method, (4) Tableting (tablet) and A granulated product of a desired detergent composition can be obtained by a compression granulation method such as ketting or compacting.

[Additive for cement]
The granular anionic surfactant of the present invention can also be suitably used as an additive for cement, particularly as an air entraining agent. The average particle diameter of the granular anionic surfactant used as the additive for cement is preferably 500 to 1500 μm, more preferably 500 to 1100 μm, from the viewpoints of solubility and handling properties. In this case, the granular anionic surfactant is added together with cement, aggregate, etc., and mixed with water to form concrete or mortar in which independent fine bubbles having a diameter of about 0.25 to 0.025 mm are evenly distributed. can get. Concrete and mortar containing these fine bubbles have many advantages such as improved durability against freeze-thaw and improved workability. When the granular anionic surfactant of the present invention is used, concrete and mortar having good stability of the formed bubbles and few cracks after construction can be obtained. There is no restriction | limiting in particular as a shape in that case, A powder form or a granular form etc. can be used. Moreover, it is also preferable to prepare and use as a dry-mixed compound together with components contained in cement such as cement, calcium oxide, calcium hydroxide, calcium sulfate and powders that do not adversely affect after construction.

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

Synthesis example 1
In a thin film flow-down reactor having an inner diameter of 16 mmφ and a length of 5 m, together with 2.0% by volume of sulfur trioxide gas, the alkyl group has 12 to 16 carbon atoms and its distribution is C ₁₂ / C ₁₄ / C ₁₆ = 67% A higher alcohol (molecular weight: 199) of / 28% / 5% was continuously added at 60 ° C. for reaction. The flow rate was adjusted so that the reaction molar ratio of sulfur trioxide gas to higher alcohol was 1.01. The obtained sulfate was neutralized with a 32.2% aqueous sodium hydroxide solution, 75% phosphoric acid (buffering agent) was added, and then finely adjusted to pH = 10 with a 32.1% aqueous sodium hydroxide solution. The active ingredient of the resulting alkyl sulfate sodium salt paste (hereinafter referred to as paste 1) was 73%.

Synthesis example 2
A higher alcohol having an alkyl group having 12 to 16 carbon atoms and a distribution of C ₁₂ / C ₁₄ / C ₁₆ = 67% / 28% / 5% and an average of ethylene oxide using a potassium hydroxide catalyst in the higher alcohol A raw material (average molecular weight 209) blended with 1.0 mol added ethoxylate in a ratio of 75%: 25% is used in place of the higher alcohol, and 30.1% aqueous sodium hydroxide solution is used. The reaction was conducted in the same manner as in Synthesis Example 1. The active ingredient of the obtained polyoxyethylene alkyl sulfate sodium salt paste (hereinafter referred to as paste 2) was 72%.

Synthesis example 3
While adjusting the drying conditions so that the jacket temperature is 85 ° C, the pressure is 4.0 kPa, and the operation product temperature is 70 ± 1 ° C, the paste 1 and paste 2 are mixed so that the weight ratio is 75:25. It is dripped at a vacuum dryer (FMD-1200JE type, manufactured by Fukae Pautech Co., Ltd.) having an internal volume of 2500 L at an average addition rate of 150 kg / Hr, the agitator rotation speed: 55 r / min, the chopper rotation speed: 2000 r / min, Average clearance between stirring blade and wall surface: Granulation was performed simultaneously with drying under a granulation condition of 5.5 mm to obtain 600 kg of a granulated product. Further, a part of the granulated product was pulverized with an atomizer (Fuji Powder Co., Ltd.) to obtain a powder raw material having an average particle size of 120 μm.

Example 1
Put a powder of sodium alkylsulfate [EMAL 10P-HD: Kao Corporation, average particle size: 100μm] 100kg into a 2500L vacuum dryer [FMD-1200JE, manufactured by Fukae Pautech Co., Ltd.] Paste at a temperature of 65 ° C., granulator pressure: 5.3 kPa, agitator rotation speed: 70 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blade and wall: 5.5 mm After starting dropping 1 into the dryer at an addition rate of 240 kg / Hr, granulation was performed simultaneously with drying while adjusting the dropping flow rate of paste 1 so that the product temperature was 46 ± 2 ° C. Then, when the total amount of paste dropped was 650 kg, the dry granulation was finished, and a granulated product of sodium alkyl sulfate sodium salt [average molecular weight: 301] was obtained. The ratio of time to reach operating temperature and paste addition time is 1/10.

Example 2
Put the alkyl sulfate sodium salt powder [EMAL 10P-HD: Kao Corporation, average particle size: 100μm] 130kg into a 2500L vacuum dryer [FMD-1200JE type, manufactured by Fukae Powtech Co., Ltd.] Paste at a temperature of 65 ° C., granulator pressure: 5.3 kPa, agitator rotation speed: 70 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blade and wall: 5.5 mm After starting dropping 1 into the dryer at an addition rate of 235 kg / Hr, granulation was performed simultaneously with drying while adjusting the dropping flow rate of paste 1 so that the product temperature was 45 ± 3 ° C. Then, when the total amount of paste dropped was 650 kg, the dry granulation was finished, and a granulated product of sodium alkyl sulfate sodium salt [average molecular weight: 301] was obtained. The ratio of time to reach operating temperature and paste addition time is 1/9.

Example 3
Put a 130 kg vacuum alkyl dryer (Fukae Powtech Co., Ltd., FMD-1200JE type) with 130 kg of alkyl sulfate sodium salt powder [EMAL 10P-HD: Kao Corporation, average particle size: 100 μm] into a jacket. Paste at a temperature of 85 ° C, pressure in the granulator: 5.3 kPa, agitator rotation speed: 70 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blade and wall: 5.5 mm After starting dropping 1 into the dryer at an addition rate of 304 kg / Hr, granulation was performed simultaneously with drying while adjusting the dropping flow rate of paste 1 so that the product temperature was 50 ± 3 ° C. Thereafter, when the total amount of the paste dropped was 650 kg, the dry granulation was finished to obtain a granulated product of sodium alkylsulfate [average molecular weight: 301]. The ratio of time to reach operating temperature and paste addition time is 1/7.

Example 4
Put the alkyl sulfate sodium salt powder [EMAL 10P-HD: manufactured by Kao Corporation, average particle size: 100 μm] 4.3 kg into a 65 L vacuum dryer [FMD-65JE type, manufactured by Fukae Pautech Co., Ltd.] , Jacket temperature 85 ° C, granulator pressure: 6.7 kPa, agitator rotation speed: 200 r / min, chopper rotation speed: 3000 r / min, average clearance between stirring blade and wall: 3.5 mm After starting dropping of paste 1 into the dryer at an addition rate of 19.7 kg / Hr, granulation was performed simultaneously with drying while adjusting the dropping flow rate of paste 1 so that the product temperature was 60 ± 2 ° C. . Then, when the total amount of paste dropped was 20 kg, the dry granulation was finished, and a granulated product of alkyl sulfate sodium salt [average molecular weight: 301] was obtained. The ratio of time to reach operating temperature and paste addition time is 1/20.

Example 5
200 kg of powder raw material [average molecular weight: 311, average particle size: 120 μm] of sodium alkylsulfate obtained in Synthesis Example 3 was added to a 2500 L vacuum dryer (FMD-1200JE type, manufactured by Fukae Pautech Co., Ltd.). , Jacket temperature 85 ° C, granulator pressure: 4.0 kPa, agitator rotation speed: 55 r / min, chopper rotation speed: 2000 r / min, average clearance between stirring blade and wall: 5.5 mm After adding the paste 1 and paste 2 mixed at a weight ratio of 75:25 into the dryer at an addition rate of 150 kg / Hr, the paste was adjusted so that the product temperature would be 70 ± 1 ° C. While adjusting the dropping flow rate of the paste in which 1 and paste 2 were mixed at a weight ratio of 75:25, granulation was performed simultaneously with drying. Thereafter, when the total amount of paste dropped was 450 kg, the dry granulation was completed, and a granulated product of polyoxyethylene alkylsulfate sodium salt [average molecular weight: 311] having an ethylene oxide average addition mole number of 0.25 was obtained. . Thereafter, 8% of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and a granular anionic surfactant having a particle size of 500 to 2000 μm was obtained by vibration sieving. The ratio of time to reach operating temperature and paste addition time is 1/12.

Example 6
3. Powder alkyl raw material of sodium alkyl sulfate obtained in Synthesis Example 3 [average molecular weight: 311; average particle size: 120 μm] in a 65 L vacuum dryer (FMD-65JE type, manufactured by Fukae Pautech Co., Ltd.) 3 kg is charged, jacket temperature is 85 ° C., pressure in granulator: 6.7 kPa, agitator rotation speed: 200 r / min, chopper rotation speed: 3000 r / min, average clearance between stirring blade and wall: 3.5 mm Depending on the grain conditions, paste 1 and paste 2 mixed at a weight ratio of 75:25 are added dropwise at a rate of 11.4 kg / Hr into the dryer, and the product temperature reaches 68 ± 2 ° C. Thus, granulation was performed simultaneously with drying while adjusting the dropping flow rate of the paste in which paste 1 and paste 2 were mixed at a weight ratio of 75:25. Thereafter, when the total amount of paste dropped was 20 kg, the dry granulation was completed, and a granulated product of polyoxyethylene alkylsulfate sodium salt [average molecular weight: 311] having an average number of moles of ethylene oxide added of 0.25 was obtained. . Thereafter, 8% of zeolite was added to the obtained granulated product, and the zeolite was uniformly coated on the granular anionic surfactant, and a granular anionic surfactant having a particle size of 500 to 2000 μm was obtained by vibration sieving. The ratio of time to reach operating temperature and paste addition time is 1/12.

Comparative Example 1
Into a 65L vacuum dryer (FMD-65JE type, manufactured by Fukae Powtech Co., Ltd.), 4.3 kg of alkyl sulfate sodium salt powder [EMAL 10P-HD: manufactured by Kao Corporation, average particle size: 100 μm] is 4.3 kg. The pressure inside the granulator is not reduced, the pressure inside the granulator: 101.23 kPa (atmospheric pressure), the rotational speed of the agitator: 200 r / min, the rotational speed of the chopper: 3000 r / min , Average clearance between stirring blade and wall surface: Under the dry granulation conditions of 3.5 mm, after dropping of paste 1 into the dryer at an addition rate of 19.7 kg / Hr, the product temperature should be 60 ± 2 ° C While adjusting the dropping flow rate of paste 1, granulation was performed simultaneously with drying. Thereafter, when the total amount of the paste dropped was 20 kg, the dry granulation was finished to obtain a granulated product of sodium alkylsulfate [average molecular weight: 301]. However, only a lump granulated product was obtained, and a granular anionic surfactant having a desired shape could not be obtained, and the water content was 4.5%. The ratio of time to reach operating temperature and paste addition time is 1/20.

Comparative Example 2
Paste 1 was dripped at a high viscosity paste pump (4NES60 type: Hyojin Equipment Co., Ltd.) at 13.3 kg / Hr from the upper receiving port of a thin film drying device (Cebucon: manufactured by Hitachi, Ltd.), and the blade rotation speed : Continuous drying was performed at 760 r / min, pressure inside the dryer of 9.2 kPa, and a drying temperature of 84.4 ° C. However, only a flaky dried product was obtained, and a granular anionic surfactant having a desired shape could not be obtained. The moisture content of the dried product was 4.8%.

  Table 1 summarizes the production conditions of Examples 1 to 6 and Comparative Examples 1 and 2 and the physical properties of the obtained granular anionic surfactants.

Test example 1
Using the granular anionic surfactants obtained in Examples 1 to 6 and Comparative Examples 1 and 2, the caking property was evaluated by the following method. The results are shown in Table 2.

<Caking properties>
70 g of a granular anionic surfactant is sealed in a plastic bag with a chuck of 0.04 × 70 × 100 mm, a load of 1000 kg / m ² is applied uniformly from above, and after storage at a storage temperature of 50 ° C. for 30 days, 2000 μm The caulking property of the sieved granulated product was evaluated according to the following criteria.
A: Almost no caking was observed after 30 days (passage rate of 90% or more)
○: Almost no caking was observed after 14 days (passage rate of 90% or more)
X: Generation of caking was observed within 14 days (passage rate 90% or more)

Test example 2
Using the granular anionic surfactant obtained in Example 5 and the commercially available products shown in Table 3 for comparison, the bulk density and dissolution rate were measured by the following methods. The results are shown in Table 3.

<Bulk density>
The measurement was performed by the method defined in JIS K 3362.

<Dissolution rate>
950 g (30 ° C.) of ion-exchanged water is stirred (900 r / min), and 50 g of a granular anionic surfactant is added all at once. The electrical conductivity was measured over time using a conductivity meter [manufactured by HORIBA; DS-8F], and the 99% value (time) of the point where the electrical conductivity was stabilized was taken as the dissolution rate.

Test example 3
Using the granular anionic surfactant obtained in Example 5 and a commercially available product (SULFOPON 1216G, manufactured by COGNIS) for comparison, the hard water resistance was evaluated by the following method. As a result, the granular anionic surfactant of Example 5 was evaluated. The hard water resistance of both the agent and the comparative commercial product was acceptable.

<Hard water resistance>
The test was conducted in accordance with a synthetic detergent test method (JIS K 3362). Add 100 mL of hard water (16 ° DH) at 50 ° C. and 100 mL of test solution with a concentration of 2.0 g / L in terms of anhydride while stirring, leave it in a 50 ° C. constant temperature bath for 10 minutes, take it out, and place it on the judgment plate. Those with a cross were allowed to pass, and others were rejected.

Test example 4
Using the granular anionic surfactant obtained in Example 6 and commercially available products shown in Table 4 for comparison, detergency (foaming power and foam stability) was evaluated by the following methods. The results are shown in Table 4.

<Detergency (foaming power and foam stability)>
The test was performed in accordance with a synthetic detergent test method (JIS K3362). A test solution was prepared by dissolving a sample in hard water (16 ° DH) at a concentration of 2.0 g / L in terms of anhydride. The bubble height (mm) generated when 200 mL of the test solution was dropped on the liquid surface (50 mL of the same test solution) in 30 seconds from a height of 900 mm under the condition of 40 ° C. was measured as a foaming force after 1 minute. The foam height (mm) after 5 minutes was defined as the foam stability. Each measurement was performed three times, the average value was obtained, and the relative value when the value of a commercially available comparative product was taken as 1.00.

Test Example 5
In order to confirm the effect of the particulate anionic surfactant obtained in Example 6 as an air entraining agent, a cement composition having the following composition was prepared using a commercial instant cement (manufactured by House Mender Co., Ltd.). . Moreover, the cement composition was similarly prepared using the commercial item shown in Table 5 for the comparison. About these cement compositions, the air quantity was measured with the following method. The results are shown in Table 5.

<Cement composition>
Instant cement 100 parts by weight Ion exchange water 32 parts by weight Air entraining agent Amount shown in Table 5 <Air amount>
Ion exchange water, Portland cement, sand and air entraining agent are mixed uniformly at 20 ° C. using a mortar cone for 30 seconds, and the bulk density of this mixture is measured with a container having a known bulk specific gravity. The amount of air was calculated.

  Air amount [%] = [(bulk specific gravity before adding air entraining agent−bulk specific gravity after adding air entraining agent) / (bulk specific gravity before adding air entraining agent)] × 100

Claims (8)

  In a granulator having a stirring blade and a crushing blade, granulation is performed simultaneously with drying while adding an anionic surfactant paste to the powder raw material under reduced pressure, and contains 80 to 99.5% by weight of anionic surfactant A method for producing a granular anionic surfactant to obtain a granular product.   The manufacturing method according to claim 1, wherein drying is performed so that the temperature of the granular material is 35 to 75 ° C and the temperature change is within ± 5 ° C.   The manufacturing method of Claim 1 or 2 whose granulator internal pressure is 0.67-40kPa.   The manufacturing method in any one of Claims 1-3 in which a powder raw material contains at least 1 sort (s) chosen from the group which consists of surfactant, water-soluble inorganic salt, and water-insoluble inorganic salt.   The manufacturing method in any one of Claims 1-4 which uses a part of obtained granular material as a powder raw material.   A granular anionic surfactant obtained by the production method according to claim 1.   A detergent composition comprising the particulate anionic surfactant according to claim 6. A cement additive containing the granular anionic surfactant according to claim 6.