JP2001019998A - Production of granules for carrying surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide granules for carrying surfactant of a large supporting properties and its production process. SOLUTION: The production process for the surfactant carrier comprises the step (I) of preparing a slurry containing at least sodium carbonate aqueous soluble salt, where excluding fumaric acid and/or its salt, and preparing the slurry including fumaric acid or its salt and the step (II) of spray-drying the slurry prepared in the step (I). The slurry is prepared so that the fumaric acid and/or its salt may dissolve in water, when sodium carbonate precipitates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing particles for supporting a surfactant and the particles.

[0002]

2. Description of the Related Art As a technique for obtaining a powder capable of absorbing and retaining (supporting) a liquid surfactant, the following techniques are available.
JP-A-57-159898 discloses that specific amounts of sodium carbonate, sodium bicarbonate, water softeners such as aluminum silicate, sodium silicate, bentonite and / or
Or polyacrylate (molecular weight 1000-5000)
A particle group (beads) for supporting a surfactant comprising the same is disclosed. This is a granule whose porous surface is made porous by thermal decomposition of sodium bicarbonate during drying, and the oil absorbing ability of the nonionic surfactant is increased.However, since inorganic salts solidify and precipitate as dense aggregates, they are fine. The pore volume is reduced and the oil absorption capacity is low.

Japanese Patent Application Laid-Open No. Sho 62-112699 discloses that when a slurry containing sodium carbonate is spray-dried, a water-soluble polymer having a crystal growth regulating action is mixed with the slurry prior to sodium carbonate in the process of preparing the slurry. By doing so, a method is disclosed in which sodium carbonate monohydrate or burkeite is crystallized to form small pores to obtain dry particles having excellent oil absorbing ability (supporting ability). However, its oil absorbing ability was insufficient.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing granules for supporting a surfactant having a large supporting ability, and to provide the granules.

[0005]

Means for Solving the Problems The present invention comprises a step (i): a water-soluble salt containing at least sodium carbonate (excluding fumaric acid and / or its salt), and fumaric acid and / or its salt. A step of preparing a slurry containing a salt (hereinafter referred to as fumaric acid or the like), and a step (ii):
Spray-drying the slurry obtained in step (i), wherein fumaric acid and / or a salt thereof is used when a salt containing sodium carbonate precipitates. The present invention relates to a method for preparing surfactant-supporting granules (hereinafter referred to as granules) for preparing the slurry so as to be dissolved in water in the slurry.

[0006]

[Step (i) (step of preparing slurry)]

In the slurry, water-soluble salts containing at least sodium carbonate (however, excluding fumaric acid and / or its salt)
(C) and (D) such as fumaric acid, and further preferably a water-insoluble inorganic substance (A) and a water-soluble polymer (B). A slurry is prepared by mixing these components with water. In order to finally obtain a homogeneous slurry, after all the components are added to the slurry, the mixture is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

The content of water in the slurry is preferably 30 to 70% by weight, more preferably 35 to 60% by weight,
0-55% by weight is particularly preferred. This range is preferable because the effect of adjusting the crystals in the slurry starts to occur, and the effect of the efficient crystal adjustment is finally exhibited.

The content (based on solid content) of water-soluble salts (excluding fumaric acid and / or its salts) in the slurry is 5%.
-75% by weight is preferable, 7-55% by weight is more preferable, and 10-45% by weight is particularly preferable. The slurry contains
At least sodium carbonate is contained as a water-soluble salt. The content of sodium carbonate in the slurry is preferably from 5 to 75% by weight, more preferably from 7 to 45% by weight, and
-37% by weight is particularly preferred. It is preferably at least 5% by weight from the viewpoint of the carrying ability, and is preferably at most 75% by weight from the viewpoint of storage stability. Further, it is more preferable that the slurry further contains sodium sulfate as a water-soluble salt. The content of sodium sulfate in the slurry is preferably from 0.1 to 3.0, and more preferably from 0.4 to
2.7 is more preferable, and 0.5 to 2.5 is particularly preferable. 0.1 or more is preferable from a viewpoint of a carrying ability, and 3.0 or less is preferable from a viewpoint of washing performance.

In order for fumaric acid or the like to exhibit a more remarkable effect, it is preferable that an effective amount of fumaric acid or the like is dissolved in the slurry when the salt containing sodium carbonate is precipitated. Here, the “effective amount” such as fumaric acid means an amount that affects the crystal form of the salt containing sodium carbonate, and specifically 0.2 to 15 based on the solid content in the slurry.
% By weight, preferably 0.5 to 10% by weight, particularly preferably 1 to 8% by weight. The amount is preferably 0.2% by weight or more from the viewpoint of the amount acting on the water-soluble salts as a crystal adjustment, and is preferably 15% by weight or less from the viewpoint of cleaning performance.
The amount of fumaric acid or the like dissolved in the slurry can be determined by a chromatographic method.

Further, in the present slurry, [weight of sodium carbonate + sodium sulfate] / [weight of fumaric acid or the like]
= 0.3 to 60 is preferable, and 2 to 45 is more preferable.
4 to 25 are particularly preferred. It is preferably at least 0.3 from the viewpoint of increasing the carrying capacity of the granules, and is preferably at most 60 from the viewpoint of suppressing a decrease in the particle strength of the granules. In particular, from the viewpoint of the above-mentioned supporting ability, it is preferable to contain sodium sulfate. By adding fumaric acid or the like to the raw material slurry, when one or more selected from the group consisting of sodium carbonate, sodium sulfate and a double salt thereof are precipitated, a crystal form having a large ratio of the major axis to the minor axis (preferably Needle-like, rod-like, etc.).

Since unneutralized fumaric acid reacts with sodium carbonate, sodium carbonate may be substantially reduced when blended with fumaric acid. Therefore, it is preferable to neutralize with another alkali compound such as sodium hydroxide, mix as a fumarate, or add a large amount of sodium carbonate in an amount commensurate with the decrease. As the fumarate, sodium fumarate, disodium fumarate, potassium fumarate and dipotassium fumarate are preferred. Further, an alkaline earth metal fumarate may be used.

The content (based on solid content) of the water-insoluble inorganic substance in the slurry is preferably 20 to 90% by weight, and 30 to 75% by weight.
% By weight, more preferably 40 to 70% by weight. The content (based on solid content) of the water-soluble polymer in the slurry is preferably 2 to 20% by weight, more preferably 4 to 12% by weight, and particularly preferably 6 to 9% by weight.

[0013] The slurry may contain other components such as a surfactant, which are usually added to the detergent composition. From the viewpoint of improving the carrying ability and the drying efficiency, the slurry may contain a surfactant. The content of the other components is preferably 10% by weight or less, more preferably 1 to 10% by weight, and particularly preferably 2 to 8% by weight in the solid components of the slurry.

The viscosity of the slurry may be such that it can be sent by a pump. The slurry temperature is preferably 30 to
80 ° C, more preferably 40 to 70 ° C. It is preferable if it is within this range because handling becomes easy in terms of viscosity of the slurry.

In order to obtain a group of granules having a higher supporting ability, at the time of precipitation of a salt containing sodium carbonate, preferably, at least one selected from the group consisting of sodium carbonate and a double salt of sodium carbonate and sodium sulfate is used. A slurry may be prepared so that fumaric acid or the like is dissolved during precipitation. Specifically, fumaric acid or the like may be mixed into the slurry before or during the precipitation of these components. When sodium carbonate is precipitated, or when sodium sulfate is further contained in the slurry, when one or more selected from the group consisting of sodium carbonate and a double salt of sodium carbonate and sodium sulfate is precipitated, fumaric acid or the like is used. Is dissolved, the precipitated crystal is adjusted to a shape having a large ratio of the major axis to the minor axis (preferably a needle shape, a rod shape, or the like).
As a result, pores having a preferable pore volume are formed in the granules, and the carrying capacity of the granules is increased.

Such a salt precipitation operation can be performed during or after preparation of the slurry as long as fumaric acid and the like are dissolved in the slurry. Specific operation methods include adjusting the temperature of the slurry so that the salt is precipitated, increasing the temperature of the slurry to reduce the amount of solvent, and adding a water-soluble salt that is more soluble. Can be Examples of the water-soluble salts that are more easily dissolved include sodium chloride, sodium bromide, sodium iodide, sodium acetate, potassium carbonate, potassium chloride, magnesium chloride and the like.

Specifically, the following embodiments are exemplified. a) In the case of containing only sodium carbonate b) In the case of containing sodium carbonate and sodium sulfate In the case of a), in order to form a crystal shape (needle shape, rod shape, etc.) suitable for carrying sodium carbonate, it is necessary to dissolve once. ,
It is important to reprecipitate a slurry in which fumaric acid and the like are dissolved in an effective amount. The reprecipitation may be during or after preparation of the slurry or during spray drying. When the precipitation operation of sodium carbonate is performed during or after preparation of the slurry, sodium carbonate is positively precipitated again in the slurry, and further re-precipitated during spray drying, and fumaric acid or the like acts on sodium carbonate more efficiently. Thus, the effect of adjusting the crystal shape (adjusting the crystal shape into a rod shape, a needle shape, or the like) is efficient, which is preferable. The most preferred method of preparing a slurry is to prepare an aqueous solution such as fumaric acid, add sodium carbonate to the aqueous solution,
This is a method in which, after further adding other components, an operation of precipitating a salt is performed, and the resulting mixture is turned into a slurry.

In the slurry preparation process, the dissolution rate of sodium carbonate is 60 to 100% by weight, 80 to 100% by weight, and 90 to 100% by weight based on 100% by weight of added sodium carbonate. Is preferred. This range is preferable because the effect of the addition of fumaric acid or the like is more remarkably exhibited. Therefore, when the dissolution rate of the added sodium carbonate is low, it is preferable to increase the dissolution rate by controlling the temperature of the slurry or increasing the blending amount of water. The dissolution rate of the components constituting the granules is
It refers to the ratio of the amount dissolved to the amount added.

In the case of b) In order for at least one selected from the group consisting of sodium carbonate and a double salt of sodium carbonate and sodium sulfate to form a crystal shape (needle shape, rod shape, etc.) suitable for loading, It is important to once dissolve and reprecipitate a slurry in which fumaric acid and the like are dissolved in an effective amount. The reprecipitation may be during or after preparation of the slurry or during spray drying. During or after the preparation of the slurry, if one or more precipitation operations selected from the group consisting of sodium carbonate and a double salt of sodium carbonate and sodium sulfate are performed, the precipitate is positively re-precipitated in the slurry and further re-precipitated during spray drying. It is preferable that fumaric acid or the like precipitates and acts on sodium carbonate more efficiently, and the effect of adjusting the crystal shape becomes more efficient. The most preferred method for preparing a slurry is to prepare an aqueous solution such as fumaric acid, add sodium sulfate to the aqueous solution, further add sodium carbonate, and further add other components, and then perform a salt precipitation operation.
In this method, the obtained mixture is converted into a slurry.

In the process of preparing the slurry, the dissolution rate of sodium sulfate is 60 to 100% by weight, 80 to 100% by weight, and 90 to 100% by weight based on 100% by weight of the added sodium sulfate. Is preferred. This range is preferable because the effect of the addition of fumaric acid or the like is more remarkably exhibited. Therefore, when the dissolution rate of the added sodium sulfate is low, it is preferable to increase the dissolution rate by controlling the temperature of the slurry or increasing the blending amount of water.

The dissolution rate of sodium carbonate in the case of containing sodium sulfate changes with the passage of time, so it is difficult to particularly define the dissolution rate. The rate is also within the range without any problem. The case where sodium sulfate may be added after sodium carbonate is a case where all of sodium carbonate is dissolved, sodium sulfate added later is dissolved by 60% by weight or more, and fumaric acid or the like is dissolved in an effective amount. . If it does not dissolve in an amount of 60% by weight or more, a method of increasing the solubility by adding a solvent (water) and adjusting the temperature may be adopted.

When the dissolved amount of fumaric acid or the like becomes an effective amount, fumaric acid or the like may be added after sodium carbonate. Before the effective amount of fumaric acid or the like is dissolved, precipitation of salts may be prevented. In this case, specifically, the fumaric acid is prepared by preparing the slurry while maintaining the temperature of the slurry at a temperature at which no salt is precipitated, or preparing the slurry by increasing the solvent to increase the dissolution rate of the entire slurry. And the like can suppress precipitation of salt in the absence.

[Step (ii) (Step of Preparing Granules)] Step (ii) is a step of spray-drying the slurry obtained in step (i). By spray drying the slurry, granules having a substantially spherical particle shape are obtained. Step (i)
Even if there is no precipitation of sodium carbonate in
Sodium carbonate precipitates as the slurry is spray-dried. In this step, since fumaric acid or the like is already present in the slurry, salts are precipitated in the presence of fumaric acid and / or fumarate. The apparatus for atomizing the slurry may be any of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but the pressure spray nozzle is particularly preferable because the average particle diameter of the obtained granules is preferably 150 to 700 μm. . Further, the spray drying tower may be any of a countercurrent tower and a cocurrent tower.

2. Composition of Granule Group The granules for supporting a surfactant are composed of a water-insoluble inorganic substance (A), a water-soluble polymer (B), a water-soluble salt (C), fumaric acid, etc. (D). It is called a group. The detergent particles are particles containing a surfactant, a builder, and the like, and the detergent particles mean an aggregate of the particles. And the detergent composition contains detergent particles,
Detergent components (fluorescent dyes, enzymes, fragrances, defoamers, bleaching agents, bleaching activators, etc.) added separately from the detergent particles
Means a composition comprising

(A) Water Insoluble Inorganic Substance The primary particles preferably have an average particle size of 0.1 to 20 μm. Specific examples include aluminosilicates, silicon dioxide, hydrated silicate compounds and the like, among which aluminosilicates are preferred because they act as sequestering agents. Compounds. (B) water-soluble polymer carboxylic acid polymer, carboxymethyl cellulose,
Soluble starch, sugars and the like. Among these, acrylic acid homopolymers, acrylic acid-maleic acid copolymers and salts thereof having a molecular weight of about 2,000 to 100,000 are preferred from the viewpoint of detergency.

(C) Water-soluble salts Sodium carbonate is an essential component as a water-soluble salt.
Further, it is preferable to further include sodium sulfate from the viewpoint of further increasing the carrying capacity. In addition, as water-soluble salts, carbonates, hydrogen carbonates, sulfates, sulfites, hydrogensulfate, alkali metal salts containing phosphates and the like, water-soluble inorganic salts represented by ammonium salts and amine salts, Examples include low molecular weight water-soluble organic acid salts such as citrate and succinate, and amorphous and crystalline silicates.

(D) Fumaric acid and the like Fumaric acid and the like may be present in the form of granules, and their production method is not limited. That is, the powder of the corresponding fumaric acid and / or fumarate may be contained in the slurry, and other fumaric acid compounds are blended in the slurry and salt exchange is performed in the slurry to precipitate fumaric acid and the like. May be. The content of the fumarate in the granules can be determined by dissolving the granules in water and measuring the filtrate by ion chromatography. Among fumaric acid and the like, sodium fumarate, disodium fumarate, potassium fumarate and dipotassium fumarate are preferred. Further, an alkaline earth metal fumarate may be used.

The water content is preferably from 1 to 8% by weight, more preferably from 1 to 5% by weight, from the viewpoint of the handling of the granules. The preferred composition of the granules (based on solid content) is the same as the composition based on the solid content in the slurry described above. The surfactant-carrying granules may contain, in addition to the above components, surfactants and auxiliary components such as fluorescent dyes, pigments, and dyes suitable for detergent compositions.

3. Physical property average particle size of granules, from the viewpoint of solubility of detergent particles, 150 ~
700 μm is preferable, and 180 to 500 μm is more preferable. The bulk density is preferably 400 g / L or more, from the viewpoint of obtaining a detergent particle group having a bulk density of 500 g / L or more.
0 to 1000 g / L is more preferable, and 500 to 800 g
/ L is particularly preferred. The particle strength is preferably 5 to 100 MPa, more preferably 10 to 50 MPa, and 15 to 40 MPa.
MPa is particularly preferred. Within this range, the granules do not disintegrate when a surfactant is added to the granules, and exhibit the desirable property that the detergent particles derived from the granules have good disintegration during washing. I do. The loading capacity is 0.
It is preferably at least 2 mL / g, more preferably at least 0.4 mL / g, particularly preferably at least 0.5 mL / g. Within this range, the amount of the oil-absorbing carrier usually used when adding a surfactant to the granules can be reduced, so that it is preferable. Regarding the pores formed in the granule group, the pore size is set to 0.1.
Since pores having a pore diameter of 1 to 10 μm are suitable for supporting a liquid surfactant, the pore volume of the pore diameter measured by a mercury porosimetry is preferably 0.4 mL / g or more, 0.45 to 0.8 mL / g is more preferable,
Particularly preferred is 0.5 to 0.7 mL / g. The granules having such a pore volume can be obtained by spray-drying the slurry, freeze-drying the slurry, and then pulverizing the slurry. Among them, it is preferable to spray-dry the slurry in view of productivity and particle size distribution of the obtained granules.

4. Method for Producing Detergent Particles A preferred production method for obtaining detergent particles comprises the following step (iii), and may further comprise step (iv) if necessary. Step (iii): a step of mixing the surfactant and the granules of the present invention under a liquid condition of the surfactant. Step (iv): a step of mixing the mixture obtained in step (iii) with fine powder.

The surfactant that can be used in step (iii), that is, the surfactant that is supported on the granules, is preferably at least liquid in step (iii). Specific examples include an anionic surfactant and a nonionic surfactant. Above all, an interface containing a nonionic surfactant (E) having a melting point of 30 ° C. or less, an anionic surfactant (F) having a sulfate group or a sulfonic acid group, and a fixing agent (G) as a component (E). Activator compositions are preferred. As the component (F) and the component (G), an unneutralized product of the component (F) and an unneutralized product of the component (G) may be used. What is necessary is just to contain an alkaline component and to neutralize such a component.

The addition amount of the surfactant is preferably from 10 to 100 parts by weight, more preferably from 20 to 80 parts by weight, particularly preferably from 30 to 60 parts by weight, based on 100 parts by weight of the granules from the viewpoint of washing performance. In addition, when the surfactant is added to the granule group, a powder material other than the granule group may be added, if desired. Parts by weight are preferred.

The mixer used in the step (iii) preferably has, for example, a nozzle for adding a liquid surfactant and a jacket for controlling the temperature in the mixer. Suitable mixing time (in the case of a batch type) and average residence time (in the case of a continuous type) are preferably, for example, 1 to 20 minutes,
More preferably, 2 to 10 minutes. The mixing method of the surfactant and the granule group is, in the case of a batch type, after charging the granule group in a mixing device in advance, it is preferable to add a liquid surfactant, and spray the liquid surfactant. More preferably, it is supplied. At that time, other powder raw materials may be preferably used in an amount of less than 150 parts by weight, more preferably less than 100 parts by weight, based on 100 parts by weight of the granules. The temperature of the surfactant at the time of mixing is preferably 10 ° C. or more of the pour point of the surfactant, and 20 ° C. of the pour point of the surfactant from the viewpoint of easy handling.
The above is more preferred. Further, from the viewpoint of the thermal stability of the surfactant, the temperature is preferably 95 ° C or lower, more preferably 90 ° C or lower. By setting the temperature of the surfactant within such a range, the mixing is performed under the condition that the surfactant is in a liquid state.

Specific examples of other powder raw materials include bases having sequestering ability such as zeolite and citrate, bases having alkaline ability such as sodium carbonate and potassium carbonate, and the like.
Sequestering ability of crystalline silicates and the like, bases having both alkaline ability, and amorphous silica or amorphous aluminosilicate having a low sequestering ability but a high supporting ability are exemplified. . By using such a powder raw material in combination with the base granule as desired, a high blending of the surfactant composition and a reduction in adhesion of the mixture into the mixer can be achieved,
Detergency can be improved.

The following are specific examples of preferred mixing apparatuses. (1)-
(3) is preferred. (1) Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Powrex Co., Ltd.), Ladyge mixer (manufactured by Matsuzaka Giken Co., Ltd.) , Proshare Mixer (Taikai Kiko Co., Ltd.)
(2) Ribbon mixer (Nichiwa Machine Industry Co., Ltd.)
And (3) Nauta mixer (manufactured by Hosokawa Micron Corporation). Among the above mixers, more preferably, there are a Loedige mixer, a pro-share mixer and the like. Alternatively, the granules and the surfactant may be mixed using a continuous device of the above mixer. In addition, examples of continuous mixers other than those described above include a flexomics type (manufactured by Powrex Corporation) and a turbulizer (manufactured by Hosokawa Micron Corporation).

By further performing step (iv), the surface of the mixture obtained in step (iii) can be coated with fine powder. This is preferable because the fluidity and the caking resistance of the detergent particles can be improved. When the mixture obtained in the step (iii) is not in the form of a powder, in the step (iv), the mixture is pulverized by using a fine powder as an auxiliary agent (that is, in the state of the above (II)). To the state of the above (I)).

The fine powder improves the coverage of the surface of the detergent particles,
From the viewpoint of improving the flowability and caking resistance of the detergent particles,
The primary particles preferably have an average particle size of 0.1 to 10 μm. The average particle size of the fine powder can be determined by a method using light scattering (for example, a particle analyzer (Horiba, Ltd.)
Method). ) Or by SEM observation. Aluminosilicate is preferred as the fine powder,
It is also possible to use inorganic fine powders such as silicate compounds such as calcium silicate, silicon dioxide, bentonite, talc, clay, amorphous silica derivatives, and crystalline silicate compounds, and metal soap having primary particles of 0.1 to 10 μm. it can. In addition, it is preferable that the fine powder has high ion exchange ability and high alkali ability in terms of detergency. The amount of the fine powder to be used is preferably 0.5 to 40 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the mixture obtained in step (iii), in terms of fluidity and feeling of use. 2-20
Part by weight is particularly preferred.

The mixer that can be used in the step (iv) is preferably equipped with a high-speed rotating crushing blade in the mixer from the viewpoint of improving the dispersibility of the added fine powder and the crushing efficiency. , And step (iii). The temperature in the mixer may be arbitrarily set according to the purpose, but the surfactant composition in which the liquid surfactant contains the component (E), the component (G), and optionally the component (F) In the case where the temperature is such that the penetration hardness of the surfactant composition is 10 kPa or more, the amount of fine powder to be added can be reduced and the crushing efficiency can be improved.

5. Composition and Properties of Detergent Particles The detergent particles of the present invention are obtained by supporting a surfactant on the particles of the present invention or the particles obtained by the production method of the present invention. A plurality of surfactants may be mixed, that is, used as a surfactant composition. in this case,
The compounding amount of the component (F) is preferably 0 to 300 parts by weight, more preferably 20 to 2 parts by weight, per 100 parts by weight of the component (E).
00 parts by weight, particularly preferably 30 to 180 parts by weight. The amount of the component (G) is preferably 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the component (E).
50 parts by weight. By setting the amount of the surfactant composition in the above range, the composition has a temperature range in which the viscosity is 10 Pa · s or less at a temperature equal to or higher than the pour point of the composition, and In a temperature range lower than the pour point and higher than the melting point of the component (E), the composition has a temperature range in which the penetration hardness of the composition is 10 kPa or more. This surfactant composition shows a liquid state in the temperature range at the time of manufacturing the detergent particles, while it hardens in the temperature range at the time of storage of the detergent particles, thereby suppressing bleeding of the nonionic surfactant, Moreover, it also has the property of improving the strength of the detergent particles. The liquid referred to herein is a state having fluidity (JIS K 2
269) (measured above the pour point measured by the method specified in 269), and naturally includes a paste. The melting point was measured using the Mettler FP of the FP800 Thermo System.
It is measured at a heating rate of 0.2 ° C./min, using 81 (Mettler Instrumente AG). The viscosity was measured using a B-type viscometer (DVM-B type, manufactured by TOKYO KEIKI), rotor No.
3. Measured at a rotational speed of 12 r / min. The penetration hardness is measured with a rheometer (NRM-3002D,
8mm in diameter and 0.5cm ^{2 in} bottom area
Using a circular adapter (No. 3, 8φ), and the adapter enters the surfactant at a speed of 20 mm / min.
It can be obtained as a value obtained by dividing the load at the time of entering 0 mm by the bottom area of the circular adapter.

The component (E) has a melting point of 30 ° C. or lower, preferably 25 ° C. or lower, particularly preferably 22 ° C. or lower. For example, polyoxyalkylene alkyl (phenyl) ether, alkyl (polyalkylene) polyglycoside, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene glycol fatty acid ester, polyoxyethylene polyoxypropylene block polymer, polyoxyalkylene alkylol (fatty acid) Amides are exemplified as preferred. Two or more nonionic surfactants may be used in combination. Further, the nonionic surfactant may be used as an aqueous solution.

As the component (F), for example, a compound having 10 carbon atoms
To 18, alcohol ethoxylates, alkyl benzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfofatty acid salts, α-sulfofatty acid alkyl ester salts, etc. Are preferred.

Examples of the component (G) include anionic surfactants having a carboxylic acid group or a phosphoric acid group (excluding those having a sulfuric acid group or a sulfonic acid group). And anionic surfactants such as salts, hydroxy fatty acid salts and alkyl phosphates. In particular, one or more selected from the group consisting of sodium or potassium alkali metal salts of fatty acids or hydroxy fatty acids having 10 to 22 carbon atoms and amine salts such as alkanolamines are preferred in terms of solubility. Further, as the component (G), a compound having a melting point of 35 ° C. or more and having compatibility with the component (E) can also be mentioned. For example, if the molecular weight is 3000
One or more selected from the group consisting of 30,000 polyoxyalkylene-type nonionic compounds, and polyether-based nonionic compounds having a molecular weight of 30,000 to 30,000 are exemplified. Particularly preferred are polyethylene glycol, polypropylene glycol and polyoxyethylene alkyl ether having a melting point of 35 ° C. or higher. The term "compatible" as used herein means a property that the component (E) and the component (G) are mixed well at any one of the temperatures equal to or higher than the melting point of the component (E) and are hardly phase-separated. These may be mixed and used as the component (G).

Preferred physical properties of the detergent particles of the present invention are as follows. The average particle size is preferably from 150 to 800 μm, more preferably from 180 to 500 from the viewpoint of dissolution rate.
μm, particularly preferably 180 to 350 μm. The bulk density is 500 g / L from the viewpoint of making the detergent composition compact.
Above, preferably 500-1000 g / L, more preferably 600-1000 g / L, particularly preferably 650-1000 g / L.
It is 850 g / L. As for the caking resistance, the sieve passage rate is preferably 90% or more, more preferably 95% or more. The stain removal property is preferably evaluated by the test method described below, preferably at least 2 ranks, more preferably at 1 rank, to prevent the liquid surfactant-containing powder from adhering to the equipment in the transport system,
This is preferable because it is not necessary to prevent the container from being stained.

6. Method of measuring physical properties of granules and detergent particles Physical properties of granules and detergent particles can be measured by the following methods. (1) Average particle size: After oscillating for 5 minutes using a standard sieve specified in JIS Z 8801, it can be measured from the weight distribution according to the size of each sieve. (2) Bulk density: It can be measured by the method specified in JIS K 3362. (3) Loading capacity: Sample 10 was placed in a stirrer having a cylindrical round bottom vessel having an inner diameter of 5 cm and a height of 15 cm equipped with a stirring blade inside.
0 g, and add 10 ml / min of linseed oil while stirring.
Feed at the speed. At this time, the loading capacity of the linseed oil when the power of the stirrer becomes the highest is defined as the carrying capacity. (4) Particle strength: 20 g of a sample is placed in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapping is performed 30 times (Tsutsui Rikagiki Kikai Co., Ltd., TVP1 type tapping-type tightly packed bulk density meter, tapping condition; 36 times / min, free fall from a height of 60 mm), and measure the sample height (initial sample height) at that time. Thereafter, the entire upper end surface of the sample held in the container is pressed at a speed of 10 mm / min by a pressure tester, and a load-displacement curve is measured. The value obtained by multiplying the initial sample height and dividing by the pressed area is defined as the particle strength. (5) Pore volume: Using a mercury porosimeter, a pore volume having a pore diameter of 0.1 to 10 μm is measured by a mercury porosimetry.

(6) Water content: 3 g of a sample is placed in a weighing dish,
The sample is dried for 2 hours with an electric dryer kept at 105 ° C., and the difference in weight between the sample before and after the drying is defined as the water content. (7) Cakeing resistance: filter paper (manufactured by ADVANTEC)
No. 2) length 10.2cm x width 6.2cm x height 4
I made a box without a cm top and stapled the four corners. An acrylic resin plate (1) was placed on the box containing 50 g of the sample.
5 g) and a lead plate (250 g). Temperature 35
The following passing rate is determined for the caked state after being left for 2 weeks in an atmosphere at 40 ° C. and a humidity of 40%. <Passage> The sample after the test was screened (JIS Z8801).
The powder is gently placed on a specified mesh size of 4760 μm), the weight of the powder that has passed through is weighed, and the transmittance (%) of the sample after the test is determined. (8) Smearing property: The state of smearing at the bottom (non-contact surface with powder) of the filter paper container subjected to the caking resistance test is visually evaluated. The evaluation was made based on the wet area of the bottom part.
Up to 5 ranks. Rank 1: Not wet. 2: About 1/4 surface is wet. 3: About 1/2 surface is wet. 4: About 3/4 surface is wet. 5: The entire surface is wet.

[0046]

Example 1 63.5 parts by weight of water was put into a mixing tank, and the temperature was raised to 40 ° C. To this, a 30% by weight aqueous sodium hydroxide solution 1.9 was added.
By weight, 2.9 parts by weight of fumaric acid was added to obtain an aqueous solution of disodium fumarate. Further, 15 parts by weight of sodium sulfate (anhydrous anhydrous sodium sulfate), 1 part by weight of sodium sulfite, sodium carbonate (dense ash, average particle size:
290 μm, manufactured by Central Glass Co., Ltd.) 20 parts by weight, 4
0% by weight sodium polyacrylate (average molecular weight 100
00) 18.8 parts by weight of an aqueous solution, a fluorescent dye (Tinopearl C)
0.5 parts by weight of BS-X, manufactured by Ciba Geigy, sodium aluminosilicate (Zeobuilder (4A type, average particle size:
(3.5 μm), 50 parts by weight of Tosoh Corporation) were added successively and stirred for 30 minutes to prepare a homogeneous slurry. After adjusting the temperature to 60 ° C., the slurry was spray-dried to obtain a granule group shown in Table 1. FIG. 1 shows an SEM photograph of a cross section of the granule group.

Examples 2 to 5 In the same manner as in Example 1, granules shown in Table 1 were obtained.

Example 6 10 parts by weight of water was put into a mixing tank, and the temperature was raised to 40 ° C. To this, 1.9 parts by weight of a 30% by weight aqueous sodium hydroxide solution and 2.9 parts by weight of fumaric acid were added to obtain an aqueous solution of disodium fumarate. 100 parts by weight of water is put into another mixing tank, and 15 parts by weight of sodium sulfate and 1 part of sodium sulfite are added.
Parts by weight and 20 parts by weight of sodium carbonate
Was obtained. No precipitate was found in this aqueous solution. Thereafter, both aqueous solutions were mixed. No precipitate was found in this mixture. 18.8 parts by weight of a 40% by weight aqueous solution of sodium polyacrylate and 0.5 part of a fluorescent dye
Parts by weight and 50 parts by weight of sodium aluminosilicate were added successively and stirred for 30 minutes to prepare a homogeneous slurry. After adjusting the temperature to 60 ° C., the slurry was spray-dried to obtain a granule group shown in Table 1.

COMPARATIVE EXAMPLE 1 63.5 parts by weight of water was placed in a mixing tank, and sodium sulfate 15
Parts by weight, 1 part by weight of sodium sulfite, 2 parts of sodium carbonate
0 parts by weight, 18.8 parts by weight of a 40% by weight aqueous solution of sodium polyacrylate, 0.5 parts by weight of a fluorescent dye, and 50 parts by weight of sodium aluminosilicate were sequentially added and stirred for 30 minutes to prepare a homogeneous slurry. After adjusting the temperature to 60 ° C., the slurry was spray-dried to obtain a granule group shown in Table 1.
FIG. 2 shows an SEM photograph of a cross section of the granule group.

Comparative Example 2 62.7 parts by weight of water was put into a mixing tank, and the temperature was raised to 40 ° C. To this, a 30% by weight aqueous sodium hydroxide solution 1.9 was added.
By weight, 2.9 parts by weight of fumaric acid was added to obtain an aqueous solution of disodium fumarate. Further, 25 parts by weight of sodium sulfate, 1 part by weight of sodium sulfite,
20% by weight of a 0% by weight aqueous solution of sodium polyacrylate,
0.5 parts by weight of fluorescent dye, sodium aluminosilicate 5
9.5 parts by weight were successively added and stirred for 30 minutes to prepare a homogeneous slurry. After adjusting the temperature to 60 ° C., the slurry was spray-dried to obtain a granule group shown in Table 1. Table 1 shows the composition and physical properties of the obtained granules.

[0051]

[Table 1]

The granules of the present invention (Examples 1 to 6) showed a desired high loading capacity.

Example 7 Polyoxyethylene alkyl ether (Emulgen 10
8KM (average number of moles of ethylene oxide added: 8.5,
Alkyl chain carbon number: 12 to 14, melting point 18 ° C), 100 parts by weight of Kao Corporation) and polyethylene glycol (K
-PEG6000 (average molecular weight: 8500, melting point 60)
C), 10 parts by weight, manufactured by Kao Corporation, palmitic acid 9.2
2 parts by weight of water and 2 parts by weight of water were mixed, heated to 80 ° C. and stirred. 93.6 parts by weight of dodecylbenzenesulfonic acid (Neoperex FS, manufactured by Kao Corporation) and 27 parts by weight of a 48% by weight aqueous sodium hydroxide solution are added thereto to prepare a surfactant composition 1 to be supported on the granules. did. The pour point of the surfactant composition 1 was 57.5 ° C, and the penetration hardness of the composition at 35 ° C was 203 kPa.

Next, a Ladyge mixer (Matsuzaka Giken Co., Ltd.)
100 parts by weight of the granules of Example 1 were added to a main shaft (stirring blade, rotation speed: 60 r).
pm, peripheral speed: 1. (6 m / s) only, stirring was started.
In addition, warm water of 80 ° C. was flowed at 10 L / min through the jacket.
Thereto, 50 parts by weight of the surfactant composition 1 adjusted to 80 ° C. was added over 2 minutes, and thereafter, stirring was performed for 5 minutes. Further, in order to impart good fluidity as a detergent particle group, an amorphous aluminosilicate having an amount shown in Table 2 (Japanese Patent Application Laid-Open No.
The amorphous aluminosilicate having an average particle size of 8 μm of Preparation Example 2 described in JP-A-2794 was crushed and used. ), A main shaft (rotational speed: 120 rpm, peripheral speed: 3.1 m / s) and a chopper (rotational speed: 3600 rpm, peripheral speed: 28 m / s).
The stirring of s) was performed for 1 minute, and the detergent particle group 1 was discharged.

Comparative Example 3 A detergent particle group 2 was obtained in the same manner as in Example 7, except that the granule group of Comparative Example 1 was used instead of the granule group of Example 1.

Table 2 shows the composition and physical properties of the obtained detergent particles. The detergent particles of the present invention were able to reduce the amount of the amorphous aluminosilicate by improving the carrying capacity of the particles.

[0057]

[Table 2]

[0058]

As described above, in the method for producing the granules, it is possible to improve the carrying capacity of the granules containing water-soluble salts containing sodium carbonate by fumaric acid or the like. Further, in the method for producing detergent particles, it is possible to obtain detergent particles containing a large amount of a surfactant.

[Brief description of the drawings]

FIG. 1 is a photograph showing a cross section of a granule group of Example 1 by SEM.

FIG. 2 is a photograph showing a cross section of a granule group of Comparative Example 1 by SEM.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Shuji Takana 1334 Minato, Wakayama City, Kao Corporation Research Institute (72) Inventor Jin Takaya 1334 Minato, Wakayama City, Kao Corporation Laboratory F-term (reference) 4H003 AB19 AC08 BA09 BA28 CA18 EA12 EA16 EA28 EB07 EB30 EB36 ED02

Claims (8)

[Claims] Step (i): a step of preparing a water-soluble salt containing at least sodium carbonate (excluding fumaric acid and / or its salt), and a slurry containing fumaric acid and / or its salt, And a step (ii): spray drying the slurry obtained in the step (i), wherein the fumaric acid is added when the salt containing sodium carbonate is precipitated. And / or a method for preparing a surfactant-supporting granule for preparing a slurry such that a salt thereof is dissolved in water in the slurry. 2. The slurry contains 5 to 75 sodium carbonate.
The method according to claim 1, wherein fumaric acid and / or a salt thereof is contained in an amount of 0.2 to 15% by weight (based on solid content). 3. The slurry prepared in step (i) further contains sodium sulfate, and at least one selected from the group consisting of sodium carbonate and a double salt of sodium carbonate and sodium sulfate precipitates. 2. The manufacturing method according to 2. 4. In the slurry, [weight of sodium carbonate + sodium sulfate] / [weight of fumaric acid + fumarate] =
The method according to any one of claims 1 to 3, which is 0.3 to 60. 5. In the step (i), 1): preparing an aqueous solution containing fumaric acid and / or a salt thereof, 2) adding sodium sulfate to the aqueous solution obtained in 1), 3): 2) The method according to claim 3 or 4, wherein a slurry is prepared by adding sodium carbonate to the aqueous solution obtained in (1). 6. 20 to 90% by weight of a water-insoluble inorganic substance, 2 to 20% by weight of a water-soluble polymer, 5 to 75% by weight of a water-soluble salt containing at least sodium carbonate (excluding fumaric acid and / or its salt). And 0.2 to 15% by weight of fumaric acid and / or a salt thereof, and has an average particle size of 150 to 7
A surfactant-supporting granule having a particle size of 00 μm and a bulk density of 400 g / L or more. 7. The particles for supporting a surfactant according to claim 6, wherein the volume of pores having a pore diameter of 0.1 to 10 μm measured by a mercury porosimetry is 0.4 mL or more per 1 g of the particles. 8. A surfactant is supported on the particles for supporting a surfactant obtained by the method according to any one of claims 1 to 5, or on the particles for supporting a surfactant according to any one of claims 6 or 7. A group of detergent particles having an average particle size of 150 to 800 μm and a bulk density of 500 g / L or more.