JP3509078B2 - Base granules and detergent particles - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surfactant-supporting base granule group (hereinafter referred to as a base granule group) and a detergent particle group, which have improved cleaning performance and are mainly useful for improving the performance of a laundry detergent. And a method for producing the base granules. The present invention also relates to zeolite for blending laundry detergents.

[0002]

2. Description of the Related Art Since the compactness of powder detergents in the latter half of the 1980s has greatly contributed to transportation, portability, and storability, compact detergents (high-density detergents) are now predominant. It has become.

Many studies have been made so far on the production method of high-density detergent, one of which is, for example, WO99 / 2.
There is a technique, as disclosed in Japanese Patent No. 9830, in which a surfactant is carried on base granules obtained by spray drying to obtain detergent particles. This detergent particle group is characterized by high solubility and disintegration.

[0004]

Since the high-speed solubility and disintegration property of the detergent particle group as described above works for improving the cleaning performance, the present inventors have further investigated the solubility and the disintegration property of the detergent particle group. We have studied in detail the relationship between disintegration and cleaning performance. As a result, it was found for the first time that zeolite incorporated as a water-insoluble inorganic substance greatly affects the cleaning performance of the detergent particles. That is, 6 kinds of A-type zeolites having the same cation exchange ability were blended with the base granules to prepare the detergent granules, and the cleaning performance was measured. The cations expressed by the base granules obtained by blending them It was revealed that the exchange capacity was different, which had a great influence on the cleaning performance of the detergent particles prepared from the base particles. Therefore, as a result of pursuing factors and causes for changing the cation exchange ability of such base granules, the present inventors have a great influence on the agglomeration morphology of the zeolite to be blended, and the primary particles of the zeolite alone are agglomerated. It was found for the first time that the more uniform the aggregate particle size distribution of the obtained secondary aggregates, the higher the cation exchange capacity of the base granules containing them. When a zeolite having a more uniform aggregate particle size distribution than the above zeolite was prepared and blended with the base granules, it was confirmed that the base granules exhibited a high cation exchange capacity that has never been achieved.

The aggregated state of zeolite can be confirmed by an electron microscope. It is generally confirmed that cubic or spherical primary particles are aggregated to form a secondary aggregate, but by measuring the particle size of the secondary aggregate, the aggregate particle size distribution is obtained, and By performing the treatment, the degree of dispersion of the aggregate particle size distribution can be known. That is, it is convenient to use the standard deviation as a measure of the degree of dispersion of the agglomerated particle size distribution, but this can only be applied to comparisons of the same agglomerated particle size and when the average agglomerated particle sizes are different. Is a measure of the variance by dividing the standard deviation of the agglomerated particle size distribution by the average agglomerated particle size (sometimes multiplied by 100 and expressed as a%, which is called the coefficient of variation in statistics). Becomes

The variation coefficient of the aggregate particle size distribution of the above 6 kinds of zeolite is 30.5% to 64.9%, and the variation coefficient is small (that is, the aggregate particle size distribution is uniform). It was confirmed that the cation exchange capacity of the base granules to which it was added was high, and the cleaning performance of the resulting detergent particles was high.

It is well known that zeolites for detergent builders having a narrower aggregate particle size distribution than before are suitable. For example, the zeolite obtained by the production method described in JP-A-53-102898 has a narrow aggregate particle size distribution, but as a reason for narrowing the aggregate particle size distribution, too fine particles stick to the woven fabric. The reason is that coarse particles tend to settle, and the purpose is to narrow the agglomerated particle size distribution as a zeolite for detergents for clothes from the viewpoint of clothes retention. In addition, zeolite obtained by the production method described in JP-A-54-147200 has also been disclosed which has an aggregate particle size of about 1 to 5 μm from the viewpoint of clothes deposition and the like. As described above, the conventionally known zeolite has a narrowed aggregate particle size distribution, but its variation coefficient is 29.9 to 43.0%, and the particle size distribution is 29% or less. No homogeneous zeolites are disclosed. Also in WO 99/29830, zeolite manufactured by Tosoh Corporation (having an average agglomerated particle size of 3.5 μm and a mutation coefficient of 30.5%) is blended in the base granules. Therefore, unlike the present invention, there is no effect of improving the cation exchange capacity of the base granules, and the cleaning performance was insufficient.

Therefore, the present invention provides a base granule having excellent cation exchange ability, a method for producing the base granule, a zeolite for blending clothes detergent used in the method for producing the base granule, and excellent cleaning performance. It is intended to provide a detergent particle group.

[0009]

Means for Solving the Problems That is, the present invention provides [1]
(A) Zeolite having an average aggregate particle size of 15 μm or less and a variation coefficient of the aggregate particle size distribution of 29% or less, (B) water-soluble polymer, (C) water-soluble salt, and (D) 5% by weight
Surfactant-supporting base granules obtained by spray-drying a slurry containing the following surfactants, [2] a detergent particle group comprising the base granules described in [1] above, [ 3] Zeolite for blending detergent into clothes, which has an average aggregate particle size of 15 μm or less and a variation coefficient of the aggregate particle size distribution of 29% or less, and [4] (A) average aggregate particle size of 15 μ
Spray-drying a slurry containing a zeolite having a coefficient of variation of aggregate particle size distribution of 29% or less, (B) a water-soluble polymer, (C) a water-soluble salt, and (D) a surfactant. (A) Zeolite 1-90 having a step of
% By weight, (B) 2 to 25% by weight of water-soluble polymer, (C)
Water-soluble salts 5 to 75% by weight, and (D) surfactant 0 to
The present invention relates to a method for producing a base particle group for supporting a surfactant, the base particle group containing 5% by weight.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION (I) Base Granule Group The base granule group of the present invention has (A) an average aggregate particle size of 15 μm.
It contains zeolite having a coefficient of variation of aggregate particle size distribution of 29% or less, (B) water-soluble polymer, (C) water-soluble salt, and (D) 5% by weight or less of a surfactant. It is obtained by spray drying the slurry. (A) ~
The substance (D) will be described below.

(A) Zeolite Examples of the zeolite of the present invention having an average aggregate particle size of 15 μm or less and a variation coefficient of the aggregate particle size distribution of 29% or less (hereinafter referred to as “inventive zeolite”) are, for example, A
Type, X type, Y type, P type and the like, and among them, A type zeolite, which is generally excellent in cation exchange ability as a builder for detergents, is preferable. A-type zeolite has an X-ray diffraction pattern of JCPDS (Joint Committee on Powder Diffract
Ion Standards) has a diffraction peak at the position shown in 4A type zeolite (No. 38-241).

The aggregate particle size of the zeolite of the present invention is measured by the microscope method described in (1-2) in the examples below.
A scanning electron microscope is used as a microscope, and the maximum distance (also referred to as the longest diameter) of the particle size of the agglomerated particles in which the primary particles of the zeolite are brought into contact with each other and collected is defined as the agglomerated particle size. The aggregate particle size measured by this method has a normal distribution, and a frequency distribution on a number basis is obtained. The number average particle diameter calculated from this number-based distribution is defined as the average aggregate particle diameter D. The average aggregate particle size of the zeolite of the present invention is 15 μm or less, preferably 13 μm or less, from the viewpoint of preventing deposition on clothes, and 10 μm or less.
m or less is more preferable.

The standard deviation σ can be calculated from the number-based distribution, and the variation coefficient is calculated by the equation: (variation coefficient) = [(standard deviation σ) ÷ (average aggregate particle size D)] × 100. This coefficient of variation is an index of the state of distribution of aggregated particles, and the smaller this value is, the smaller the variation in particle diameter and the more uniform the particle size distribution. The variation coefficient of the zeolite of the present invention is 29% from the viewpoint of improving the cation exchange capacity of the base granules obtained by adding them.
It is below, preferably 28% or less, more preferably 25% or less, still more preferably 20% or less.

The zeolite of the present invention can be produced by the following method. (1) The raw material zeolite is crushed. (2) Classify the raw material zeolite.

Used in the above method (1) and / or (2)
As a raw material zeolite, the coefficient of variation exceeds 29%
There is no particular limitation as long as it is a commercially available detergent builder.
Zeolite or the like can be used. Of raw material zeolite
Cation exchange capacity is CaCO ₃100 ppm salt converted
Raw material zeolite in calcium fluoride aqueous solution (temperature is 10 ° C)
Was added to a concentration of 0.4 g / L for 1 minute or 1
It is evaluated by the amount of Ca ion exchange when cation exchange is performed for 0 minutes.
(Detailed measurement method is described in (1-3) in Examples below.
Posted). Cation exchange capacity after 1 minute of raw material zeolite
Is obtained by the method of (1) and / or (2) above.
Improves the cation exchange capacity of the zeolite of the present invention
From the viewpoint, the measuring method described in (1-3) in Examples described later.
The value measured by 70 mg CaCO₃/ G or more is preferred
80 mg CaCO₃/ G or more is more preferable, and 100
mgCaCO₃/ G or more is particularly preferable. Also, the raw material Zeo
The cation exchange capacity after 10 minutes of light is 170 mg.
CaCO₃/ G or more is preferable, 180 mg CaCO₃/
g or more is more preferable, 190 mg CaCO₃/ G or more
Particularly preferred.

The primary particle diameter of the raw material zeolite is a value measured by the measuring method described in (1-1) in the examples from the viewpoint of improving the cation exchange rate of the zeolite of the present invention obtained by the post-treatment. However, 2 μm or less is preferable, 1.5 μm or less is more preferable, and 1 μm or less is particularly preferable.

Next, details of the methods (1) and (2) will be described in order. First, regarding the method (1), as the pulverization method, for example, the Chemical Engineering Handbook edited by the Society of Chemical Engineering (Maruzen, 1988)
The crusher described in the fifth edition, pages 826 to 838 can be used. It may be wet pulverization or dry pulverization, but when the zeolite composition of the present invention is added to the detergent composition in the form of a slurry,
From the viewpoint of simplifying the production process, wet grinding is more preferable. As a dispersion medium used for wet pulverization, an alcohol solvent such as ethanol, a surfactant such as polyoxyethylene alkyl ether, a polymer dispersant, etc., alone or in addition to water, may be used as the dispersion medium.
It can be used as a mixed solution of one or more kinds. In the case of wet pulverization, the concentration of the raw material zeolite in the slurry is preferably 5% by weight or more, more preferably 10% by weight or more, from the viewpoint of productivity. The concentration of the raw material zeolite in the slurry is preferably 60% by weight or less, and more preferably 50% by weight or less, from the viewpoint of handleability of the raw material zeolite slurry during wet pulverization and from the viewpoint of preventing reaggregation of the zeolite after pulverization. As the average aggregate particle size of the zeolite of the present invention after pulverization,
It is preferably equal to or larger than the primary particle diameter of the raw material zeolite before pulverization. When pulverized until the average aggregate particle size becomes smaller than the primary particle diameter of the raw zeolite before pulverization, a large amount of zeolite constituent ions (eg, Si, Al, Na, etc.) elute due to the collapse of the primary particles of the zeolite. As a result, when pulverized zeolite is mixed in the detergent composition, the dispersibility is lowered, the washing performance is lowered, and the like. Further, since over-pulverization accompanied by disintegration of primary particles promotes aggregation of particles and the like, the aggregated particle size becomes non-uniform and the coefficient of variation tends to increase, which is not preferable for obtaining the zeolite of the present invention.

Next, the method (2) will be described. Uniformization of the aggregate particle size distribution of the raw material zeolite is also performed by classification. As the classification method, for example, the classification method described in Chemical Engineering Handbook (Chemical Engineering Handbook, edited by The Society of Chemical Engineering, 5th edition, pages 795 to 809) can be used. Either wet classification or dry classification may be used, but wet classification is preferred from the viewpoint of classification accuracy.
As a dispersion medium for wet classification, an alcohol solvent such as ethanol can be used in addition to water. In the case of wet classification, the concentration of the raw material zeolite in the slurry at the time of classification is preferably 5% by weight or more, more preferably 10% by weight or more, from the viewpoint of productivity. Also, from the viewpoint of classification accuracy,
It is preferably 40% by weight or less, more preferably 30% by weight or less. For example, when classifying at 20 ° C using gravity sedimentation in an aqueous solution with a starting zeolite concentration of 20% by weight,
From the viewpoint of classification accuracy, the sedimentation time is preferably 1 to 24 hours, more preferably 6 to 18 hours. When the classification accuracy is low, the classification accuracy can be improved by supplying the dispersion medium again to uniformly disperse the zeolite and repeating the classification.

The above two methods for producing the zeolite of the present invention having a uniform aggregated particle size distribution may be carried out individually or in combination.

The zeolite of the present invention can be obtained by subjecting the starting zeolite to a secondary treatment as in the above-mentioned methods (1) and (2). The production method described below provides (1) It is possible to directly obtain the zeolite of the present invention without performing the treatment such as (2). This method is particularly preferable because it does not require a secondary treatment step such as classification or pulverization. The method is shown below. (3) In the method for producing zeolite in which an aluminum source and / or a silica source are supplied to the circulation line of a reaction tank having a circulation line with a mixing device to carry out the reaction, the peripheral speed of the mixing device is 11 m / Perform vigorous stirring for s or more.

Specifically, the general composition formula of the anhydride is xM ₂
O · ySiO ₂ · Al ₂ O ₃ · zMeO (where M represents an alkali metal, Me represents an alkaline earth metal, and x =
0.5 to 1.5, y = 0.5 to 6, and z = 0 to 0.1) are used to synthesize an aluminum source and / or a silica source in a line. By carrying out the synthesis with stirring, the zeolite of the present invention can be obtained.

In that case, the silica source and the aluminum source are preferably in solution form from the viewpoint of, for example, the uniformity and dispersibility of the reaction. For example, commercially available water glass is suitably used as the silica source, and in some cases, the composition and concentration may be adjusted by adding water or caustic alkali to form the silica source. As the aluminum source, for example, aluminum hydroxide, aluminum sulfate, aluminum chloride, alkali aluminate, etc. are used, and among these, sodium aluminate is particularly preferably used. These are used as an aluminum source after adding caustic alkali and water as needed to adjust to an appropriate molar ratio and concentration. For example, aluminum hydroxide and sodium hydroxide may be mixed in water and dissolved by heating to prepare an aqueous solution of sodium aluminate, and this aqueous solution may be added to water with stirring to form an aluminum source aqueous solution. Further, such adjustment of the molar ratio and the concentration can also be carried out, for example, by previously introducing water into the reaction tank and adding a high-concentration alkali metal aluminate salt solution and caustic alkali thereto.

Further, by allowing an alkaline earth metal to coexist during the reaction between the silica source and the aluminum source, zeolite having a more uniform aggregate particle size distribution can be obtained. Examples of alkaline earth metals that are allowed to coexist in the reaction system include Mg, Ca, Sr, and B.
a or the like is used, and of these, Mg and Ca are preferably used. These are added to the reaction system as alkaline earth metal salts such as hydroxides, carbonates, sulfates, chlorides and nitrates. Among them, a water-soluble salt is preferable from the viewpoint of reaction uniformity, and a chloride aqueous solution of Mg, Ca or the like is particularly preferably used. These alkaline earth metal salts may coexist with these components during the reaction between the silica source and the aluminum source, but are added to the silica source and / or the aluminum source in advance in an aqueous solution or slurry state. It is preferable to add it to the silica source, and it is particularly preferable to add it to the silica source. Next, it is preferable to mix these silica source and aluminum source to carry out the synthesis reaction of the zeolite of the present invention.

In the present specification, "preliminarily added" means that a compound containing an alkaline earth metal is previously added to the silica source and / or the aluminum source before supplying the silica source and the aluminum source. A mode in which they are substantially uniformly mixed, for example, a compound containing an alkaline earth metal is directly added to a silica source and / or an aluminum source and mixed, and then the silica source and the aluminum source are mixed. The reaction may be performed, and in another embodiment, it is not always necessary to directly add and mix the compound containing the alkaline earth metal in the silica source and / or the aluminum source, and the silica source and / or A mode in which a compound containing an alkaline earth metal is mixed during the supply of the aluminum source, for example, a silica source and / or
Alternatively, the aluminum source raw material supply line and the alkaline earth metal-containing compound raw material supply line may be connected before the circulation line to perform line mixing. Alternatively, a method of directly adding a compound containing an alkaline earth metal to the reaction tank may be used.

The alkaline earth metal reacts with a silica source or an aluminum source to form a sparingly soluble micronucleus such as an alkaline earth metal silicate or aluminate in the reaction system. Amorphous aluminosilicates and zeolites are uniformly generated from the nuclei as starting points, and the resulting zeolites act so that the aggregate particle size distribution becomes uniform.

The composition of the raw material to be used when reacting the silica source and the aluminum source, and if necessary, the alkaline earth metal, is, for example, total SiO ₂ / Al ₂ O.
From the viewpoint of crystal structure stability, the molar ratio of ₃ is preferably 0.5 or more, more preferably 1.5 or more. Further, from the viewpoint of improving the cation exchange ability, 6 or less is preferable, 4 or less is more preferable, and 2.5 or less is particularly preferable.

From the viewpoint of reaction rate, the total molar ratio of M ₂ O / Al ₂ O ₃ of the raw materials is preferably 0.2 or more,
1.5 or more is more preferable, and from the viewpoint of improving the yield, it is preferably 8.0 or less, more preferably 4.0 or less. In this case, Na, K and the like are preferable as the M component, and Na is particularly preferable.

The total MeO / Al ₂ O ₃ molar ratio of the raw materials is preferably 0 or more, more preferably 0.005 or more, particularly preferably 0.01 or more, from the viewpoint of making the aggregate particle size distribution uniform. Further, from the viewpoint of improving the cation exchange rate of the zeolite of the present invention, 0.1 or less is preferable,
0.05 or less is more preferable, 0.03 or less is further preferable, and 0.025 or less is particularly preferable.

As the total concentration of the silica source, the aluminum source and the alkaline earth metal in the slurry during the reaction, the weight of all the added Si, M component, Al and Me components is converted to oxides. Assuming that the amount of solids relative to the total amount of water-containing slurry is the reaction concentration,
From the viewpoint of productivity, 10% by weight or more is preferable, and 15% by weight or more is particularly preferable. Further, from the viewpoint of the fluidity of the slurry and the viewpoint of preventing excessive aggregation of the zeolite of the present invention, 6
It is preferably 0% by weight or less, particularly preferably 50% by weight or less.

The zeolite of the present invention can be obtained by agitating and synthesizing by the method described below with the above composition. That is, using a silica source and an aluminum source as main raw materials,
If necessary, the raw materials are mixed in the circulation line of a reaction tank having a circulation system (circulation line) in the presence of an alkaline earth metal to carry out the reaction. Mixing is done in a mixer connected to the circulation line. As the other raw material, preferably a compound containing an alkaline earth metal as described above is mixed in advance with a silica source and / or an aluminum source and supplied to a circulation line as a substantially uniform mixture to carry out the reaction.

As the mixer connected to the circulation line, for example, a homomic line mixer, a homomic line mill, a homogenizer, a turbine pump, a centrifugal pump, or a mixer having an in-line rotary mixing mechanism is used. preferable. Of these, a homomic line mixer and a homomic line mill are particularly preferable because they have excellent mixing power. The mixing force of the mixer is not particularly limited, but the peripheral speed of the rotating rotor or turbine is preferably 11 m / s or more, more preferably 12 m / s.
/ S or more, and more preferably 15 m / s or more, it is preferable to rotate and synthesize by stirring. Further, the stirring state of the slurry at that time is preferably a state in which a laminar flow state and a turbulent flow state are mixed, that is, a transition state, and more preferably a turbulent flow state. Specifically, the stirring Reynolds number is 20.
It is preferably 0 or more, more preferably 800 or more, further preferably 1000 or more, and particularly preferably 4000 or more. The stirring Reynolds number is Re = nd ² ρ /
Formula of μ [however, d: stirring blade diameter (m) of a stirrer, n: rotational speed (s ⁻¹ ), ρ: density of slurry (kg / m ³ ), μ: viscosity of slurry (Pa · s)] The value obtained based on.

It is preferable that the reaction tank is equipped with a stirring blade so that the zeolite produced in the reaction tank does not aggregate nonuniformly. The peripheral speed of the stirring blade installed in the reaction tank, from the viewpoint of producing a zeolite aggregate particle size distribution is uniform,
0.8 m / s or more is preferable, 2.0 m / s or more is more preferable, and stirring synthesis is particularly preferable at 2.5 m / s or more. The stirring state of the slurry in the reaction tank is
A state in which a laminar flow state and a turbulent flow state are mixed, that is, a transition state is preferable, and a turbulent flow state is more preferable. Specifically, the stirring Reynolds number is preferably 50 or more, more preferably 300 or more, further preferably 500 or more, and particularly preferably 1000 or more.

The physical properties such as the size, structure and materials of the mixer, reaction vessel and stirring blade are not particularly limited as long as the zeolite of the present invention can be efficiently produced.

The reaction temperature is preferably 25 ° C. to 100 ° C., and is preferably 25 ° C. or higher from the viewpoint of reaction rate.
A temperature of not less than 0 ° C is particularly preferable. From the viewpoint of energy load and pressure resistance of the reaction vessel, 100 ° C or lower is preferable, and 70 ° C
The following are particularly preferred. The reaction time is 0 to 60 after the addition is completed.
Minutes are preferable, and 5 to 20 minutes are more preferable.

The above is the reaction step of the silica source and the aluminum source. After the completion of this step, the crystallization is promoted by the aging step to obtain the zeolite of the present invention. The aging temperature at that time is, for example, preferably 50 ° C. or higher, more preferably 80 ° C. or higher, from the viewpoint of the crystallization rate. Further, from the viewpoint of energy load and pressure resistance of the reaction vessel, 100 ° C. or lower is preferable. The aging time is usually 1 from the viewpoint of productivity.
It is preferably ˜300 minutes, in which case it is preferred to age until the strongest peak intensity of the X-ray diffraction pattern is maximized or the cation exchange capacity of the zeolite is maximized.

In the aging step, the zeolite crystallizes, but at this time, if the homogeneity of the slurry in the system is impaired, the crystals will disorderly aggregate with each other.
It is preferable that the slurry always maintains a uniform mixed state. Therefore, it is preferable to continue stirring in the reaction tank even during aging and to rotate the mixer as it is. Regarding the circulation flow rate of the circulation line, the linear velocity of the slurry circulating in the circulation line is preferably 0.7 m / s or more, and 1.0 m from the viewpoint of producing zeolite with a uniform aggregate particle size distribution.
/ S or more is more preferable, and it is particularly preferable to carry out stirring synthesis at 1.5 m / s or more.

After completion of the aging, the obtained slurry is filtered and washed or neutralized with an acid to terminate the crystallization. When cleaning the slurry by filtration, the pH of the cleaning solution
It is preferable to perform washing until the value becomes 12 or less. When the slurry is neutralized, examples of the acid used include sulfuric acid, hydrochloric acid, nitric acid, carbon dioxide, oxalic acid, citric acid,
Tartaric acid, fumaric acid and the like can be used, and among them, sulfuric acid and carbon dioxide gas are preferable from the viewpoint of equipment corrosion and cost.
In this case, the pH of the neutralized slurry is preferably adjusted to 7-12.

According to the above method (3), the composition of the anhydride is xM ₂ O.ySiO ₂ .Al ₂ O ₃ .zMeO (where M
Is an alkali metal, Me is an alkaline earth metal, and x =
The zeolite of the present invention represented by 0.5 to 1.5, y = 0.5 to 6, and z = 0 to 0.1 are obtained. Such stirring synthesis is a method for obtaining the zeolite of the present invention by vigorously stirring in the reaction step and the aging step in the synthesis of zeolite. That is, this is because the zeolite precursor produced in the reaction step and the crystals of the zeolite produced in the aging step collide non-uniformly and agglomerate in the reaction or aging step, resulting in the aggregate particle size distribution of the finally obtained zeolite. Is a method for preventing unevenness. As such a method, it is optimal to use a reaction tank having a circulation line and a mixer, but it is not always necessary as long as it is a means for avoiding nonuniform collision of zeolite precursors and zeolite crystals. It is not necessary to use such a reaction tank. That is, as the component (A) of the present invention,
Preferred examples include those obtained by stirring and synthesizing an aluminum source and / or a silica source in the presence of an alkaline earth metal.

Further, by subjecting the zeolite obtained by the stirring synthesis method of (3) above to post-treatment ((1) pulverization and / or (2) classification described above), a zeolite with a more uniform aggregate particle size distribution can be obtained. Can be obtained.

From the viewpoint of improving the cation exchange capacity, the primary particle size of the zeolite of the present invention obtained by the above-mentioned methods (1) to (3) is the measuring method described in (1-1) in the examples described later. The value measured by is preferably 2 μm or less,
It is more preferably 1.3 μm or less, further preferably 1 μm or less, particularly preferably 0.8 μm or less. Regarding the cation exchange capacity of the zeolite of the present invention, since the aggregate particle size distribution is uniform, the adhesion between particles in water is small and the dispersibility in water is high, resulting in cation exchange capacity (particularly 1
The cation exchange capacity after a minute) is high.

The cation exchange capacity after 1 minute of the present invention the zeolite is a value obtained by the measuring method described in Examples below (1-3) is preferably at 120mgCaCO ₃ / g or more, 150MgCaCO ₃ / G or more is more preferable, and 170 mg CaCO ₃ / g or more is particularly preferable.

As for the cation exchange capacity after 10 minutes, the value obtained by the method described in (1-3) in the examples below is preferably 190 mgCaCO ₃ / g or more, and 200
More preferred is mgCaCO ₃ / g or more, 210 mgCaC
O ₃ / g or more is particularly preferable.

Further, the zeolite of the present invention exhibits an excellent oil absorbing ability because the primary particles are uniformly gathered to form an aggregate. This oil absorption ability is effective in increasing the ability of the base granules to carry the surfactant. Therefore, the zeolite of the present invention can be suitably blended in a laundry detergent.

The oil absorption capacity of the zeolite of the present invention is JIS K 5101.
From the viewpoint of improving the oil absorption capacity of the base granules, the value of the oil absorption capacity obtained by the measurement method is preferably 80 mL / 100 g or more, more preferably 100 mL / 100 g or more, and 150 mL.
/ 100 g or more is particularly preferable.

The content of the zeolite of the present invention in the base granules is preferably 1% by weight or more, more preferably 5% by weight or more, particularly preferably 10% by weight or more, from the viewpoint of cleaning performance. From the viewpoint of particle strength, 90% by weight or less is preferable, 80% by weight or less is more preferable, and 70% by weight or less is particularly preferable.

(B) Water-Soluble Polymer The water-soluble polymer is an organic polymer having a solubility in 100 g of water at 25 ° C. of 0.5 g or more and a molecular weight of 1,000 or more, and has improved cleaning performance and / or particles of base granules. There is no particular limitation as long as it has an effect of improving strength. For example, carboxylic acid-based polymers, cellulose derivatives such as carboxymethyl cellulose, polyglyoxylate salts, aminocarboxylic acid-based polymers such as polyaspartate,
One or more selected from the group consisting of soluble starch, sugars and the like can be exemplified as preferable ones, and among them, carboxylic acid type polymers are preferable from the viewpoint of cleaning performance.

The content of the water-soluble polymer in the base granules is preferably 2 to 25% by weight, more preferably 3 to 20% by weight, and most preferably 4 to 15% by weight. Within this range, the particle strength of the base granules will be sufficiently high, and the solubility of the detergent composition will also be favorable.

(C) Water-Soluble Salts Examples of water-soluble salts include carbonates, hydrogen carbonates, sulfates, sulfites, hydrogen sulfites, phosphates, chlorides, bromides, iodides, and fluorides. , Water-soluble inorganic salts whose bases are alkali metals, ammonium, amines, and the like,
Examples thereof include low molecular weight water-soluble organic acid salts such as citrate and fumarate. Of these, carbonates, sulfates, sulfites and chlorides are preferred. These water-soluble salts may be composed of a single component or a plurality of components, or may form a double salt composed of a plurality of components.

Further, when anions different from carbonate ions such as sulfate ions and sulfite ions and cations different from sodium ions such as potassium ions and ammonium ions are mixed in the base granules, non-paste in water is obtained. It is effective in terms of formability. Specifically, the compound containing the anion and the cation may be blended in the base granules.

The content of water-soluble salts in the base granules is
5 to 75 wt% is preferable, 10 to 70 wt% is more preferable, and 20 to 60 wt% is the most preferable. Within this range, the base granules have sufficiently high particle strength, and are also preferable from the viewpoint of solubility of the detergent particles.

(D) Surfactant As the surfactant, for example, an anionic surfactant is preferably used. Examples of anionic surfactants include, for example, the Japan Patent Office publication, "Known and Common Techniques (Powdered Detergent for Clothes)"
Known anionic surfactants described in "1 of Chapter 3" can be preferably blended.

The content of the surfactant in the base granules of the present invention is preferably 0 to 5% by weight, but when the detergent particles are manufactured by a method in which the base granules absorb the surfactant solution. From the viewpoint of improving the ability of the base granules to absorb the surfactant (oil absorption ability), it is preferable that the surfactant is substantially not contained. Therefore, no surfactant is included, ie, 0% by weight, or if an optional surfactant is included, an amount greater than 0% by weight and up to 5% by weight is included. Is preferred. Further, the use of the zeolite of the present invention in the base granules substantially free of such a surfactant has the effect of remarkably improving the cation exchange ability of the base granules.

(E) Other components In addition to the components (A) to (D) described above, in the base granules,
Zeolites such as commercially available zeolites may be added to the extent that the cation exchange capacity of the base granules is not impaired. The degree of not impairing the cation exchange capacity of the base granules means that the cation exchange capacity of the base granules, which will be described later, is not exceeded. The base granules contain 1% by weight of auxiliary components such as fluorescent dyes, pigments and dyes.
The following content may be included.

The base granules of the present invention include (A) a zeolite having an average aggregate particle size of 15 μm or less and a variation coefficient of the aggregate particle size distribution of 29% or less, (B) a water-soluble polymer,
By spray-drying a slurry containing (C) water-soluble salts and (D) a surfactant, preferably an aqueous slurry, (A) zeolite 1 to 90% by weight, (B) water-soluble polymer 2 to 25% by weight, (C) water-soluble salts 5 to 75
%, And (D) 0-5 wt% surfactant.

In a preferred embodiment, the slurry contains 0.5 to 70% by weight of (A) zeolite, 1 to 20% by weight of (B) water-soluble polymer, and (C) 1 to 60% of water-soluble salt.
% By weight, and (D) 0 to 5% by weight of surfactant.

The content of the component (A) in the slurry to be spray-dried is preferably 0.5 to 70% by weight, more preferably 1 to 50% by weight, and the content of the component (B).
The content of the component is preferably 1 to 20% by weight,
More preferably, the content of the component (C) is 1% by weight.
-60% by weight is preferable, 2-50% by weight is more preferable, the content of the component (D) is preferably 5% by weight or less, more preferably 0-4% by weight, most preferably 0-3% by weight. , The content of the component (E) is 0 to 70% by weight.
Is preferred, and 0-60 wt% is more preferred. The balance of the slurry is preferably water. The slurry can be prepared by adding the components (A) to (D) and, if necessary, the component (E) to water and mixing them. A known method can be used as a method for spray-drying the slurry.

From the viewpoint of the cation exchange capacity of the base granules, the water content in the base granules obtained as described above is 8 when measured with an infrared moisture meter (measurement condition: 105 ° C., 2 hours). It is preferably not more than 5% by weight, more preferably not more than 5% by weight, particularly preferably not more than 3% by weight.

Here, the water generally present in the base granules obtained by spray drying causes liquid-crosslinking between the agglomerated particles of the zeolite in the base granules, so that the agglomerated particles of the zeolite are agitated by the crosslinking force. Adhesion is caused and the dispersibility of zeolite in water is reduced, and the cation exchange ability of the zeolite alone is not directly reflected in the cation exchange ability of the base granules. It is effective to add the zeolite of the present invention to the raw material slurry of the base granules as a means for preventing the deterioration of the dispersibility of the zeolite due to such liquid crosslinking. The adhesive force between two particles due to liquid crosslinking is influenced by the radius ratio of two particles, and the larger the radius ratio (the larger the difference in particle size between the two particles), the stronger the liquid crosslinking force. That is, the liquid bridging force is minimized when the two particles have the same size, that is, the particle size distribution is uniform. Therefore, the base granules to which the zeolite of the present invention is added have a small liquid crosslinking force due to the residual water content in the base granules, and as a result, the zeolite in the base granules is easily dispersed in water, and has a cation exchange ability that the zeolite has. Because of rapid expression, the base granules express high cation exchange capacity.

Cation exchange capacity of the base granules means Ca
Aqueous solution of calcium chloride 100ppm at CO ₃ terms (temperature 10 ° C.) was added so that the base particles obtained by drying 1 hour at 160 ° C. in a concentration of 0.35 g / L, when the cation exchange 3 minutes or 10 minutes It is evaluated by the amount of Ca ion exchange (the detailed measurement method is described in (2-1) in Examples described later.
Described in). From the viewpoint of cleaning performance, the cation exchange capacity of the base granules after 3 minutes is (2-1) in the examples described later.
The value obtained by the measuring method described in 1.
O ₃ / g or more is preferable, 145 mg CaCO ₃ / g or more is more preferable, 150 mg CaCO ₃ / g or more is particularly preferable, and 160 mg CaCO ₃ / g or more is further preferable.

From the viewpoint of cleaning performance, the cation exchange capacity of the base granules after 10 minutes is (2) in the examples described later.
-1) The value obtained by the measuring method described is 190 mgC
aCO ₃ / g or more is preferable, and 195 mg CaCO ₃ / g
The above is more preferable, and 200 mgCaCO ₃ / g or more is particularly preferable.

As described above, the base granules have a high cation exchange ability, and therefore the powder detergent (detergent particle group) containing the base granules exhibits a high cleaning performance.

(II) Detergent Particle Group The detergent particles of the present invention refer to particles containing the base granules of the present invention and, if necessary, a surfactant and a detergent builder. The detergent particle group is an aggregate thereof. Say. The detergent particle group of the present invention may be either a mononuclear detergent particle group or a polynuclear detergent particle group, but is preferably a mononuclear detergent particle group. The mononuclear detergent particles are detergent particles in which a surfactant is supported on base granules, and are detergent particles having one base granule as a core in one detergent particle. Further, the polynuclear detergent particles refer to detergent particles having several base granules as cores in one detergent particle. Here, the detergent particle group is preferably one in which a surfactant is supported in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the base particle group of the present invention, and the average particle diameter of the detergent particle group is 150 to 75.
0 μm, and the bulk density is preferably 500 g / L or more.

As the surfactant, for example, an anionic surfactant and a nonionic surfactant are preferable. The anionic surfactant and the nonionic surfactant can be used alone, but it is more preferable to use both as a mixture.
Further, an amphoteric surfactant or a cationic surfactant can be used together depending on the purpose. Further, an anionic surfactant such as alkylbenzene sulfonate is added to the detergent particle group in an amount of 5 to 2
When blended in an amount of 5% by weight, the effect is exhibited in terms of non-paste formation in water.

The above-mentioned surfactants (anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants) are described, for example, in the Japanese Patent Office, "Known and Conventional Techniques (Powdered detergent for clothing)". Known surfactants described in "1 of Chapter 3" can be used.

In addition, for example, when the above-mentioned anionic surfactant is blended, it may be blended by a method of blending in an acid form and separately adding an alkali.

The detergent particles of the present invention may contain a water-soluble organic solvent as a viscosity modifier in the above surfactant. As the water-soluble organic solvent, for example, polyethylene glycol is preferably used.

The mixing ratio of the water-soluble organic solvent is preferably 1 to 50 parts by weight, and 5 to 100 parts by weight of the surfactant.
30 parts by weight is more preferred. This blending ratio is suitable from the viewpoint that the viscosity of the surfactant is such that it is easily absorbed by the base granules and hardly exudes.

The above-mentioned detergent builder means a powdery detergency enhancer other than a surfactant, and specifically, zeolite (including the zeolite of the present invention), amorphous aluminosilicate, citrate, etc. A base having a cation exchange ability, a base showing an alkali ability such as sodium carbonate and potassium carbonate, a base having both a cation exchange ability and an alkali ability such as a crystalline alkali metal silicate, and other sodium sulfate and the like. It shows a base or the like for increasing the ionic strength.

The amount of the detergent builder used is preferably 0.5 to 12 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the base granules. The amount of the detergent builder used is preferably in this range from the viewpoint of enhancing the fluidity of the detergent particles and excellent caking resistance during storage.

As a method for producing the detergent particles, a known method can be used, and examples thereof include a method in which a surfactant is sprayed on the base particles and a detergent builder is further added if necessary.

[0071]

EXAMPLES The measured values in Examples and Comparative Examples were measured by the following methods. (1) Zeolite evaluation method (1-1) Primary particle size scanning electron microscope (manufactured by Shimadzu Corporation, SUPER SCAN-22)
0, same below), based on SEM image of zeolite photographed at 5000 times magnification, 50 or more confirmed as one particle (encircled by small circle in Fig. 2) was digitized (Graftic Co., Ltd.). (Manufactured by Digitizer KW3300, the same applies hereinafter) was used to measure the longest width of the particles. The average value of the obtained measured values was defined as the primary particle size.

(1-2) Average Coagulation Particle Size and Variation Coefficient of Coagulation Particle Size Distribution In a SEM image of zeolite photographed at 1000 times using a scanning electron microscope (for example, FIG. 1), aggregates of primary particles ( The portion surrounded by a large circle in FIG. 2) was used as an agglomerated particle, and its longest diameter was measured by a digitizer. The number average value of the particle sizes of the obtained 50 or more agglomerated particles was defined as the average agglomerated particle size (D). Also, the standard deviation (σ) is calculated from the particle size distribution of the agglomerated particles, and the standard deviation (σ) / average agglomerated particle size (D)
× 100 was calculated, and this value was used as the coefficient of variation (unit is%).

(1-3) Cation exchange capacity of zeolite In a 100 mL beaker, a calcium chloride aqueous solution (C
Add 100 mL (100 ppm in terms of aCO ₃ ), 30 mm x 8 mm
Stir with a stirrer piece of 400 rpm. Next, a sample (0.04 g when the zeolite is powder, 0.04 g in terms of solid content in the case of water slurry) is precisely weighed and put into a stirred calcium chloride aqueous solution. After stirring at 10 ° C. for a predetermined time (1 minute or 10 minutes), a 0.2 μm membrane filter is used for filtration. Take 10 mL of the filtrate and change the amount of Ca in the filtrate to EDTA.
Measured by titration and after 1 minute or 10 according to the following formula
After a minute, the amount of Ca ion-exchanged per 1 g of the sample (CaC
The cation exchange capacity of the zeolite after 1 minute or 10 minutes was calculated based on O ₃ conversion. Cation exchange capacity after 1 or 10 minutes of zeolite =
((B -V) × M × 100.09 × 100/10) / S B: blank (calcium chloride solution (100 ppm) in terms of CaCO ₃₎ EDTA titer (mL) V: Sample solution EDTA titer (mL) M: EDTA molar concentration (mol / L) 100.09: CaCO ₃ molecular weight (g) 100: Calcium chloride solution amount (mL) used for measurement 10: Titrated liquid amount (mL) S: Zeolite powder amount (g )

(2) Evaluation method of base granules (2-1) Cation exchange capacity of base granules 3 g of base granules are weighed on a glass petri dish and dried at 160 ° C. for 1 hour in a dryer. 0.35g of which
Precisely weighed, and the calcium chloride aqueous solution (CaCO ₃
It is added to 1000 mL (100 ppm in terms of conversion). The resulting mixture was stirred at 400 r / min for 3 minutes or 10 minutes at a constant temperature of 10 ° C, filtered through a 0.2 μm filter, and the Ca amount in 10 mL of the filtrate was measured by EDTA titration. The amount of Ca ion-exchanged per 1 g of zeolite in the granule group after 3 minutes or 10 minutes (CaCO
₃ conversion) was taken as the cation exchange capacity after 3 minutes or 10 minutes of the base granules. Cation exchange capacity after 3 minutes or 10 minutes of the base granules =
((B−V) × M × 100.09 × 1000/10) / SB: Blank (calcium chloride solution (100 ppm in terms of CaCO ₃ )) EDTA titer (mL) V: EDTA titer of sample solution (mL) M: EDTA molar concentration (mol / L) 100.09: CaCO ₃ molecular weight (g) 1000: calcium chloride solution amount (mL) used for measurement 10: titrated liquid amount (mL) S: in base granule group Zeolite content (g)

(3) Method for evaluating detergent particle group (cleaning performance) Preparation of artificially contaminated cloth: An artificially contaminated cloth was prepared by adhering an artificially contaminated liquid having the following composition to the cloth. Adhesion of artificial pollution liquid to cloth is
According to Japanese Patent Application Laid-Open No. 7-270395, printing was carried out by printing the artificial contaminant on a cloth using a gravure roll coater. Process, cells of the gravure roll capacity 58cm ³ / cm ² to produce an artificial contaminated cloth artificially contaminated liquid is adhered to cloth, coating speed 1.0
m / min, drying temperature 100 ° C., drying time 1 minute. As the cloth, cotton cloth 2003 cloth (manufactured by Tanigami Shoten) was used.

(Composition of artificial pollutant) (where% is% by weight)
Lauric acid 0.44%, myristic acid 3.09%, pentadecanoic acid 2.31%, palmitic acid 6.18%, heptadecanoic acid 0.44%, stearic acid 1.57%, oleic acid 7.75. %, Trioleic acid 13.06%, n-hexadecyl palmitate 2.18%, squalene 6.
53%, yolk lecithin liquid crystal 1.94%, Kanuma red clay 8.
11%, carbon black 0.01%, and tap water are balanced.

(Washing conditions and evaluation method) 22 g of detergent particle groups used for the evaluation were weighed. Next, 2.2 kg of clothing (cotton underwear) was prepared. Next, 10c produced above
35 cm x 30 cm of 10 m x 10 cm artificially contaminated cloths
Sew on 3 cotton base cloths, along with the clothing you prepared earlier,
It was put in the washing machine "Aizuma-go NA-F70AP" manufactured by Matsushita Electric Industrial Co., Ltd. The detergent particle group previously taken was added thereto and washed. The washing conditions are as follows. Washing course: Standard course, detergent concentration 0.067%, water hardness 4 ° DH, water temperature 20 ° C, bath ratio (water / clothing) 15L / k
g.

The detergency was measured by measuring the reflectance at 550 nm of the unfabricated original cloth and the contaminated cloth before and after cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate (%) was calculated by the following formula. The measured average value of the cleaning rate of 10 sheets was shown as the cleaning power. Cleaning rate (%) = [(reflectance of contaminated cloth after cleaning-reflectance of contaminated cloth before cleaning) / (reflectance of original cloth-reflectance of contaminated cloth before cleaning)] x 100

Example 1 A stirring and synthesizing apparatus (a reaction tank 3 (a stainless steel tank having a volume of 350 L) equipped with an external circulation line 6 having a mixer 5) as shown in the schematic view of FIG. Is a liquid feed pump 2 (WP pump manufactured by Daido Metal Co., Ltd.
WP3WL140C0 type) can be used to feed the liquid, and from the raw material tank 1 (200 L stainless steel tank) via the raw material supply line 7 immediately before the entrance of the mixer 5 (line mixer, manufactured by Tokushu Kika Kogyo Co., Ltd., 2S6 type). Zeolite was synthesized by the following method using a raw material that can be supplied.

In the raw material tank 1, an aqueous solution of No. 3 water glass (Na
₂ O: 9.68% by weight, SiO ₂ : 29.83% by weight)
105.6 kg was charged and stirred with a stirring blade 8 having a length of 210 mm at a stirring speed of 100 rpm. Then 48% by weight
28.3 kg of caustic soda aqueous solution is added, and then 0.81
Put 72.2 kg of weight% calcium chloride aqueous solution at 50 ° C
The temperature was raised to. Next, in the reaction tank 3, an aqueous solution of sodium aluminate (Na ₂ O: 21.01% by weight, Al ₂ O ₃ : 28.
18 wt%) 95.0 kg, and the mixture was heated to 50 ° C. while stirring at a stirring speed of 100 rpm with a stirrer 4 having one pitched paddle (not shown) and anchor paddle (not shown) of 500 mm each. While moving the stirrer 4,
While circulating the aqueous solution of sodium aluminate in the circulation line 6 in advance by the liquid feed pump 2 at a flow rate of 40 kg / min (the linear velocity of the circulation line is 0.35 m / s), the rotation speed of the mixer 5 was 3600 rpm (turbine At a peripheral speed of 16 m / s), the solution in the raw material tank 1 was supplied to the circulation line 6 via the raw material supply line 7 to start the reaction. After completion of the reaction (after adding all the raw materials in the raw material tank 1), the raw materials have a SiO ₂ / Al ₂ O ₃ molar ratio of 2, a Na ₂ O / Al ₂ O ₃ molar ratio of 2.5, and Ca.
It had a composition ratio such that the O / Al ₂ O ₃ molar ratio was 0.02. Adjust the liquid feed pump 2 so that the circulation flow rate is 130 kg / min (the linear velocity of the circulation line is 1.5 m / s), and while circulating the slurry obtained by the reaction, 80
The temperature was raised to 0 ° C., and aging was performed for 60 minutes while maintaining 80 ° C.

The obtained slurry was taken out from the stirring and synthesizing apparatus, filtered and washed until the pH of the filtrate became 11.4, and dried at 100 ° C. for 13 hours to obtain zeolite powder.

An X-ray diffractometer (stock)
Using RINT2500VPC manufactured by Rigaku Co., CuKα ray,
Measured under the conditions of 40 kV and 120 mA and provided to JCPDS.
Qualitative result based on the diffraction pattern shown, type 4A
It was found to be a zeolite of In addition, this Zeora
The general formula of Ito is 1.02Na₂O ・ 2.05SiO ₂
・ Al₂O₃-It was 0.02 CaO.

Further, the obtained zeolite powder was subjected to SEM.
The SEM image of 1000 times was taken using the
(A)). FIG. 4B shows the distribution of the aggregate particle size measured by the digitizer based on FIG. 4A. Table 1 shows the physical properties of the obtained zeolite.

Example 2 The zeolite obtained in Example 1 was classified by the following method. 35 kg of an aqueous solution having a zeolite concentration of 20% by weight was placed in a cylindrical stainless steel container (inner diameter 400 mm × height 300 mm), uniformly stirred and dispersed, and then allowed to stand at 20 ° C. for 12 hours. From the bottom of the container, a 70-mm-high precipitate and a 230-mm-high supernatant liquid were obtained. After removing the supernatant liquid by decantation, a zeolite precipitate was obtained, of which 100 g was 500
It was placed in a beaker of mL volume and dried at 100 ° C. for 13 hours. A 1000 times SEM image of the obtained zeolite powder was taken using an SEM (FIG. 5 (a)). Figure 5 (a)
FIG. 5 (a) shows the distribution of the aggregate particle size measured by a digitizer based on the above. Table 1 shows the physical properties of the obtained zeolite.

Example 3 The zeolite obtained in Example 1 was pulverized by the following method. 500 g of an aqueous solution having a zeolite concentration of 40% by weight was put together with 2000 g of zirconia balls having a diameter of 5 mm in a polystyrene closed container having an internal capacity of 1 L, and ball milling (300 rpm) was performed for 12 hours, and 100 g of the obtained slurry was 500 g.
It was put in a beaker of mL volume and dried at 100 ° C. for 13 hours.
The obtained zeolite powder is 1000 times S using SEM.
An EM image was taken (FIG. 6 (a)). FIG. 6 shows the distribution of the aggregate particle size measured by a digitizer based on FIG. 6 (a).
It shows in (b). Table 1 shows the physical properties of the obtained zeolite.

Comparative Example 1 Using the same reactor as in Example 1, the rotation speed of the mixer 5 was changed.
3600 rpm to 2400 rpm (turbine peripheral speed 10.7 m /
Example 1 except that the circulation flow rate in the aging step after the reaction was changed from 130 kg / min in Example 1 to 54.5 kg / min (the linear velocity of the circulation line was 0.64 m / s). 4A type zeolite was synthesized by the same method. The obtained powder is S
An SEM image was taken using EM (FIG. 7 (a)).
FIG. 7B shows the distribution of the aggregate particle size measured by a digitizer based on FIG. 7A. Table 1 shows the physical properties of the obtained zeolite.

Comparative Example 2 Of the raw materials used in Comparative Example 1, ion-exchanged water 71.
4A was prepared in the same manner as in Comparative Example 1 except that 7 kg was used.
Type zeolite was synthesized. The obtained 4A-type zeolite powder was photographed with a SEM image at 1000 times with SEM (FIG. 8 (a)). Based on FIG. 8 (a), FIG. 8 (b) shows the distribution of the aggregate particle size measured by the digitizer. Table 1 shows the physical properties of the obtained zeolite.

Comparative Examples 3-5 As Comparative Example 3, a commercially available 4A zeolite (Toyo Builder,
Tosoh Co., Ltd.), Comparative Example 4 4A zeolite (synthetic zeolite, manufactured by Nippon Builder Co., Ltd.), Comparative Example 5 4A zeolite (SILTON B, Mizusawa Chemical Co., Ltd.), 1000 times SEM image of each powder using SEM. Were photographed (FIG. 9 (a), FIG. 10 (a), FIG. 11 (a)). 9 (b), 10 (b), and 11 (b) show the distribution of the aggregate particle size measured by a digitizer based on these figures. Table 1 shows the physical properties of the obtained zeolite.

[0089]

[Table 1]

From the results in Table 1, it can be seen that the zeolites obtained in Examples 1 to 3 are all superior in cation exchange ability to those in Comparative Examples 1 to 5. In addition, Example 1
From ~ 3, it is understood that the more the zeolite is classified and pulverized to reduce the mutation coefficient, the higher the cation exchange ability, particularly the cation exchange ability after 1 minute.

Example 4 Base particles containing the 4A type zeolite obtained in Example 1 were prepared by the following procedure. The composition of the base granules is as shown in Table 2.

[0092]

[Table 2]

Ion-exchanged water was added to a mixing tank (volume: 180 L) having a 200 mm long stirring blade, and heated while stirring. After the water temperature reached 55 ° C., sodium carbonate (Dense ash, manufactured by Central Glass Co., Ltd.) was added, and then sodium sulfate (anhydrous neutral Glauber, manufactured by Shikoku Chemicals Co., Ltd.) was added and stirred for 15 minutes. After that, 40% by weight aqueous sodium polyacrylate solution (weight average molecular weight 10,000, manufactured by Kao Corporation) was added, and then sodium chloride (yaki salt, manufactured by Nippon Salt Co., Ltd.) was added and stirred for 15 minutes, and then the example. Add 4A type zeolite obtained in 1 and stir for 30 minutes to obtain a homogeneous slurry (water content 53% by weight) 60 kg
Got Spray drying this slurry to a water content of 1.2% by weight.
To obtain a group of base granules.

Next, a detergent particle group was prepared by the following procedure.
At a temperature of 80 ° C., 10.5 parts by weight of polyoxyethylene alkyl ether (Emulgen 108KM, manufactured by Kao Corporation), polyethylene glycol (K-PEG6000, Kao Corporation)
0.4 parts by weight, palmitic acid equivalent to 2 parts by weight of sodium palmitate (Lunack P-95, manufactured by Kao Corporation)
And a LAS acid precursor (Neopex FS, manufactured by Kao Corporation) corresponding to 12.5 parts by weight of LAS-Na, and a sodium hydroxide aqueous solution as a neutralizing agent are mixed to prepare a mixed solution containing a surfactant. did. Next, 50 parts by weight of the previously prepared base granules were put into a Ledige mixer (capacity 20 L, manufactured by Matsuzaka Giken Co., Ltd.), and the surfactant-containing mixed liquid was sprayed onto the base granules while stirring. After that, 10 parts by weight of crystalline silicate (SKS6, manufactured by Clariant) and commercially available zeolite (Toyo Builder, manufactured by Tosoh Corporation) 7
Parts by weight were added to obtain a detergent particle group. The physical properties of the obtained base granules and detergent particles are shown in Table 2 below.

Example 5 A group of base particles containing the 4A type zeolite obtained in Example 2 was prepared by the following procedure. The composition of the base granules is as shown in Table 2. Ion-exchanged water was added to the same mixing tank as in Example 4, and the water slurry of zeolite obtained in Example 2 (20 wt% slurry) was added and heated with stirring. After the water temperature reached 55 ° C., sodium carbonate (Dense ash, manufactured by Central Glass Co., Ltd.) was added, and then sodium sulfate (anhydrous neutral Glauber, manufactured by Shikoku Chemicals Co., Ltd.) was added and stirred for 15 minutes. Thereafter, a 40 wt% sodium polyacrylate aqueous solution (weight average molecular weight: 10,000, manufactured by Kao Corporation) was added. After adding sodium chloride (Yaki salt, manufactured by Nippon Salt Co., Ltd.) and stirring for 15 minutes, Comparative Example 3
Commercially available zeolite used in (Toyo Builder, Tosoh Corporation)
Was added and stirred for 30 minutes to obtain a homogeneous slurry (water content 5
3 wt%) 60 kg was obtained. This slurry was spray-dried to obtain a base granule group having a water content of 1.2% by weight. Next, a detergent particle group was prepared in the same manner as in Example 4 except that the obtained base particle group was used.

Example 6, Comparative Examples 6 to 8 Base granules and detergent granules were prepared in the same manner as in Example 5, except that the zeolite obtained in Example 3 was used as Example 6. Further, as Comparative Example 6, the commercially available zeolite described in Comparative Example 3 (Toyo Builder, manufactured by Tosoh Corporation), as Comparative Example 7 the commercially available zeolite described in Comparative Example 4 (synthetic zeolite, manufactured by Nippon Builder Co., Ltd.), and as Comparative Example 8 compared. Commercially available zeolite described in Example 5 (SILTON B, manufactured by Mizusawa Chemical Co., Ltd.)
A base particle group and a detergent particle group were prepared in the same manner as in Example 4 except that each of the above was used.

From the results shown in Table 2, the cation exchange capacity of the base granules obtained in Examples 4 to 6 and the cleaning performance of the detergent particles are higher than those of Comparative Examples 6 to 8. there were.

Further, the commercially available zeolites of Comparative Example 4 and Comparative Example 5 have almost the same cation exchange capacity of the zeolite itself as shown in Table 1. However, there is a clear difference in the cation exchange capacity of the base granules of the base granules containing them (Comparative Example 7 and Comparative Example 8), and the zeolite of Comparative Example 4 is superior. This reflects the difference in the aggregate particle size distribution of both zeolites, and Comparative Example 4 (the variation coefficient of the aggregate particle size distribution is 33.3%).
Comparative Example 5 (the variation coefficient of the aggregate particle size distribution is 47.
7%), the zeolite has a more uniform agglomerated particle size distribution, so the cation exchange capacity of the base granules containing it is improved. As described above, in order to improve the performance of the base granules, it is effective to mix zeolite with a uniform aggregate particle size distribution, and the results of the examples of the present invention support this.

[0099]

EFFECTS OF THE INVENTION The base granules containing a zeolite having a uniform aggregated particle size distribution of the present invention are excellent in cation exchange ability. Therefore, by adding them to the detergent particles containing the base granules, A detergent having a high cation exchange ability can be obtained, and the cleaning performance can be improved.

[Brief description of drawings]

FIG. 1 shows an SEM image of the zeolite of the present invention taken at 1000 × with a scanning electron microscope (SEM).

FIG. 2 is a 5000 × SEM image of a magnified portion surrounded by a square frame in FIG. 1, showing aggregated particles (large circles) that are aggregates of primary particles (portions surrounded by small circles). (Enclosed in).

FIG. 3 is a schematic explanatory view of a stirring and synthesizing apparatus for zeolite of the present invention.

4 (a) is a 1000 times SEM image of the zeolite obtained in Example 1, and FIG. 4 (b) is a distribution of the average aggregate particle size of the zeolite obtained in Example 1. The figure is shown.

5 (a) is a 1000 times SEM image of the zeolite obtained in Example 2, and FIG. 5 (b) is a distribution diagram of the aggregate particle size of the zeolite obtained in Example 2. Indicates.

6 (a) is a 1000 times SEM image of the zeolite obtained in Example 3, and FIG. 6 (b) is a distribution diagram of the aggregate particle size of the zeolite obtained in Example 3. Indicates.

7 (a) is a 1000 times SEM image of the zeolite obtained in Comparative Example 1, and FIG. 7 (b) is a distribution diagram of the aggregated particle size of olite obtained in Comparative Example 1. Indicates.

8 (a) is a 1000 times SEM image of the zeolite obtained in Comparative Example 2, and FIG. 8 (b) is a distribution diagram of the aggregate particle size of the zeolite obtained in Comparative Example 2. Indicates.

FIG. 9 (a) shows the zeolite used in Comparative Example 3.
It is a 1000 times SEM image, and FIG. 9 (b) shows a distribution chart of the aggregate particle size of the zeolite used in Comparative Example 3.

10 (a) is a 1000 times SEM image of the zeolite used in Comparative Example 4, and FIG. 10 (b) is a distribution diagram of the aggregate particle size of the zeolite used in Comparative Example 4. .

11 (a) is a 1000 times SEM image of the zeolite used in Comparative Example 5, and FIG. 11 (b) is a distribution diagram of the aggregate particle size of the zeolite used in Comparative Example 5. .

[Explanation of symbols]

1 raw material tank 2 Liquid feed pump 3 reaction tanks 4 stirrer 5 mixer 6 circulation lines 7 Raw material supply line 8 stirring blades

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C11D 3/12 C11D 3/12 3/37 3/37 10/02 10/02 11/02 11/02 17/06 17/06 (72) Inventor Kimihiro Mizusawa, 1334 Minato, Wakayama City Kao Corporation Research Laboratory (56) Reference JP 2000-345199 (JP, A) JP 58-2399 (JP, A) JP 56-59618 ( JP, A) JP 61-270211 (JP, A) JP 54-147200 (JP, A) JP 53-102898 (JP, A) JP 61-138697 (JP, A) Special table Flat 3-504734 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/00-19/00 C01B 39/00-39/54 C01B 33/00-39/46 B01J 39/14 B01J 2/00-2/30

Claims (12)

(57) [Claims] 1. (A) A zeolite having an average aggregate particle size of 15 μm or less and a variation coefficient of the aggregate particle size distribution of 29% or less, (B) a water-soluble polymer, (C) a water-soluble salt, and (D). ) Base particles for supporting a surfactant, which are obtained by spray-drying a slurry containing 5% by weight or less of a surfactant. 2. The component (A) has a general composition formula xM ₂ O.y.
SiO ₂ · Al ₂ O ₃ · zMeO (where M represents an alkali metal, Me represents an alkaline earth metal, and x = 0.5 to 5).
1.5, y = 0.5 to 6, z = 0 to 0.1), The group of base particles according to claim 1, which is a zeolite. 3. The base granules according to claim 1 or 2, wherein the component (A) is obtained by stirring and synthesizing an aluminum source and / or a silica source in the presence of an alkaline earth metal. 4. The composition of the raw materials used for the synthesis of the component (A) has a molar ratio of SiO ₂ / Al ₂ O ₃ of 0.5 or more and 6 or less and a molar ratio of M ₂ O / Al ₂ O ₃ of 0. The base granules according to claim 2, wherein the base granules are 0.2 or more and 8.0 or less, and the MeO / Al ₂ O ₃ molar ratio is 0 or more and 0.1 or less. 5. The molar ratio of MeO / Al ₂ O ₃ is 0.00.
The base granules according to claim 4, which are 5 or more and 0.1 or less. 6. The cation exchange capacity of the base granules after 10 minutes is 190 mg CaCO ₃ / g or more.
The base granules described. 7. The primary particle diameter of component (A) is 2 μm or less.
The base granules according to any one of claims 1 to 6. 8. A water content of 8% by weight or less.
7. A base granule group according to any one of 7. 9. A detergent particle group comprising the base particle group according to any one of claims 1 to 8 . 10. The average agglomerated particle size is 15 μm or less, and
Zeolite for blending detergents for clothes, which has a coefficient of variation in the aggregate particle size distribution of 29% or less. 11. A zeolite having (A) an average aggregate particle size of 15 μm or less and a variation coefficient of an aggregate particle size distribution of 29% or less, (B) a water-soluble polymer, (C) a water-soluble salt, and (D). ) 1-90% by weight of zeolite (A), which has a step of spray-drying a slurry containing a surfactant,
(B) 2 to 25% by weight of water-soluble polymer, (C) 5 to 75% by weight of water-soluble salts, and (D) 0 to 5% by weight of surfactant.
A method for producing a base particle group for supporting a surfactant, comprising: 12. A slurry containing 0.5 to 0.5 parts of (A) zeolite.
70% by weight, (B) water-soluble polymer 1 to 20% by weight,
The production method according to claim 11 , which comprises (C) 1 to 60% by weight of a water-soluble salt and (D) 0 to 5% by weight of a surfactant.