JP2011127104A - Method for producing detergent granules - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing detergent granules, comprising a step for dry neutralization of an acid precursor with an alkali powder material, where the particle size distribution is sharp, and the detergent granules exhibiting excellent solubility can be obtained at a high yield. <P>SOLUTION: The method for producing the detergent granules, comprises the step for dry neutralization of the acid precursor of a non-soap anionic surfactant with the alkali powder material wherein, a vessel-rotating mixer is used at the dry neutralization, and the acid precursor having an average droplet diameter of ≤200 μm is supplied thereto. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing detergent particles using a container rotating mixer.

  Many detergent compositions based on non-soap anionic surfactants such as alkyl benzene sulfonates have been produced. As a method for producing a detergent particle group which is one of the components constituting such a detergent composition, an acid precursor of the non-soap anionic surfactant is added instead of directly adding a surfactant, There is a method of dry neutralization with a water-soluble solid alkaline inorganic material such as sodium carbonate in situ (in this specification, "acid precursor of a non-soap anionic surfactant" is referred to as "acid precursor" May be described).

  For example, in a high speed mixer / granulator, after dry neutralization at a temperature of 55 ° C. or less, a method for producing a detergent composition granulated by adding a liquid binder (Patent Document 1), in a high speed mixer / granulator, 55 A method for producing a detergent composition that is granulated by adding a liquid binder after dry neutralization at a temperature of ℃ or higher (Patent Document 2), followed by dry neutralization with a continuous high-speed mixer, followed by high bulk density with a medium-speed mixer, followed by cooling And / or the manufacturing method (patent document 3) of the detergent composition granulated by drying is disclosed.

  However, when a detergent particle group is produced using these methods, the particles tend to aggregate / coarse due to the stickiness of the non-soap anionic surfactant produced by neutralization. In order to suppress the occurrence of such a phenomenon, it is necessary to operate the stirring mechanism for mixing and the cutting mechanism for crushing / dispersing at a high speed so as to maintain the particles. In this case, it is possible to produce detergent particles having a desired small particle size by optimizing the stirring / cutting conditions, but it is difficult to obtain a good yield, and the particle size distribution of the obtained particle group Will also be broad. In addition, regarding the solubility, in the conventional method as described above, there are relatively many agglomerated particles of the starting material generated by using the non-soap anionic surfactant as a binder. Therefore, it is not easy to improve the solubility.

  As described above, the method by dry neutralization is a method suitable for easily producing a detergent particle group mainly composed of an anionic surfactant, but it is possible to granulate while agglomerating raw materials. Basic. In such a method, when the anionic surfactant is blended in a high amount, due to its strong binder force, aggregation proceeds, making it difficult to reduce the particle size and reducing the granulation yield. Even if a relatively small particle size range is obtained by crushing, it is difficult to obtain a detergent particle group having a sharp particle size distribution and excellent solubility in high yield.

  On the other hand, Patent Document 4 describes a method for producing a granular material by distributing a liquid component between a mixer / granulator and a fluid bed granulator. As an example, a continuous free-fall mixer ( In a drum with a baffle), an example is disclosed in which alkylbenzene sulfonic acid is dry-neutralized with sodium carbonate or the like. Although this method uses a continuous free-fall mixer, the aggregates are not crushed and the shearing force applied to the particles is suppressed, but the type of nozzle and spray droplet diameter when spraying alkylbenzenesulfonic acid are suppressed. There is no suggestion about the problem, and problems remain regarding sharpening of the particle size distribution, yield, and solubility.

JP-A-3-33199 JP-A-4-363398 JP-A-3-146599 Special table 2007-531803 gazette

  Accordingly, an object of the present invention is a method for producing a detergent particle group comprising a step of dry neutralizing an acid precursor with an alkaline powder raw material, and the detergent particle group having a sharp particle size distribution and excellent solubility is collected. It is to provide a production method that can be obtained efficiently.

  That is, the gist of the present invention is a method for producing a detergent particle group including a step of dry neutralizing an acid precursor of a non-soap anionic surfactant with an alkaline powder raw material. The present invention relates to a method for producing a detergent particle group, characterized in that a mixer is used and the acid precursor is supplied with an average droplet diameter of 200 μm or less.

  By the method for producing the detergent particle group of the present invention, the effect is obtained that the detergent particle group having a sharp particle size distribution and excellent solubility can be obtained with high yield.

  The method for producing a detergent particle group of the present invention is a method for producing a detergent particle group comprising a step of dry neutralizing an acid precursor of a non-soap anionic surfactant with an alkaline powder raw material. One feature is that the acid precursor is supplied using a multi-fluid nozzle using a container rotating mixer.

  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, when granulation is performed using such a mixer, since the granulation does not proceed unless the liquid component to be supplied comes in contact with the powder, the adhesiveness is in contact with the powder. Must be expressed. Generally, an acid precursor of a non-soap anionic surfactant exhibits adhesiveness when it is dry-neutralized by contact with an alkaline powder raw material. Such an acid precursor is used in a container-rotating mixer. In addition, when supplying with a one-fluid nozzle or pipe which is a general supply method, it is difficult to uniformly disperse the supplied liquid component in the mixer, and coarse particles are likely to be formed due to large liquid mass generated locally. I understood.

  Therefore, when the acid precursor that expresses tackiness when sprayed with a powder using a multi-fluid nozzle such as a two-fluid nozzle is sprayed and supplied into the container rotary mixer, it is surprisingly coarse. It was found that uniform granulation was possible while suppressing the formation of particles. This is presumably because high dispersion can be achieved by making the acid precursor into fine droplets in advance using a multi-fluid nozzle, and a large liquid mass forming coarse particles is not generated. Therefore, it is also one of the features of the present invention that the acid precursor that exhibits adhesiveness when it comes into contact with the powder is added to the container rotating mixer using a multi-fluid nozzle.

  In this way, by deliberately adopting the combination of a container rotation type mixer and a multi-fluid nozzle, it is possible to collect detergent particles that have a sharp particle size distribution and excellent solubility that cannot be expected from the case of using each independently. The effect that it can manufacture efficiently is produced.

  As a hypothesis of the mechanism by which particles with sharp particle size distribution can be obtained in high yield, by using a container rotating mixer, uniform particles with reduced shearing force applied to the powder can be obtained, and It is considered that this is due to a synergistic effect that the droplets are finely dispersed and highly dispersed by the multi-fluid nozzle, and thus aggregation caused by the stickiness of the non-soap anionic surfactant produced by dry neutralization can be suppressed.

  Furthermore, the hypothesis of the mechanism for improving the solubility is that voids are generated in the particles by a non-consolidated granulation method using a dissolving rotary mixer, and droplets are made finer and highly dispersed by a multi-fluid nozzle. Therefore, it is thought to be due to a synergistic effect of suppressing the formation of a continuous layer of surfactant in the particles.

  As an aspect of dry neutralization in the production method of the present invention, a container rotating type mixer is used, and the acid precursor is sprayed using a multi-fluid nozzle to be supplied to the alkaline powder raw material in the mixer and further mixed. There is no particular limitation as long as dry neutralization is achieved by stirring (mixing) the components in the machine. Hereinafter, the aspect as an example of the manufacturing method of this invention is demonstrated in detail.

A. Method for producing detergent particles (1) Acid precursor of non-soap anionic surfactant The acid precursor of non-soap anionic surfactant is a precursor of non-soap anionic surfactant, An acid form, which is liquid at room temperature, forms a salt by a neutralization reaction. Therefore, the acid precursor is not particularly limited as long as it is a precursor of a known non-soap anionic surfactant and has the above-mentioned properties, but linear alkylbenzene sulfonic acid (LAS), α-olefin sulfone Examples include acid (AOS), alkyl sulfuric acid (AS), internal olefin sulfonic acid, fatty acid ester sulfonic acid, alkyl ether sulfuric acid, and dialkyl sulfosuccinic acid. Such an acid precursor may use only one component, and may use it in combination of 2 or more components. Among these, linear alkylbenzene sulfonic acid (LAS) is preferable 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.

  The amount of the non-soap anionic surfactant in the obtained detergent particle group is preferably 10 to 45% by weight, preferably 13 to 35% by weight in the detergent particle group from the viewpoints of detergency and granulation properties. Is more preferable.

  Although the temperature of the acid precursor at the time of supply is not specifically limited, For example, 10-80 degreeC is preferable from a stability viewpoint of an acid precursor, and 20-70 degreeC is more preferable.

(2) Alkaline powder raw material Examples of the alkaline powder raw material include those usually used as alkaline agents in detergent compositions, such as sodium carbonate, sodium hydrogen carbonate, sodium silicate, potassium carbonate, calcium carbonate and the like. . These may be used alone or in combination of two or more. Among alkaline powder raw materials, sodium carbonate is mentioned as a preferred embodiment.

  From the viewpoint of granulation, the average particle size of the alkaline powder raw material is preferably 1 to 500 μm, more preferably 3 to 450 μm, still more preferably 5 to 350 μm, and still more preferably 5 to 250 μm.

  As the sodium carbonate, either light soda ash (light ash) or heavy soda ash (dense ash) can be used, but it is preferable to use light ash from the viewpoint of reactivity with the acid precursor. . When using dense ash, it is more preferable to use light ash having a particle size of 1 to 50 μm, which makes it possible to use detergent particles with high bulk density while maintaining reactivity with the acid precursor. Groups can be manufactured.

  The alkaline powder raw material can function as a detergent builder and an alkaline agent in the final composition. Therefore, the addition amount of the alkaline powder raw material is preferably an amount obtained by adding the alkaline powder raw material for exhibiting the above function to the amount necessary for neutralization of the acid precursor (neutralization equivalent). That is, the amount of the alkaline powder material added is preferably substantially larger than the neutralization equivalent, for example, preferably 1 to 35 times the neutralization equivalent, more preferably 2 to 30 times, still more preferably. 3 to 25 times. When an inorganic acid is used in combination with an acid precursor, the neutralization equivalent further adds an amount necessary for neutralization of the inorganic acid.

  Moreover, the average particle diameter of the alkaline powder raw material is not particularly limited, but 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 alkaline powder raw material is calculated on a volume basis, and is a value measured using, for example, a laser diffraction particle size distribution measuring device: LA-920 (manufactured by Horiba, Ltd.). is there.

(3) Container rotation type mixer As the container rotation type mixer, a drum type mixer or a pan type 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 rotary mixer is small and it is difficult to apply sufficient ascending force to the detergent particle group, a plurality of baffle plates (baffles) are formed on the container inner wall. ) 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 rotation type mixer is not particularly limited as long as the components in the mixer can be stirred, but the operating condition is that the fluid number defined by the following formula is 0.005 to 1.0. Is preferable, and the operating condition of 0.01 to 0.6 is more preferable.
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 ]

(4) Other powder components To the container rotating mixer, known substances generally used in the field of detergent compositions may be added together.

  Such materials include tripolyphosphates, crystalline or amorphous alkali metal aluminosilicates (zeolites), crystalline silicates, fluorescent agents, pigments, recontamination inhibitors (polycarboxylate polymers, sodium carboxymethylcellulose, etc.) , Particulate surfactant (fatty acid or salt thereof, linear alkylbenzene sulfonate, alkyl sulfate, etc.), spray dried powder, silica, diatomaceous earth, calcite, kaolin, bentonite, sodium sulfate, sodium sulfite, etc. . Such a substance is arbitrarily used depending on its application. In the case of adding tripolyphosphate or sodium sulfate, from the viewpoint of suppressing aggregation of the detergent particles accompanying the neutralization reaction of the acid precursor, it may be added after pulverizing in advance and reducing the average particle size. . The smaller the average particle size of tripolyphosphate and sodium sulfate, the better the yield. From the viewpoint of productivity for industrially obtaining detergent particles having a small particle size, the average particle size is preferably 1 μm or more. From the viewpoint of suppressing particle aggregation, it is preferably 50 μm or less. The average particle size of tripolyphosphate and sodium sulfate 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.

  Among the above substances, when alkali metal aluminosilicate (zeolite) is used, the content of alkali metal aluminosilicate (zeolite) in the detergent particle group improves fluidity, suppresses smudge and caking, and cleans. From the viewpoint of improving the strength, 0.1% by weight or more is preferable, 0.5% by weight or more is more preferable, 1% by weight or more is more preferable, and from the viewpoint of rinsing properties and solubility, 20% by weight or less is preferable, 15% by weight % Or less is more preferable, 10% by weight or less is more preferable, and 5% by weight or less is more preferable.

  The above substances may be added together with the alkaline powder raw material before adding the acid precursor, or may be added after adding the acid precursor, but alkali metal aluminosilicate, silica, When adding diatomaceous earth and calcite, it is possible to improve fluidity and storage stability by using these as surface modifiers. preferable.

(5) Multi-fluid nozzle In this invention, it is preferable to supply an acid precursor 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 flow path to the vicinity of the nozzle tip. A fluid nozzle or the like can be used. The mixing portion of the acid precursor and atomizing gas may be either an internal mixing type that mixes in the nozzle tip portion or an external mixing type that mixes outside the nozzle tip portion.

  As such a multi-fluid nozzle, an internal mixed type two-fluid nozzle such as made by Spraying Systems Japan Co., Ltd., Kyoritsu Alloy Manufacturing Co., Ltd., or Ikeuchi Co., Ltd., or made 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 acid precursor droplet can be adjusted by changing the balance between the flow rate of the acid precursor and the flow rate of the atomizing gas. That is, as the flow rate of the atomizing gas is increased with respect to an acid precursor having a certain flow rate, the droplet diameter becomes smaller. Furthermore, the droplet diameter becomes smaller as the flow rate of the acid precursor is decreased with respect to the atomizing gas at a certain flow rate.

  For example, when using a two-fluid nozzle, for example, it is preferable to supply the acid precursor under the following conditions. Adjustment of the atomizing gas flow rate is easy by adjusting the atomizing gas spray pressure. From the viewpoint of liquid dispersion, the atomizing gas atomizing pressure is preferably 0.1 MPa or more, and the equipment load From the viewpoint of 1.0 MPa, 1.0 MPa or less is preferable. The spray pressure of the acid precursor is not particularly limited, but is preferably 1.0 MPa or less, for example, from the viewpoint of equipment load.

  As a result of intensive studies on the influence of the difference in droplet size on the yield and coarse particle amount of the resulting detergent particles, the average particle size of the acid precursor droplet size should be 200 μm or less. From 1 to 200 μm, more preferably from 3 to 150 μm, and even more preferably from 10 to 58 μm. The smaller the droplet diameter, the more reliably the aggregation during dry neutralization can be suppressed. However, reducing the flow rate of the acid precursor increases the addition time and decreases the production capacity. Therefore, for example, by using a plurality of multi-fluid nozzles and reducing the flow rate per nozzle, it is effective to increase the addition speed while maintaining the fineness of the droplets.

  On the other hand, by setting the addition rate within a predetermined range, accumulation of unreacted acid on the particle surface is suppressed, and a high yield can be obtained due to the fine dispersion effect by the multi-fluid nozzle. Therefore, for example, the addition rate [% / min] which is a value obtained by dividing the liquid powder ratio ((weight of acid precursor / weight of charged powder) × 100) [%] by addition time [min], It is preferable to add in the range of 0.1 to 15% / min, and it is more preferable to add in the range of 0.5 to 10% / min. When the component described in (4) above is charged into the mixer, the “weight of the charged powder” includes the weight of the component. When the inorganic acid is used in combination, the weight of the acid precursor does not include the weight of the inorganic acid.

  In addition, the average particle diameter of the droplet diameter of the acid precursor is calculated on a volume basis, and is, for example, a value measured using a laser diffraction particle size distribution analyzer: Spray Tech (manufactured by Malvern). is there.

(6) Other liquid components In the present invention, a detergent particle group may be produced by further adding other liquid components. The other liquid component to be added can be appropriately selected according to the composition of the detergent particle group to be obtained, and a desired liquid component can be used. The addition timing of the liquid component is not particularly limited. For example, the liquid component may be added before, during or after the dry neutralization of the acid precursor and the alkaline powder raw material. When added, it is preferable to add the surface modifier.

  When a liquid component is added after the dry neutralization step, it may be added to the container rotary mixer used for dry neutralization, or the detergent particles obtained by the production method of the present invention may be mixed in the container rotary mixer. After discharging from the machine, it may be added using another mixer / granulator.

  Examples of the liquid component include any liquid component used in ordinary detergent compositions such as nonionic surfactants, water-soluble polymers (polyethylene glycol, sodium polyacrylate, maleic acrylate copolymer, etc.) and fatty acids. . As the liquid component, only one component may be used, or two or more components may be used in combination. As the liquid component, the component may be added as a liquid, or may be added in the form of an aqueous solution or a dispersion. The amount of the net liquid component excluding the medium is preferably 15% by weight or less, more preferably 10% by weight or less, of the final product detergent particle group 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.

B. Detergent composition and its manufacturing method A detergent composition can be manufactured by adding a desired component further to the detergent particle group manufactured as mentioned above. That is, the detergent composition of the present invention comprises a detergent particle group obtained by the production method of the present invention.

  Examples of the component to be added include enzymes, fragrances, bleaches, dyes and the like. Such components may be added to the container rotary mixer after dry neutralization, or the detergent particles obtained by the production method of the present invention are discharged from the container rotary mixer and then mixed separately. You may add using a machine.

C. Physical properties and evaluation Examples of physical properties such as detergent particles obtained by the present invention include bulk density, average particle size, and fluidity. Moreover, detergent yield is mentioned as an index of productivity. The bulk density of the detergent particle group is preferably 400 to 1000 g / L. As an average particle diameter of a detergent particle group, 200-800 micrometers is preferable, 200-600 micrometers is more preferable, 260-600 micrometers is still more preferable. The fluidity of the detergent particle group is preferably 4 to 10 seconds, and more preferably 4 to 7 seconds. The detergent yield is preferably as close to 100% as possible. For example, 80 to 100% is preferable, and 90 to 100% is more preferable.

  Furthermore, sharpness of particle size distribution and solubility are mentioned as quality evaluation items of the obtained detergent particle group.

  These physical properties and quality evaluation methods are as described below.

<Method of measuring physical properties>
1. Average particle diameter About 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 weight fraction by the size of a mesh. More specifically, using a 12-stage sieve having a mesh opening 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 tray 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 (manufactured by HEIKO, tapping 156 times / minute, rolling: 290 times / minute) After vibrating for 5 minutes, the weight of the particles remaining on each sieve and the saucer is measured, and the weight ratio (%) of the particles on each sieve is calculated. The average particle size is determined by accumulating the weight ratio of the particles on the sieve having a small mesh size in order from the saucer, and the total particle size becomes 50%.

2. 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.

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. The flow time is preferably 10 seconds or less, more preferably 8 seconds or less, and even more preferably 7 seconds or less. 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). Detergent yield The detergent yield in the present invention indicates the ratio of particles of 1410 μm or less in the manufactured detergent particle group.

<Quality evaluation method>
1. Sharpness of the particle size distribution As an index of the particle size distribution, a detergent particle group that has been passed through a 1410 μm sieve is fitted, and a Rosin-Rammler number (RR number) is calculated and used. The following formula is used to calculate the number of Rosin-Rammlers.

log (log (100 / R (Dp))) = nlog (Dp) + log (β)
R (Dp): Cumulative rate [%] of powder having a particle diameter of Dp μm or more
Dp: particle size [μm]
n: Rosin-Rammler number β: Particle size characteristic coefficient More specifically, the weight of the particles remaining on each sieve and the saucer is measured by the same method as the measurement of the average particle diameter, and each sieve (mesh size) Dp [μm]) is calculated as the weight ratio of the particles (cumulative rate R (Dp) [μm]). Then, the slope n of the least square approximation line when log (log (100 / R (Dp))) is plotted against each logDp is defined as the Rosin-Rammler number.

  The higher the Rosin-Rammler number n, the sharper the particle size distribution. n is preferably 1.5 or more, more preferably 2.0 or more, from the viewpoint of improving solubility.

2. Solubility As a solubility index in the present invention, a 60-second dissolution rate of a detergent particle group described below can be used. The dissolution rate is preferably 90% or more, and more preferably 95% or more.

The dissolution rate of the detergent particle group for 60 seconds is calculated by the following method.
1 liter of hard water (Ca / Mg molar ratio 7/3) adjusted to 20 ° C. corresponding to a hardness of 71.2 mg CaCO ₃ / liter, 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd.) Filled into a 1 liter glass beaker and kept constant at a water temperature of 20 ° C. in a water bath, a stirrer (length 35 mm, diameter 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) SA ( In the round thin type)), stirring is performed at a rotational speed (800 r / m) at which the depth of the vortex with respect to the water depth is approximately 1/3. The detergent particles, which have been reduced and weighed so as to be 1.000 ± 0.0010 g, are charged and dispersed in water with stirring, and stirring is continued. 60 seconds after charging, the detergent particle group dispersion in the beaker is filtered through a standard sieve (diameter: 100 mm) having an opening of 74 μm as defined in JIS Z 8801, which has a known weight, and the detergent particles in the water state remaining on the sieve are filtered. Collect in an open container with known weight along with sieve. The operation time from the start of filtration until the sieve is collected is 10 ± 2 seconds. The collected residue of detergent particles is dried in an electric dryer heated to 105 ° C. for 1 hour, and then cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total weight of the dissolved residue of the dried detergent, the sieve, and the collection container is measured, and the dissolution rate (%) of the detergent particle group is calculated by the equation (1).

Dissolution rate (%) = {1- (T / S)} × 100 (1)
S: input weight of detergent particles (g)
T: When the aqueous solution obtained under the above stirring conditions is subjected to the sieve, the dry weight (g) of the residue of the detergent particles remaining on the sieve

In this example, the following raw materials were used unless otherwise specified.
・ Alkaline powder raw material Light ash: Average particle size 100 μm, manufactured by Central Glass Co., Ltd. Ground light ash: Average particle size 8 μm (obtained by pulverizing the above light ash)
Dens ash: average particle size 300μm, acid precursor of non-soap anionic surfactant, manufactured by Central Glass Co., Ltd. Linear alkylbenzene sulfonic acid (LAS), “Neopelex GS” manufactured by Kao Corporation
・ Other raw materials Polyoxyethylene alkyl ether (POE), "Emulgen 121" manufactured by Kao Corporation
Zeolite: Average particle size of 3.5 μm, manufactured by Zeobuilder Co., Ltd. Pulverized salt cake: An average particle size of 200 μm pulverized to an average particle size of 10 μm

  In the following examples and the like, a 75 L drum mixer (φ40 cm × L60 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 BN90) was used.

Example 1
100 parts by weight of light ash (5.7 kg; 22 times the neutralization equivalent) was stirred in a drum mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 28.4 parts by weight of LAS at 60 ° C. was sprayed with a two-fluid nozzle under a spraying condition of an addition rate of 4.1% / min and an atomizing air spraying pressure of 0.3 MPa. Added for 3 minutes and stirred for 3 minutes after addition. Thereafter, stirring was stopped, 3.9 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer. In addition, it was 35 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 2
100 parts by weight of light ash (5.5 kg; 18 times the neutralization equivalent) was stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 35.4 parts by weight of LAS at 60 ° C. was applied with a two-fluid nozzle under a spraying condition of an addition rate of 4.3% / min and an atomization air pressure of 0.3 MPa for atomization. Added for 3 minutes and stirred for 3 minutes after addition. Thereafter, stirring was stopped, 6.8 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer. In addition, it was 35 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 3
100 parts by weight of light ash (5.5 kg; 18 times the neutralization equivalent) was stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 35.4 parts by weight of LAS at 60 ° C. was sprayed with a two-fluid nozzle under a spraying condition of an addition rate of 8.1% / min and an atomization air spray pressure of 0.44 MPa for atomization. Added for 3 minutes and stirred for 3 minutes after addition. Thereafter, stirring was stopped, 4.1 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the resulting detergent particles were discharged from the mixer. In addition, it was 46 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 4
100 parts by weight of light ash (5.5 kg; 18 times the neutralization equivalent) was stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 35.4 parts by weight of LAS at 60 ° C. was sprayed with a two-fluid nozzle under a spray condition of an addition rate of 8.1% / min and an atomization air spray pressure of 0.17 MPa. Added for 3 minutes and stirred for 3 minutes after addition. Thereafter, stirring was stopped, 4.1 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the resulting detergent particles were discharged from the mixer. In addition, it was 98 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 5
100 parts by weight of light ash (5.5 kg; 18 times the neutralization equivalent) was stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 35.4 parts by weight of LAS at 60 ° C. was sprayed with a two-fluid nozzle under a spray condition of an addition rate of 8.1% / min and an atomization air spray pressure of 0.14 MPa. Added for 3 minutes and stirred for 3 minutes after addition. Thereafter, stirring was stopped, 4.1 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions, and the resulting detergent particles were discharged from the mixer. In addition, when the spray droplet diameter (average particle diameter) of LAS under this spray condition was measured, it was 133 μm.

Example 6
100 parts by weight of pulverized light ash (4.9 kg; 12 times the neutralization equivalent) was stirred in a drum mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 54.5 parts by weight of LAS at 60 ° C. was added with a two-fluid nozzle for 11.0 minutes under a spraying condition of an addition rate of 4.9% / min and an atomization pressure of 0.3 MPa for atomization. And stirred for 3 minutes after the addition. Thereafter, stirring was stopped, 4.7 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the resulting detergent particles were discharged from the mixer. In addition, it was 35 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 7
100 parts by weight of pulverized light ash and 100 parts by weight of dense ash (5.8 kg; 24 times the neutralization equivalent) were stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 50.3 parts by weight of LAS at 60 ° C. was applied with a two-fluid nozzle for 6.3 minutes under a spraying condition of an addition rate of 4.0% / min and an air spraying pressure of 0.3 MPa for atomization. And stirred for 3 minutes after the addition. Thereafter, stirring was stopped, 5.0 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer. In addition, it was 35 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Example 8
100 parts by weight of light ash (2.4 kg; 9 times the neutralization equivalent) and 133 parts by weight of pulverized mirabilite were stirred in a drum type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 46.7 parts by weight of LAS and 4.7 parts by weight of 98% sulfuric acid were mixed in advance, and the temperature was adjusted to 60 ° C., and the addition rate was 7.2% / min with a two-fluid nozzle. It added in 2.8 minutes on the spray conditions of Air spray pressure 0.3MPa, and stirred for 2 minutes after the addition. Thereafter, 10.0 parts by weight of polyoxyethylene alkyl ether was added in 0.5 minutes, followed by stirring for 2 minutes. Thereafter, 2.3 parts by weight of sodium polyacrylate was added in 0.5 minutes and stirred for 2 minutes after the addition. Thereafter, stirring was stopped, 6.7 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer. In addition, when the spray droplet diameter (average particle diameter) of LAS under this spray condition was measured, it was 58 μm.

Example 9
100 parts by weight of light ash (1.9 kg; 7 times the neutralization equivalent) and 213 parts by weight of pulverized mirabilite were stirred in a drum type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 65.2 parts by weight of LAS and 6.5 parts by weight of 98% sulfuric acid were mixed in advance, and then the temperature was adjusted to 60 ° C., and the addition rate was 7.5% / min with a two-fluid nozzle. It added in 2.8 minutes on the spray conditions of Air spray pressure 0.3MPa, and stirred for 2 minutes after the addition. Thereafter, 8.7 parts by weight of polyoxyethylene alkyl ether was added in 0.5 minutes, followed by stirring for 2 minutes. Thereafter, 2.6 parts by weight of sodium polyacrylate was added in 0.5 minutes and stirred for 2 minutes after the addition. Thereafter, stirring was stopped, 21.7 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the resulting detergent particles were discharged from the mixer. In addition, when the spray droplet diameter (average particle diameter) of LAS under this spray condition was measured, it was 58 μm.

Comparative Example 1
100 parts by weight of light ash (5.5 kg; 18 times the neutralization equivalent) was stirred in a drum-type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 30 seconds, 35.4 parts by weight of LAS at 60 ° C. was sprayed using a one-fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd .: Model No. Unijet 8003) at an addition rate of 13.0% / min. In 2.7 minutes, and stirred for 3 minutes after the addition. Thereafter, stirring was stopped, 6.8 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer. In addition, it was 860 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Comparative Example 2
100 parts by weight of light ash (26.4 kg; 22 times the neutralization equivalent) was stirred in a Redige mixer FKM-130D (manufactured by Matsubo). After stirring for 30 seconds under the conditions of a stirring blade rotation speed of 130 r / m and a shearing machine rotation speed of 3600 r / m, 28.4 parts by weight of LAS at 60 ° C. was added to a two-fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd. SU29) was added in 7.0 minutes at an addition rate of 4.1% / min and an air spray pressure for atomization of 0.3 MPa, and the mixture was stirred for 3 minutes after the addition. Thereafter, the stirring was stopped, 6.4 parts by weight of zeolite was added, the mixture was stirred for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the Readyge mixer. In addition, it was 60 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Comparative Example 3
100 parts by weight of light ash (25.3 kg; 18 times the neutralization equivalent) was stirred in a Redige mixer FKM-130D (manufactured by Matsubo). After stirring for 30 seconds under the conditions of a stirring blade rotation speed of 130 r / m and a shearing machine rotation speed of 3600 r / m, 35.4 parts by weight of LAS at 60 ° C. was made into one fluid nozzle (manufactured by Spraying Systems Japan Co., Ltd. Unijet 8010) was added at a rate of 10.5% / min in 3.4 minutes and stirred for 3 minutes after the addition. Thereafter, the stirring was stopped, 6.8 parts by weight of zeolite was added, the mixture was stirred for 1 minute under the same conditions as described above, and the resulting detergent particle group was discharged from the Readyge mixer. In addition, it was 510 micrometers when the spraying droplet diameter (average particle diameter) of LAS in this spraying condition was measured.

Comparative Example 4
100 parts by weight (4.93 kg) of light ash was stirred in a drum type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 10 seconds, 35.2 parts by weight of polyoxyethylene lauryl ether (Emulgen 106 manufactured by Kao Corporation) at 60 ° C. was added to a two-fluid nozzle (addition rate 3.7% / min, Air spraying pressure for atomization of 0. 3 MPa) and added in 9.4 minutes. After the addition, granulation was continued by further mixing for 1 minute. Thereafter, stirring was stopped, 6.8 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the obtained detergent particles were discharged from the mixer.

Comparative Example 5
100 parts by weight (4.93 kg) of light ash was stirred in a drum type mixer (rotation speed 30 r / m, fluid number 0.2). After stirring for 10 seconds, 35.2 parts by weight of polyoxyethylene lauryl ether (Emulgen 106 manufactured by Kao Corporation) at 60 ° C. was added to a two-fluid nozzle (addition rate 3.7% / min, Air spraying pressure for atomization of 0. 3 MPa) and added in 9.4 minutes. After the addition, granulation was continued by further mixing for 1 minute. Thereafter, stirring was stopped, 40.9 parts by weight of zeolite was added, stirring was performed for 1 minute under the same conditions as described above, and the resulting detergent particles were discharged from the mixer.

  The composition, conditions, and results of the detergent particle group raw materials in the above examples and the like are shown in the following table.

  The detergent particle groups obtained in Examples 1 to 9 have a detergent yield as high as 80% or higher, the Rosin-Rammler number (RR number in the table) as an index of the particle size distribution is 1.5 or more, and the particle size It was found that particles with a sharp distribution were obtained in high yield.

  On the other hand, in Comparative Example 1, the detergent yield was as low as 67%, the Rosin-Rammler number was 1.0, and it was found that the particle size distribution of the obtained detergent particles was broadened. About Comparative Example 2, although the fall of a yield was not seen, the Rosin-Rammler number was set to 1.1, and it turned out that the particle size distribution of the obtained detergent particle group has become broad. In Comparative Example 2, many deposits on the wall surface and the stirring shaft in the mixer were observed. In Comparative Example 4, the obtained detergent particle group was a wet powder, and physical properties could not be measured. In Comparative Example 5, a detergent particle group capable of measuring physical properties was obtained by increasing the amount of zeolite as compared with Comparative Example 4, and the average particle diameter of the obtained detergent particle group was 138 μm. Since the average particle diameter of the light ash before granulation was 100 μm, granulation hardly progressed, and this is because the adhesiveness when contacting with the powder is weak.

  Regarding the solubility, from the comparison between Example 2 and Comparative Example 3, the dissolution rate of Example 2 is 97%, while the dissolution rate of Comparative Example 3 is 78%. Despite the large average particle size, the dissolution rate was excellent.

  Further, when Examples 3 to 5 were compared, the detergent yield was better in Example 3 in which the average particle diameter of the acid precursor droplet diameter was made finer.

  According to the present invention, a detergent particle group having a sharp particle size distribution and excellent solubility can be produced with high yield. 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 (5)

  A method for producing a detergent particle group comprising a step of dry neutralizing an acid precursor of a non-soap anionic surfactant with an alkaline powder raw material, and using a container rotary mixer for dry neutralization, the acid A method for producing a detergent particle group, characterized in that the precursor is supplied at an average particle diameter of 200 μm or less.   The production method according to claim 1, wherein the acid precursor of the non-soap anionic surfactant is supplied using a multi-fluid nozzle.   The manufacturing method of Claim 1 or 2 whose quantity of the alkaline powder raw material added is 1 to 35 times the neutralization equivalent of the acid precursor of a non-soap anionic surfactant.   The production method according to any one of claims 1 to 3, wherein 10 to 45% by weight of a non-soap anionic surfactant is contained in the obtained detergent particle group.   The detergent composition formed by containing the detergent particle group obtained by the manufacturing method of any one of Claims 1-4.