JP2012107165A - Method for manufacturing detergent particle group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a detergent particle group having good fluidity, controlled sortability and medium to low bulk density, by which a ratio of spray-dried particles to be used is reduced and the detergent particle group is obtained in high yield and at a low coarse particle ratio.SOLUTION: The method for manufacturing the detergent particle group comprises a step (A) of spray-drying the slurry containing an anionic surfactant to prepare particles (A) containing 5-40 mass% anionic surfactant; a step (B) of granulating a powdery raw material for a detergent in a vessel-rotating type mixer while adding the anionic surfactant and/or a precursor thereof into the vessel-rotating type mixer from a multi-fluid nozzle to prepare particles (B); and a step (C) of mixing the particles (A) with the particles (B).

Description

  The present invention relates to a method for producing detergent particles, and more particularly, to a method for producing detergent particles including particles prepared using a spray dryer and particles prepared using a container rotating mixer.

  At present, commercially available detergents are roughly classified into high bulk density detergents (greater than 600 g / L), medium bulk density detergents (400 to 600 g / L), and low bulk density detergents (250 g / L to 400 g). / L) and liquid detergents. For example, high bulk density detergents are often used in Japan, but there are also many demands for medium and low bulk density detergents in Asia, Oceania and Europe.

  In a low bulk density type detergent, the manufacturing method includes a method in which an anionic surfactant and other builder are blended in a slurry and manufactured by spray drying. On the other hand, in a high bulk density type detergent, a method has been proposed in which an anionic surfactant and other builder are blended in a slurry and spray-dried, followed by a high bulk density treatment.

  In medium bulk density detergent, an anionic surfactant and other builder are mixed in a slurry and spray dried to prepare low bulk density spray dried particles, and then the spray dried particles and previously obtained high bulk density particles For example, and a method of mixing to increase the bulk density (see Patent Document 1).

  In recent years, there has been a demand for a method for producing a medium-low bulk density detergent while reducing spray-dried particles as much as possible from the viewpoint of energy saving and environmental load reduction. In the production method described in Patent Document 1, high bulk density particles are mixed, and there is a problem that the ratio of spray-dried particles becomes high to produce a medium and low bulk density detergent. Furthermore, although the production method described in Patent Document 1 has an effect of suppressing classification in transportation, it still remains dissatisfied with the fluidity of the product.

JP2008-63419

  Accordingly, an object of the present invention is to provide a method for producing a medium and low bulk density detergent particle group having good fluidity and suppressed classification, and capable of reducing the ratio of spray-dried particles to be used. It is to be. Furthermore, the subject of this invention is providing a detergent particle group with a sufficient yield and a low coarse particle rate.

That is, the gist of the present invention is as follows.
Step (A): a step of spray-drying a slurry containing an anionic surfactant to prepare particles (A) containing 5 to 40% by mass of the anionic surfactant in the particles,
Step (B): A step of preparing particles (B) by granulating a powder raw material for detergent using a container rotary mixer, wherein an anionic surfactant and / or a precursor thereof are mixed with a multi-fluid. A step of preparing particles (B) by adding them into the container rotary mixer using a nozzle, and a step (C): a step of mixing the particles (A) and the particles (B),
The manufacturing method of the detergent particle group containing this.

  By the method for producing the detergent particle group of the present invention, a medium and low bulk density detergent particle group having good fluidity and reduced classification with a reduced spray-dried particle ratio to be used is obtained with a high yield and a low coarse particle ratio. I can do it.

One of the features of the present invention is that
Step (A): a step of spray-drying a slurry containing an anionic surfactant to prepare particles (A) containing 5 to 40% by mass of the anionic surfactant in the particles,
Step (B): A step of preparing particles (B) by granulating a powder raw material for detergent using a container rotary mixer, wherein an anionic surfactant and / or a precursor thereof are mixed with a multi-fluid. A step of preparing particles (B) by adding them into the container rotary mixer using a nozzle, and a step (C): a step of mixing the particles (A) and the particles (B),
A detergent particle group is obtained using a method for producing a detergent particle group.

  In general, in granulation using a rotating container mixer, it is possible to make the powder flow uniformly, and because of the mixing mechanism involving lifting of the particles by rotation and sliding / falling by their own weight, The shearing force applied to is suppressed. Therefore, it can be said that the granulation method using such a mixer is a non-consolidated granulation method. In addition, an anionic surfactant and / or an acid precursor thereof (in this specification, “an anionic surfactant and / or an acid precursor thereof” is indicated as “component C”). Since the granulation does not proceed unless the adhesiveness when in contact with the powder is strong, it is necessary to develop the adhesiveness when in contact with the powder. When such a component C is supplied to a container rotation type mixer by a one-fluid nozzle or pipe, which is a general supply method, the supplied liquid component is not easily dispersed in the mixer and is locally generated. There was a problem that coarse particles were easily formed by a large liquid mass.

  Therefore, when a multi-fluid nozzle such as a two-fluid nozzle is used to spray the component C that develops tackiness when it comes into contact with the powder and is supplied into the rotating container of the container, unexpectedly, the coarse particles It was found that uniform granulation was possible while suppressing formation. This is because component C is made into fine droplets in advance using a multi-fluid nozzle, so that high dispersion of component C can be achieved even in a container-rotating mixer, and a large liquid mass forming coarse particles is generated. It is thought that it does not. Therefore, it is also one of the features of the present invention that the component C that develops adhesiveness when it comes into contact with the powder is added into the container rotary mixer using a multi-fluid nozzle.

  As described above, in the present invention, a combination of a container rotating type mixer and a multi-fluid nozzle can be used to contain an anionic surfactant in a high ratio, which cannot be expected from the case where each is used alone. Bulk density particles can be obtained, and further, by mixing the particles and spray-dried particles, an effect of obtaining a medium / low bulk density detergent having good fluidity at a low spray-dry particle ratio can be obtained.

  Hereinafter, the aspect as an example of the manufacturing method of this invention is demonstrated in detail.

  In the present invention, the detergent particles are particles containing a surfactant, a builder and the like, and the detergent particle group means an aggregate thereof. The detergent composition contains detergent particles and is optionally added separately from the detergent particles (for example, builder granules, fluorescent dyes, enzymes, fragrances, antifoams, bleaches, bleach activators) Etc.).

A. Manufacturing method of detergent particle group <Process (A)>
In the step (A), a slurry containing an anionic surfactant is spray-dried to prepare particles (A) (spray-dried particles) containing 5 to 40% by mass of the anionic surfactant in the particles. is there. The bulk density of the particles (A) is preferably 200 to 600 g / L, more preferably 200 to 550 g / L, and more preferably 200 to 550 g / L, from the viewpoint of reducing the ratio of spray-dried particles to obtain a medium and low bulk density detergent particle group. 500 g / L is more preferable. The average particle diameter of all the particles (A) is preferably 150 to 500 μm, more preferably 200 to 400 μm, and still more preferably 200 to 350 μm from the viewpoint of solubility. The fluidity of the particles (A) is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and still more preferably 4 to 8 seconds, from the viewpoint of ease of charging into the mixer. The angle of repose of the particles (A) is preferably from 20 to 55 °, more preferably from 25 to 50 °, and further preferably from 30 to 50 °, from the viewpoint of ease of charging into the mixer and difficulty in bridging of the particles. preferable. Below, each component used for this invention is demonstrated.

1. Anionic surfactant What is generally used can be used as an anionic surfactant. Examples thereof include linear alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfate, polyoxyethylene alkyl sulfate, and fatty acid ester sulfonate. Such an anionic surfactant may be used alone or in combination of two or more components. The counter ion is preferably an alkali metal, particularly sodium. Of these, linear alkylbenzene sodium sulfonate and sodium alkyl sulfate are preferred from the viewpoints of economy, thermal stability and foaming.

  As an addition method of the anionic surfactant, the acid precursor is added to the slurry, and the acid precursor is neutralized in the slurry with a sodium hydroxide aqueous solution or the like added to the slurry separately. Alternatively, a method of adding a previously neutralized anionic surfactant to the slurry may be used.

  By containing the anionic surfactant in the slurry, the bulk density of the resulting spray-dried particles can be reduced. The amount of the anionic surfactant added to the slurry is preferably 5% by mass or more, more preferably 10% by mass or more, and further 15% by mass or more in the obtained spray-dried particles. preferable. In addition, from the viewpoint of thermal stability and energy efficiency of the anionic surfactant, the amount added is preferably 40% by mass or less, and more preferably 35% by mass or less.

  As an essential component for the spray-dried particles in the present invention, only an anionic surfactant is used, but from the viewpoint of cleaning performance, particle size distribution, and particle strength, it is usually used in detergent compositions as needed. Other ingredients can be included in the spray-dried particles. Examples of other components include water-soluble solid alkali inorganic substances, chelating agents, water-soluble inorganic salts, water-soluble polymers, water-insoluble excipients, nonionic surfactants, and other auxiliary components. It is preferable to blend a water-soluble solid alkali inorganic substance, a chelating agent, a water-soluble inorganic salt and / or a water-soluble polymer. Such other components are added to the spray-dried particles by being added to the slurry in the same manner as the anionic surfactant. The amount of other components added to the slurry is not particularly limited, and is the remaining amount of the anionic surfactant and water in the resulting spray-dried particles. The amount of other components added to the slurry is preferably 45 to 94% by mass in the resulting spray-dried particles. Specific examples of other components will be described below.

2. Water-soluble solid alkali inorganic substance Water-soluble solid alkali inorganic substance is an alkali inorganic substance that is solid at room temperature (20 ° C.), and the water-soluble solid alkali inorganic substance is not particularly limited. Examples thereof include sodium, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium silicate and the like. Among them, sodium carbonate and sodium silicate are preferable as an alkaline agent that exhibits a suitable pH buffer region in the washing liquid.

3. Chelating agents Chelating agents can be incorporated into spray-dried particles in order to suppress the cleaning action inhibition by metal ions. Examples include water-soluble chelating agents and water-insoluble chelating agents. It is also possible to mix.

  The water-soluble chelating agent is not particularly limited, but for example, tripolyphosphate, orthophosphate, pyrophosphate, etc. can be used. Further, as the counter ion, an alkali metal salt is preferable, and sodium and / or potassium is particularly preferable.

  The water-insoluble chelating agent may be added for the purpose of improving the sequestering ability and the strength of the spray-dried particles. Examples thereof include crystalline or non-crystalline alkali metal aluminosilicates (zeolites), and metal ions. A-type zeolite is preferable in terms of sealing ability and economy. From the viewpoint of dispersibility in water, the average particle size of the particles is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm.

4). Water-soluble inorganic salt The water-soluble inorganic salt is preferably added to the spray-dried particles in order to increase the ionic strength of the washing liquid and improve the effect of cleaning sebum dirt. As the water-soluble inorganic salt, for example, sodium sulfate, sodium chloride, sodium sulfite and potassium sulfate having a high degree of ionic dissociation are preferable. From the viewpoint of improving the dissolution rate of the detergent particles, the combined use of magnesium sulfate is also effective.

5. Water-soluble polymer It is also preferable to blend a water-soluble polymer having effects such as metal ion scavenging ability and mud dirt dispersibility. For example, polyethylene glycol, carboxylic acid polymer, carboxymethyl cellulose, soluble starch, saccharide and the like can be mentioned. Among these, polyethylene glycol having a mass average molecular weight of 5000 to 20000 and a carboxylic acid polymer having a mass average molecular weight of several thousand to 100,000 are preferable from the viewpoints of sequestering ability, dispersibility of solid dirt, particle dirt, etc. Particularly preferred are salts of acrylic acid-maleic acid copolymers and polyacrylates.

6). Water-insoluble excipient The water-insoluble excipient is not particularly limited as long as it is a substance that has good dispersibility in water and does not adversely affect detergency. For example, clay compounds such as silicon dioxide, hydrated silicate compound, barlite, bentonite and the like can be mentioned. From the viewpoint of dispersibility in water, the primary particles preferably have an average particle size of 0.1 to 20 μm, more preferably 0.5 to 10 μm.

7). Moisture The moisture in the spray-dried particles is preferably 15% by mass or less in the spray-dried particles from the viewpoint of the particle strength of the spray-dried particles, and preferably 0.5% by mass or more from the viewpoint of energy efficiency.

8). Other auxiliary components Fluorescent dyes, pigments, dyes and the like may be blended in the spray-dried particles.

  The spray-dried particles used in the present invention can be obtained by spray-drying the slurry in which the above components are added and mixed. In addition, there is no limitation in particular about the moisture content and spray-drying conditions of a slurry. Spray-dried particles can be obtained by the production method described in, for example, the well-known collection of conventional techniques (powder detergent for clothing) issued by the Japan Patent Office.

<Process (B)>
Step (B) is a step of preparing particles (B) that are granulated products using a container rotating mixer and a multi-fluid nozzle. That is, the particle (B) is prepared by adding the component C using a multi-fluid nozzle into the container rotary mixer into which the powder raw material for detergent is charged.

The bulk density of the particles (B) is preferably 400 to 650 g / L, more preferably 420 to 620 g / L, and still more preferably 440 to 600 g / L. The bulk density of the particles (B) is preferably 650 g / L or less, more preferably 620 g / L or less, and even more preferably 600 g / L or less from the viewpoint of reducing the ratio of spray-dried particles and from the viewpoint of suppressing classification during transportation. From the viewpoint of transportation cost, 400 g / L or more is preferable, 420 g / L or more is more preferable, and 440 g / L or more is more preferable. The average particle diameter of the particles (B) is preferably 150 to 700 μm, more preferably 180 to 650 μm, and still more preferably 200 to 600 μm, from the viewpoints of solubility and powdering. The fluidity of the particles (B) is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and still more preferably 4 to 8 seconds, from the viewpoint of ease of charging into the mixer. The angle of repose of the particles (B) is preferably from 20 to 60 °, more preferably from 25 to 55 °, and more preferably from 30 to 50 °, from the viewpoint of ease of charging into the mixer and difficulty in bridging the particles. Is more preferable, and 35 to 45 ° is more preferable. The granulation yield of the particles (B) is preferably 85 to 100%, more preferably 90 to 100%, still more preferably 95 to 100%. The coarse particle ratio of the particles (B) is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less from the viewpoints of appearance and solubility.
Below, each component which can be used in a process (B), a container rotation type mixer, a multifluid nozzle, etc. are demonstrated.

[Anionic surfactant and / or its precursor (component C)]
1. Anionic Surfactant Acid Precursor The anionic surfactant acid precursor used in step (B) is an anionic surfactant precursor that shows an acid form and is liquid at room temperature. Good, salt is formed by neutralization reaction. Therefore, the acid precursor is not particularly limited as long as it is a known anionic surfactant precursor and has the above-mentioned properties, but linear alkylbenzene sulfonic acid, α-olefin sulfonic acid, alkyl sulfuric acid, polysulfate, Examples thereof include oxyethylene alkyl sulfuric acid and fatty acid ester sulfonic acid. Such an acid precursor may use only one component, and may use it in combination of 2 or more components. Of these, linear alkylbenzenesulfonic acid and alkylsulfuric acid are preferred from the viewpoints of economy, storage stability and foaming.

  As described in Japanese Patent No. 3313372, a predetermined amount of an inorganic acid such as sulfuric acid may be mixed in advance with the acid precursor.

2. Anionic surfactants Anionic surfactants as component C are: This was obtained by neutralizing the acid precursor of the anionic surfactant. Such an anionic surfactant may be used alone or in combination of two or more components. Of these, alkyl sulfates and polyoxyethylene alkyl sulfates are preferred from the viewpoints of economy and foaming. 1. An aqueous alkali solution is used as a neutralizer for the acid precursor of the anionic surfactant. Although it does not specifically limit as a kind of aqueous alkali solution, For example, strong alkali aqueous solutions, such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, are mentioned, Sodium hydroxide aqueous solution is preferable from an economical viewpoint.

  The anionic surfactant used in the step (B) contains an anionic surfactant and water, and has a viscosity at 60 ° C. of 100 Pa · s or less. The viscosity of an anionic surfactant varies greatly depending on its water content. Therefore, it is preferable to adjust the concentration of the aqueous alkali solution used for neutralizing the acid precursor to prepare an anionic surfactant having a desired water content, that is, having a desired viscosity. When the anionic surfactant contains 25 to 70 parts by mass (water content of the surfactant composition is about 20 to 40%) of water based on 100 parts by mass of the anionic surfactant, It is generally known that it becomes a paste-like anionic surfactant having a reduced viscosity and is easy to handle, and in the present invention, the paste-like anionic interface in which the moisture of the anionic surfactant is adjusted within this range. It is preferred to use an activator. The viscosity of the paste-like anionic surfactant has a temperature range of preferably 10 Pa · s or less, more preferably 5 Pa · s or less, from the viewpoint of handleability in production. Such a use temperature range is preferably up to 70 ° C., more preferably up to 60 ° C., from the viewpoint of the stability of the anionic surfactant. Here, the viscosity is determined by measuring at a shear rate of 50 [1 / s] with a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN).

  Among the acid precursors of the anionic surfactant, those which are very unstable and easily decomposed are preferably prepared so that the decomposition can be suppressed. The preparation method is not particularly limited, and a known method can be used. For example, using a loop reactor, the heat of neutralization is removed by a heat exchanger or the like, and the production may be performed while paying attention to the temperature control of the acid precursor and the anionic surfactant.

  Moreover, it is preferable that this obtained anionic surfactant has excess alkalinity from a viewpoint of suppressing decomposition | disassembly.

  In addition, unreacted alcohol and unreacted polyoxyethylene alkyl ether at the time of producing the acid precursor, sodium sulfate as a by-product during the neutralization reaction, and neutralization reaction can be added to the anionic surfactant A pH buffering agent, a decoloring agent, etc. may be contained.

  The amount of the anionic surfactant is preferably 10 to 45% by mass and more preferably 13 to 35% by mass in the particles (B) from the viewpoints of detergency and granulation. Since the anionic surfactant acid precursor is neutralized in the detergent particle group, the anionic interface in the detergent particle group can be obtained even when the anionic surfactant acid precursor is added. Calculated as the amount of activator.

  In the present invention, the anionic surfactant and / or its acid precursor has the ability to form a granulated product by combining powder raw materials for detergent, and as described in the above paragraph, component C It is one of the important points that the adhesiveness develops when it comes into contact with the powder raw material for detergent. The presumed mechanism about adhesive expression is demonstrated below.

  When an anionic surfactant acid precursor is used, when added to a water-soluble solid alkaline inorganic material that is a powder raw material for detergents, the neutralization reaction proceeds on the surface of the particles, and the anionic surfactant has an adhesive property. A neutralized product of the acid precursor of the ionic surfactant is formed. When an anionic surfactant is used, when the anionic surfactant is added to the detergent powder raw material, the water in the anionic surfactant is hydrated with the detergent powder raw material. Or when the temperature of the powder raw material for detergent is lower than the temperature of the anionic surfactant, the temperature of the anionic surfactant is lowered to near or below its melting point. When the anionic surfactant is solidified, adhesiveness is developed.

  Thus, granulation of the powder raw material for the detergent proceeds when the component C comes into contact with the powder raw material for the detergent, and as a guideline for the expression of the adhesive, the component C is a detergent. The viscosity when contacted with the powder raw material is preferably 2 Pa · s or more, and more preferably 3 Pa · s or more. The viscosity is measured when the component C comes into contact with the powder raw material for detergent at a shear rate of 50 [1 / s] with a coaxial double cylindrical rotational viscometer (manufactured by HAAKE, sensor: SV-DIN). The temperature and moisture value may be adjusted and measured so as to be the same.

[Powder raw material for detergent]
Examples of the powder raw material for the detergent include water-soluble solid alkali inorganic substances and water-soluble inorganic salts.

1. Water-soluble solid alkaline inorganic substance In the present invention, when an anionic surfactant acid precursor is used as a component added by a multi-fluid nozzle, a water-soluble solid alkaline inorganic substance is used to dry neutralize the acid precursor. Is an essential component.

  The water-soluble solid alkali-inorganic substance is an alkali inorganic substance that is solid at room temperature (20 ° C.), and the water-soluble solid alkali-inorganic substance is not particularly limited. For example, sodium carbonate, sodium bicarbonate, carbonate Examples thereof include potassium and sodium silicate. Among them, sodium carbonate is preferable as an alkaline agent that exhibits a suitable pH buffer region in the washing liquid. These water-soluble solid alkali inorganic materials may be used alone or in combination of two or more.

  As sodium carbonate, both light soda ash (light ash) and heavy soda ash (dense ash) can be used, but light ash is used from the viewpoint of reactivity with the acid precursor. preferable.

  The water-soluble solid alkali inorganic material is capable of functioning as a detergent builder and alkaline agent in the final composition. Therefore, the addition amount of the water-soluble solid alkaline inorganic substance is the amount necessary for neutralizing the acid precursor of the anionic surfactant blended as component C (neutralization equivalent) to exert the above function. Preferably an amount is added. That is, the addition amount of the water-soluble solid alkali inorganic material is preferably the neutralization equivalent or an amount substantially larger than the amount, for example, preferably 1 to 35 times the neutralization equivalent, more preferably 2 -30 times, more preferably 3-25 times. In the present invention, an inorganic acid may be used in combination with an acid precursor. In that case, the neutralization equivalent is added with an amount necessary for neutralization of the inorganic acid. The amount specified here does not include water-soluble solid alkaline inorganic materials derived from spray-dried particles.

  Moreover, the average particle diameter of the water-soluble solid alkali inorganic substance is not particularly limited. However, when the surfactant is highly blended, it may be pulverized to 1 to 50 μm from the viewpoint of improving the yield. The average particle size of the water-soluble solid alkali inorganic substance is calculated on a volume basis, and is measured using, for example, a laser diffraction particle size distribution analyzer: LA-920 (manufactured by Horiba, Ltd.). Value.

2. Water-soluble inorganic salt The water-soluble inorganic salt is preferably used as a powder raw material for detergents in order to increase the ionic strength of the washing liquid and improve the effects of sebum stain cleaning. As the water-soluble inorganic salt, for example, sodium sulfate, sodium chloride, sodium sulfite and potassium sulfate having a high degree of ionic dissociation are preferable. From the viewpoint of improving the dissolution rate, the combined use of magnesium sulfate is also effective.

  The average particle size of the water-soluble inorganic salt is not particularly limited, but when an anionic surfactant is highly blended, it may be pulverized to 1 to 50 μm from the viewpoint of improving the yield of detergent particles. . In addition, the average particle diameter of the water-soluble inorganic salt is calculated on a volume basis, and is, for example, a value measured using a laser diffraction particle size distribution analyzer: LA-920 (manufactured by Horiba, Ltd.). is there.

  As the powder raw material for detergent, among the water-soluble solid alkali inorganic substance and the water-soluble inorganic salt, the exemplified raw materials may be used alone, or two or more kinds may be mixed and used. The amount of the water-soluble solid alkali inorganic substance and the water-soluble inorganic salt in the particles (B) is preferably 30% by mass to 88% by mass, and preferably 35% by mass from the viewpoint of detergency and powdering of the particles (B). 85 mass% is more preferable, and 40 mass%-80 mass% is still more preferable.

[Other powder components]
You may add together the well-known substance generally used in the field | area of a detergent composition other than "the powder raw material for detergents" to a container rotation type mixer. The amount of the other powder component in the particles (B) is preferably 0.2 to 30% by mass, and more preferably 0.3 to 25% by mass. The amount specified here does not include powder components derived from spray-dried particles.

  Such materials include surface modifiers (aluminosilicate, sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, crystalline silicate, primary particles having an average particle size of 0. .1-10 μm metal soap, powdered surfactant (eg, alkyl sulfate), water-soluble organic salt, etc., chelating agent (tripolyphosphate, orthophosphate, pyrophosphate, etc., crystalline or non-crystalline Alkali metal aluminosilicate), water-soluble polymer powder (carboxylic acid polymer, carboxymethylcellulose, soluble starch, sugar, polyethylene glycol), water-insoluble excipient (silicon dioxide, hydrated silicate compound, bar) In addition to those that can be used as components of spray-dried particles, such as clay compounds such as light and bentonite) Surface active agents (fatty acid or salt thereof, linear alkylbenzene sulfonates, alkyl sulfates, etc.).

  The above substances may be added together with the powder raw material for detergent before adding Component C, or may be added after adding Component C. When adding a surface modifier such as an alkali metal aluminosilicate, it is possible to improve fluidity and storage stability by using after adding Component C. It is preferable to add.

  The operation of adding other powder components may be performed in a container rotary mixer, or after discharging the particles (B) obtained in the step (B) from the container rotary mixer, another mixer / manufacturer is prepared. You may carry out using a granulator.

[Other liquid components]
In the present invention, other liquid components may be added to produce the detergent particle group. Other liquid components to be added can be appropriately selected according to the composition of the detergent particle group to be obtained. The addition timing of the liquid component is not particularly limited. For example, the liquid component may be mixed with the component C in advance, or may be performed before, during or after the addition of the component C. When performing, it is preferable before the addition of the surface modifier.

  When the liquid component is added after component C is added, the liquid component may be added using a container rotary mixer, or the detergent particles obtained by the production method of the present invention are removed from the container rotary mixer. After discharging, the obtained detergent particles may be charged into another mixer / granulator and the liquid component added thereto.

  As a liquid component, as a surfactant, for example, a nonionic surfactant, a fatty acid, a water-soluble polymer (carboxylic acid polymer, carboxymethyl cellulose, soluble starch, saccharides, polyethylene glycol, etc.) and the like are used in ordinary detergent compositions. Any liquid component may be mentioned. As the liquid component, only one component may be used, or two or more components may be used in combination. The liquid component may be added as a liquid at a temperature equal to or higher than its melting point, or may be added in the form of an aqueous solution or dispersion. The amount of the net liquid component excluding the medium is preferably 15% by mass or less, and more preferably 10% by mass or less of the detergent particle group as the final product, from the viewpoint of suppressing aggregation of the detergent particle group.

  Although it does not specifically limit as a nonionic surfactant used as a liquid component, From a viewpoint of detergency, for example, polyoxyalkylene alkyl which added 6-22 mol of alkylene oxides to C10-14 alcohol Ether is preferred.

  As a method for adding these liquid components, spraying can be performed with any nozzle, not depending on the multi-fluid nozzle described in the present invention.

[Rotating container mixer]
As the container rotating mixer, a drum mixer or a pan mixer is preferable. The drum-type mixer is not particularly limited as long as the drum-shaped cylinder rotates and performs processing. In addition to the drum-type mixer that is horizontally or slightly inclined, the conical drum-type granulator is used. (Mixer), multi-stage conical drum granulator (mixer), etc. can also be used. These apparatuses can be used in both batch and continuous processes.

  If the coefficient of wall friction between the detergent particle group and the inner wall of the container rotating mixer is small and it is difficult to apply sufficient lifting force to the detergent particle group, a plurality of baffle plates (baffles ( ) May be attached. This makes it possible to cause the particle group to perform an upward movement, and improves the powder mixing property and the solid-liquid mixing property.

  The operating condition of the container rotating mixer is not particularly limited as long as the components in the mixer can be stirred, but the operating condition in which the fluid number defined by the following formula is 0.005 to 1.0 is used. Preferably, the operating condition is 0.01 to 0.6.

Fluid number: Fr = V ² / (R × g)
V: Circumferential speed [m / s]
R: Radius from the center of rotation to the circumference of the rotating object [m]
g: Gravity acceleration [m / s ² ]

[Multi-fluid nozzle]
In the present invention, it is one feature that the component C is supplied using a multi-fluid nozzle. By using such a nozzle, the droplets can be made fine and dispersed. A multi-fluid nozzle is a nozzle that mixes and atomizes a liquid and atomizing gas (air, nitrogen, etc.) through an independent channel to the vicinity of the nozzle tip. A four-fluid nozzle or the like can be used. Further, the type of the mixing part of the component C and the atomizing gas may be either an internal mixing type for mixing inside the nozzle tip or an external mixing type for mixing outside the nozzle tip.

  As such a multi-fluid nozzle, an internal mixed type two-fluid nozzle such as manufactured by Spraying Systems Japan Co., Ltd., manufactured by Kyoritsu Alloy Manufacturing Co., Ltd., or manufactured by Ikeuchi Co., Ltd., manufactured by Spraying Systems Japan Co., Ltd. And an external mixing type two-fluid nozzle manufactured by Kyoritsu Alloy Mfg. Co., Ltd. and Atmax Co., Ltd., an external mixing type four-fluid nozzle manufactured by Fujisaki Electric Co., Ltd., and the like.

  The droplet diameter of the component C droplet can be adjusted by changing the balance between the flow rate and the atomization gas flow rate. That is, as the flow rate of the atomizing gas is increased with respect to the component C having a certain flow rate, the droplet diameter becomes smaller. Furthermore, the droplet diameter becomes smaller as the flow rate of the component C is decreased with respect to the atomizing gas having a certain flow rate.

  For example, when a two-fluid nozzle is used, for example, it is preferable to supply the component C under the following conditions. The flow rate of the atomizing gas can be easily adjusted by adjusting the atomizing gas spray pressure. From the viewpoint of liquid dispersion, the atomizing gas atomizing pressure [gauge pressure] is 0.1 MPa or more. Preferably, 1.0 MPa or less is preferable from the viewpoint of equipment load. Moreover, there is no restriction | limiting in particular as the spraying pressure [gauge pressure] of the component C, but 1.0 MPa or less is preferable from a viewpoint of equipment load, for example.

  As a result of intensive studies on the influence of the difference in droplet size on the yield and the amount of coarse particles obtained, the average particle size of the component C droplet size is 1 to 300 μm. From the viewpoint, it is preferably 1 to 200 μm, and more preferably 1 to 150 μm.

  In addition, when it is desired to increase the addition speed of the component C, it is also effective to use a plurality of these multi-fluid nozzles and increase the addition speed while maintaining finer droplets.

  By using such a method, even an anionic surfactant that is a high-viscosity paste can be uniformly dispersed, and the yield is improved and a detergent particle group having a sharp particle size distribution can be obtained.

  In addition, the average particle diameter of the droplet diameter of the component C is calculated on a volume basis, and is a value measured using a laser diffraction particle size distribution measuring apparatus: Spray Tech (manufactured by Malvern).

  Since component C is added through the multi-fluid nozzle, it is supplied to the multi-fluid nozzle as a fluid. The anionic surfactant and / or the acid precursor thereof may be supplied as they are if they are liquid or paste at room temperature, may be diluted with water or the like to be liquid or paste, and heated to be liquid or paste It is good. Therefore, the temperature range at the time of supplying the component C to the nozzle (that is, at the time of addition into the mixer) is preferably 10 to 80 ° C. and more preferably 20 to 70 ° C. from the viewpoint of stability and handling properties.

<Process (C)>
Step (C) is a step of mixing particles (A) and particles (B). 20-70 mass% of the total mass of particle | grains (A) and particle | grains (B) is preferable, and, as for the compounding quantity of particle | grain (A), 20-60 mass% is more preferable.

  In this step, in addition to the particles (A) and the particles (B), components such as a surface modifier, an enzyme, a fragrance, a bleaching agent, and a pigment may be added and mixed. Examples of the surface modifier include those described in the item [Other powder components]. As addition amount of these components, 0.1-30 mass parts is preferable with respect to 100 mass parts of total mass of particle | grains (A) and particle | grains (B) from a viewpoint of exhibiting the desired effect by addition, 0.2-20 mass parts is more preferable, 0.3-10 mass parts is further more preferable, and 0.5-5 mass parts is still more preferable.

  The mixing in the step (C) may be performed using a known mixer. As a suitable mixer in this case, a mixer which is difficult to be compacted against detergent particles is preferable, and examples thereof include a rotary kiln, a ribbon mixer, a drum mixer, a planetary mixer, and the like.

  A smaller difference in bulk density between the particles (A) and the particles (B) is preferable from the viewpoint of suppressing classification. For example, the value obtained by dividing the bulk density of the particles (B) by the bulk density of the particles (A) is preferably 0.5 to 3.5 or less, more preferably in the range of 0.7 to 3.0, 0 A range of .8 to 2.5 is more preferable.

  Thus, according to the method for producing a detergent particle group of the present invention, by mixing (A) particles and (B) particles, fluidity that can be produced at a low spray-dried particle ratio is good and classification is suppressed. In addition, a medium and low bulk density detergent particle group can be obtained with a high yield and a low coarse particle ratio.

B. Physical properties and evaluation Examples of physical properties of the detergent particles obtained by the present invention include bulk density, average particle size, fluidity, angle of repose, granulation yield, and coarse particle ratio. The bulk density of the detergent particles is preferably a medium to low bulk density of 250 to 600 g / L, more preferably 300 to 550 g / L, and still more preferably 300 to 500 g / L. As an average particle diameter of a detergent particle group, 200-800 micrometers is preferable and 200-600 micrometers is more preferable. From the viewpoint of appearance and solubility, the average particle size is preferably 800 μm or less. The fluidity of the detergent particles is preferably 4 to 12 seconds, more preferably 4 to 10 seconds, and still more preferably 4 to 8 seconds. In addition, the angle of repose is preferably 20 ° to 45 ° from the viewpoint of easy filling of the product. The granulation yield of the detergent particle group is preferably 90 to 100%, more preferably 95 to 100%. The coarse particle ratio of the detergent particle group is preferably 25% or less, more preferably 20% or less, still more preferably 15% or less, and particularly preferably 10% or less from the viewpoint of appearance and solubility. The measuring method of these physical properties about each particle | grain, detergent particle group, etc. is as explaining below.

<Method of measuring physical properties>
1. Bulk density The bulk density is measured by a method defined by JIS K 3362. The bulk density is measured with the remaining particles obtained by cutting the particles remaining on the 2000 μm sieve.

2. About average particle diameter About an average particle diameter, it vibrates for 5 minutes using the standard sieve (mesh 2000-45 micrometers) of JISZ8801, and calculates a median diameter from the mass fraction by the size of a sieve mesh. More specifically, using a 12-stage sieve having a mesh size of 45 μm, 63 μm, 90 μm, 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1410 μm, and 2000 μm, a small sieve with a mesh on the saucer. Stack in order, add 100 g of particles from the top of the top 2000 μm sieve, cover and attach to a low-tap sieve shaker (made by HEIKO, tapping 156 times / minute, rolling: 290 times / minute) After vibrating for 5 minutes, the mass of the particles remaining on each sieve and the saucer is measured, and the mass ratio (%) of the particles on each sieve is calculated. The average particle size is obtained by accumulating the mass ratios of the particles on the sieve having a small mesh size in order from the saucer to give a total of 50%.

3. Flowability The flow time is defined as the time required for 100 mL of powder to flow out from the bulk density measurement hopper defined by JIS K 3362. In addition, fluidity | liquidity is measured with the remaining particle | grains which cut | disconnected the particle | grains which remained on the 2000 micrometer sieve.

4). Angle of repose A cylinder having an inner diameter of 77 mm and a height of 55 mm is placed on a fluidity measurement table (80 mm diameter circular platform) installed on a flat place, and a sample is poured from the upper surface of the cylinder at a height of 1 to 2 cm above. Fill from the upper surface of the cylinder to a position of 0 to 1 cm in a pile shape. The cylinder is then gently moved upwards and removed, and the filled sample is naturally discharged by gravity. Thereafter, an angle (inclination angle) between the surface of the sample remaining on the approximate measurement table and the horizontal plane is read using a protractor, and the angle is defined as an angle of repose.

5. Granulation yield The granulation yield in this invention shows the ratio (mass) of the particle | grains of 2000 micrometers or less in the manufactured detergent particle group. In addition, the mass of the particles of 2000 μm or less is the above-mentioned 2. The measurement was performed using the same apparatus as used for the average particle diameter. The granulation yield of the particles (B) is also determined by the same method.

6). Coarse Grain Ratio The coarse grain ratio in the present invention indicates the ratio (mass) of particles of 1000 μm or more in the manufactured detergent particle group. The mass of the particles of 1000 μm or more is the above 2. The measurement was performed using the same apparatus as used for the average particle diameter. The coarse particle ratio of the particles (B) is also obtained by the same method.

  Hereinafter, the present invention will be described in more detail based on examples. However, the present invention is not limited to such examples.

In the following preparation examples and the like, the following raw materials were used unless otherwise specified. In Tables 1 and 2,% of the composition means mass%, and the numerical values of particles (A), particles (B) and zeolite in Tables 3 and 4 mean parts by mass.
Linear alkylbenzene sulfonic acid, “Neopelex GS” manufactured by Kao Corporation
Sodium alkyl sulfate (pure content 65%, balance water; carbon number of alkyl group is C12 / C14 / C16 = 64/24/12 (% by weight))

Light ash (sodium carbonate), average particle size 100 μm, manufactured by Central Glass Co., Ltd. Ground light ash: Average particle size 8 μm (obtained from the above light ash)
Sodium sulfate (sodium sulfate): average particle size 200μm, “Neutral anhydrous sodium sulfate” manufactured by Shikoku Chemicals Co., Ltd.
Crushed mirabilite, average particle size 14μm (crushed mirabilite)
Zeolite: Average particle size 3.5 μm, manufactured by Zeo Builders Fluorescent dye: “AMS-GX” manufactured by Ciba Specialty Chemicals Co., Ltd.
Sodium silicate: “No. 2 silicate” manufactured by Fuji Chemical Co., Ltd. (40% pure)
Sodium polyacrylate: weight average molecular weight 10,000 (pure content 40%) (manufactured by Kao Corporation)
Polyethylene glycol: having a mass average molecular weight of 13,000 (pure content 60%) (manufactured by Kao Corporation)

  In the following preparation examples and the like, a 122 L drum mixer (φ50 cm × L62 cm) having a baffle plate was used as a container rotating mixer. As the multi-fluid nozzle, a two-fluid nozzle (manufactured by Atmax Co., Ltd .: model number BN160) was used. The value described as the spray pressure of the two-fluid nozzle is the gauge pressure.

<Preparation Example of Particle (A)>
(A-1)
After adding 239.7 kg of water at a temperature of 25 ° C. and 47.8 kg of a 48 mass% sodium hydroxide aqueous solution in this order to a 1 m ³ mixing tank having a stirring blade set at 60 ° C., 171.9 kg of linear alkylbenzene sulfone was added. Acid was added. After stirring for 5 minutes, 59.7 kg of sodium polyacrylate was added. After stirring for 2 minutes, 223.1 kg of sodium sulfate, 1.2 kg of fluorescent dye, 194.0 kg of sodium silicate, 3.0 kg of polyethylene glycol, and 59.7 kg of zeolite were added, followed by stirring for 120 minutes to obtain a slurry. The water content in this slurry was 43% by mass.

  The slurry was sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the spray drying tower to obtain spray-dried particles. The hot gas supplied to the spray-drying tower was supplied at a temperature of 220 ° C. from the bottom of the tower and discharged at 110 ° C. from the top of the tower. The obtained spray-dried particles are designated as spray-dried particles (A-1), and their compositions and physical properties are shown in Table 1.

(A-2)
Spray-dried particles (A-2) were obtained in the same manner as (A-1) except that the amount of water and the like added to the mixing tank was changed and silicate was not added. The composition and physical properties of (A-2) are shown in Table 1.

(A-3)
Spray-dried particles (A-3) were obtained in the same manner as (A-1) except that the amount of water and the like added to the mixing tank was changed and that zeolite and silicate were not added. Table 1 shows the composition and physical properties of (A-3).

(A-4)
Sprayed in the same manner as in (A-1), except that the amount of water added to the mixing tank was changed, and paste-like (60 ° C.) sodium alkyl sulfate was added as an anionic surfactant. Dry particles (A-4) were obtained. The addition of sodium alkyl sulfate was performed after the addition of sodium polyacrylate. Table 1 shows the composition and physical properties of (A-4).

(A-5)
Spray-dried particles (A-5) were obtained in the same manner as (A-1) except that the amount of water and the like added to the mixing tank was changed and silicate was not added. Table 1 shows the composition and physical properties of (A-5).

<Preparation Example of Particle (B)>
As sodium carbonate, light ash was used in (B-4) and (B-9), and pulverized light ash was used in the preparation of the other particles (B). As sodium sulfate, mirabilite was used only for (B-4), and pulverized mirabilite was used for (B-6), (B-7), and (B-8).

(B-1)
11.4 kg of sodium carbonate (10.2 times the neutralization equivalent) was added to the drum mixer, stirred for 30 seconds at a fluid number of 0.2, and then 5.6 kg of liquid linear alkylbenzene sulfonic acid at 60 ° C. Using two two-fluid nozzles, the mixture was added under spray conditions of an addition rate of 0.67 kg / min and an atomization air spray pressure of 0.3 MPa, and the mixture was stirred for 1 minute after the addition. Thereafter, stirring was stopped, 1.3 kg of zeolite was added, and stirring was performed for 1 minute under the same conditions as described above, to obtain particles (B-1) as a granulated product. Table 2 shows the composition and physical properties of the obtained particles.

(B-2) and (B-3)
Particles were obtained by the same method as (B-1) except that the amount of raw material added to the drum mixer and the amount of anionic surfactant to be sprayed were changed. Table 2 shows the composition and physical properties of the obtained particles (B-2) and (B-3).

(B-4)
The amount of the raw material added to the drum mixer and the amount of the anionic surfactant to be sprayed were changed. From the acid precursor of the anionic surfactant, the anionic surfactant paste form (60 ° C.) Particles were obtained in the same manner as in (B-1) except that sodium alkyl sulfate was changed and sodium sulfate was added. Table 2 shows the composition and physical properties of the obtained particles (B-4).

(B-5)
Particles were obtained in the same manner as (B-4) except that sodium sulfate was not added. Table 2 shows the composition and physical properties of the obtained particles (B-5).

(B-6)
Particles were obtained by the same method as (B-1) except that the amount of raw material added to the drum mixer and the amount of anionic surfactant to be sprayed were changed and sodium sulfate was added. Table 2 shows the composition and physical properties of the obtained particles (B-6).

(B-7)
1.6 kg of sodium carbonate and 1.4 kg of sodium sulfate in a Redige mixer (manufactured by Matsubo Co., Ltd., capacity 20 L, with jacket) under conditions of a stirring blade speed of 80 r / m and a shearing machine speed of 3600 r / m Stir for 2 seconds. In addition, 40 degreeC warm water was poured through the jacket at 10 L / min. 1.4 kg of liquid alkylbenzenesulfonic acid at 60 ° C. was added at an addition rate of 0.7 kg / min, and stirred for 1 minute after the addition. Thereafter, stirring was stopped, 0.023 kg of zeolite was added, and stirring was performed for 2 minutes under the same conditions as described above, and the obtained detergent particles were discharged from the mixer to obtain particles (B-7). Table 2 shows the composition and physical properties of the obtained particles.

(B-8)
Particles were obtained by the same method as (B-7) except that the amount of zeolite added was changed. Table 2 shows the composition and physical properties of the obtained particles (B-8).

(B-9)
5.4 kg of sodium carbonate was added to a drum type mixer (75 L drum type mixer (φ40 cm × L60 cm) with baffle plate), stirred for 30 seconds at a fluid number of 0.2, and then liquid alkylbenzene sulfone at 60 ° C. 1.7 kg of acid was added using one fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd.) under spray conditions of an addition rate of 0.63 kg / min and a binder spray pressure of 0.2 MPa. Stir for minutes. Thereafter, stirring was stopped, 0.35 kg of zeolite was added, and stirring was performed for 1 minute under the same conditions as described above to obtain particles (B-9) as a granulated product. Table 2 shows the composition and physical properties of the obtained particles.

<Examples 1-14, Comparative Examples 1-5>
Each (A) particle | grain, (B) particle | grains, and zeolite which were obtained as mentioned above were added to the plastic bag in the mass ratio as shown in Table 3 and Table 4. The plastic bag was shaken up and down 30 times to mix the particles to obtain detergent particles. Tables 3 and 4 show the physical properties of the obtained detergent particles.

  The detergent particle groups obtained in Examples 1 to 14 have a spray-dried particle ratio in the range of 20 to 70%, good fluidity, and a medium and low bulk density detergent particle having a bulk density of 350 to 600 g / L. It turned out to be a group. (B) Particles (B-1) to (B-6) have a bulk density of 470 to 600 g / L and medium bulk density, and (A) there is little difference in bulk density from the particles. Even if A) particles and (B) particles are mixed, classification during transportation or the like is suppressed. Furthermore, the granulation yield of the obtained detergent particle group was as high as 90% or more, and the coarse particle ratio was as low as 20% or less.

  On the other hand, about Comparative Examples 1-3, since fluidity | liquidity is very bad and the angle of repose is large, the operation which inject | pours the detergent particle group as a product into a container is difficult, and it is also inferior to the handling property of the consumer at the time of use Met. Further, it was found that each of Comparative Examples 1 to 3 had a bulk density of 77 g / L or more higher than that of the detergent particle group of Example when the spray-dried particle ratio was the same as that of Example (Example 12). To 14, Comparative Examples 1 to 3). Therefore, in order to obtain a detergent particle group having the same bulk density as that of the detergent particle group produced according to the present invention, it is necessary to increase the spray-dried particle ratio, which increases the environmental load. Moreover, regarding the granulation yield and the coarse particle ratio of the detergent particles, the performance was lower than that obtained by the production method of the present invention.

  About the comparative example 4, although fluidity | liquidity and a repose angle are favorable, since the difference of the bulk density of (A) particle | grains and (B) particle | grains is large, it is estimated that classification will arise. The reason why the bulk density of the particles (B-8) is high is that the shear force exerted by the Redige mixer on the object to be mixed is strong, so that the particles are consolidated together with the granulation, and further in the particles (B-8) It is presumed that the increase in the amount of zeolite to be added improved the fluidity and increased the particle filling rate. Moreover, regarding the granulation yield and the coarse particle ratio of the detergent particles, the performance was lower than that obtained by the production method of the present invention.

  Also in Comparative Example 5, although the fluidity and the angle of repose are good, the difference in the bulk density between the particles (B) and the particles (A) is large because one fluid nozzle was used for producing the particles (B-9). It is expected that classification will occur. Moreover, regarding the granulation yield and the coarse particle ratio of the detergent particles, the performance was lower than that obtained by the production method of the present invention.

  According to the present invention, it is possible to produce a medium and low bulk density detergent particle group with good flowability and a low coarse particle ratio while reducing the spray-dried particle ratio. Such a detergent particle group can be preferably used as a detergent composition for various uses such as clothing, or as one component of such a detergent composition.

Claims (4)

Step (A): a step of spray-drying a slurry containing an anionic surfactant to prepare particles (A) containing 5 to 40% by mass of the anionic surfactant in the particles,
Step (B): A step of preparing particles (B) by granulating a powder raw material for detergent using a container rotary mixer, wherein an anionic surfactant and / or a precursor thereof are mixed with a multi-fluid. A step of preparing particles (B) by adding them into the container rotary mixer using a nozzle, and a step (C): a step of mixing the particles (A) and the particles (B),
A method for producing a detergent particle group.   The manufacturing method of Claim 1 whose compounding quantity of particle | grains (A) is 20-70 mass% of the total mass of particle | grains (A) and particle | grains (B).   The anionic surfactant used in the step (B) and / or its precursor is composed of linear alkylbenzene sulfonic acid, alkyl sulfuric acid, polyoxyethylene alkyl sulfuric acid, α-olefin sulfonic acid, fatty acid ester sulfonic acid and salts thereof. The manufacturing method of Claim 1 or 2 which is 1 or more types selected from the group which consists of.   The manufacturing method according to claim 1, wherein the multi-fluid nozzle is a two-fluid nozzle.