JP5705525B2 - Zeolite composite particles - Google Patents

Description

  The present invention relates to a zeolite composite particle group, in particular, a zeolite composite particle group treated with a polycarboxylic acid polymer, a powder detergent composition containing the same, and a method for producing the zeolite composite particle group.

  The powder detergent for clothing is required to have excellent cleaning performance for quickly removing dirt, dissolution performance for quick dissolution / dispersion in water, and storage stability performance that does not deteriorate the quality even when stored under severe conditions. In order to achieve these washing performance and storage stability performance, 4A-type zeolite having excellent cation exchange ability and water vapor adsorption ability is generally blended in a powder detergent for clothing.

  However, since zeolite is insoluble in water, when washed under harsh conditions such as stuffed laundry, stain-like unmelted residue may be generated in clothing due to insufficient rinsing. When the blending amount of zeolite is extremely reduced in order to prevent this undissolved residue, the storage stability is deteriorated such as a decrease in fluidity and occurrence of blocking. In addition, the physical properties, quality and detergency are adversely affected, such as a decrease in detergency due to insufficient cation exchange capacity. In order to reduce stain residue in clothing without adversely affecting physical properties, quality, and detergency, it is important to improve the dispersibility of zeolite in water.

  In order to improve this point, with respect to zeolite, for example, Patent Document 1 proposes a zeolite dispersant to which a specific acrylic carboxylic acid or a salt thereof and an acrylic ester copolymer are added. It is intended to improve the stationary stability, does not improve the dispersibility of the zeolite blended in the powder detergent composition, and the copolymer does not have the effect of suppressing spot-like undissolved residue. .

  On the other hand, Patent Document 2 describes the production of high-density zeolite-containing particles by granulating a uniform powder mixture of microcrystalline zeolite and (co) polymer carboxylate. Patent Document 2 describes that it is preferable to use spray-dried fine powder zeolite for the particles. Furthermore, according to the method of Patent Document 2, since the treated zeolite particles are larger than 10 μm, the high-density zeolite-containing particles obtained by granulating from a uniform powder mixture comprising the fine powder zeolite and the polymer powder are In addition, the effect of suppressing stain-like undissolved residue cannot be obtained.

JP-A-3-254828 JP-A-4-501730

  An object of the present invention is to provide a zeolite composite particle group having improved dispersibility in water, particularly a zeolite composite particle group treated with a polycarboxylic acid polymer, and a powder detergent composition containing the same. It is in. Here, the “group” of the particle group means that a plurality of particles exist, and since the zeolite is treated as a zeolite particle group during the polymer treatment, naturally, the resultant is the zeolite composite particle group.

The present invention relates to a zeolite particle group (a) having an average particle diameter of 0.1 to 8 μm, a polycarboxylic acid-based polymer having a monomer constituent unit having a weight average molecular weight of 20,000 to 300,000 and having a carboxylic acid group ( a zeolite composite particle group obtained by drying after mixing with the solution of b),
The average particle size is 0.5-10 μm,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more.
The present invention relates to a zeolite composite particle group.

The present invention also relates to a zeolite particle group (a) and a zeolite composite particle group comprising a polycarboxylic acid polymer (b) having a monomer structural unit having a carboxylic acid group and a weight average molecular weight of 20,000 to 300,000. And
The average particle size is 0.5-10 μm,
The volume diameter of 90% (D90) is 12 μm or less,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more,
Zeolite particles are coated with a polycarboxylic acid polymer,
The present invention relates to a zeolite composite particle group.

  Moreover, this invention relates to the powder detergent composition containing the zeolite composite particle group of the said invention.

Further, the present invention relates to a zeolite particle group (a) [hereinafter referred to as component (a)] having an average particle size of 0.1 to 8 μm, having a weight average molecular weight of 20,000 to 300,000 and having a carboxylic acid group. After mixing with a solution of a polycarboxylic acid polymer (b) having a unit (hereinafter referred to as component (b)), it is dried,
An average particle diameter is 0.5 to 10 μm, and a zeolite composite particle group in which the ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more is obtained.
The present invention relates to a method for producing a zeolite composite particle group.

  ADVANTAGE OF THE INVENTION According to this invention, the zeolite composite particle which improved the dispersibility to water, and the powder detergent composition formed by containing it can be provided.

<Zeolite composite particles>
The zeolite composite particle group of the present invention is a composite particle group of fine zeolite particles obtained by treating the component (a) with the component (b).

  Component (a) is an aggregate of zeolite particles, and examples of zeolite include A type, X type, Y type, and P type. Among them, A type zeolite that is generally excellent in cation exchange ability is preferable as a builder for detergents. . The A-type zeolite has a diffraction peak at the position indicated by the 4A-type zeolite (No. 38-241) whose X-ray diffraction pattern is presented by JCPDS (Joint Committee on Powder Diffraction Standards). As the component (a), those commercially available as zeolite can be used.

Zeolite has an anhydrous general formula of xM ₂ O.ySiO ₂ .Al ₂ O ₃ (where M represents an alkali metal, x = 0.5 to 1.5, y = 0.5 to 6) It is represented by

  The zeolite particles constituting the zeolite particle group of component (a) in the present invention are preferably finely divided zeolite particles, and the primary particle zeolite itself is ideal. However, from an economical point of view at the time of production, it is not necessary to be a zeolite having a high purity so long as this effect is not hindered, and it may contain an amorphous material or impurities. Moreover, it is difficult to exist as a primary particle as a fine powder. The zeolite of the present invention may be one in which several primary particles or primary particles are aggregated. “Several agglomeration” is a number that can be counted under a microscope. If it is explained, the primary particles are agglomerated within 10 particles, particularly within 6 particles.

  The average particle size of the component (a) is 0.1 to 8 μm. In the present invention, a refractive index of 1. is used by using a laser diffraction / scattering particle size distribution measuring device (“LA950” manufactured by Horiba, Ltd.). The value of volume median particle size (D50) when measuring the particle size distribution after irradiation with ultrasonic waves for 5 minutes at a circulation speed of 4 and an ultrasonic intensity of 7, using 30 water as a dispersion medium, is the average of the component (a). The particle size. Generally, it may be called a volume-based median diameter. The average particle size of the component (a) is 8 μm or less from the viewpoint of preventing adhesion to an object to be cleaned (clothing, etc.) when blended in a detergent or the like, and prevents excessive aggregation of the components (a). From the viewpoint, it is 0.1 μm or more. The average particle diameter of the component (a) is preferably 1 μm or more as the lower limit, more preferably 3 μm or more, and preferably 8 μm or less, more preferably 5 μm or less as the upper limit. Furthermore, in addition to these average particle diameters, in order to show the particle size distribution situation, D90 by the above measurement method, that is, the particle diameter that becomes 90% on a volume basis is preferably 12 μm or less, more preferably 10 μm or less, and more preferably 8 μm or less. More preferably.

  The component (b) is preferably such that the monomer structural unit having a carboxylic acid group is 80 to 100 mol%, more preferably 90 to 100 mol%, of all monomer structural units.

  Moreover, the weight average molecular weight of (b) component is 20,000-300,000, Preferably it is 30,000-200,000. The weight average molecular weight of the component (b) is measured by gel permeation liquid chromatography using polyethylene glycol as a standard and a mixed solution of acetonitrile and water (phosphate buffer) as a developing solvent.

  (B) As a component, the polymer of the monomer chosen from acrylic acid and methacrylic acid is mentioned. Specific examples include homopolymers of monomers having a carboxylic acid group, such as polyacrylic acid and polymethacrylic acid, and carboxylic acid-based polymers such as copolymers of acrylic acid and maleic acid. Of these, acrylic acid / maleic acid copolymers having an acrylic acid / maleic acid monomer ratio of 20/80 to 80/20, more preferably 30/70 to 70/30 are preferred.

  In the zeolite composite particle group of the present invention, the proportion of the component (b) with respect to 100 parts by mass of the component (a) is 5% from the viewpoint of preventing stains remaining on an object to be cleaned (clothes, etc.) when blended in a detergent or the like. More than a part. The proportion of the component (b) relative to 100 parts by mass of the component (a) is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and preferably 10 parts by mass or less from the viewpoint of preventing deterioration of the powder physical properties of the zeolite composite particles. Further preferred.

  The zeolite composite particle group of the present invention has an average particle diameter of 0.5 μm to 10 μm. The average particle diameter is substantially equal to a single zeolite particle in which several primary particles or primary particle zeolites are aggregated (b The average particle size of a mixture of particles obtained by agglomerating zeolite with the polymer of component (b) from the zeolite composite particles coated with component polymer), and hereinafter referred to as the average composite particle size. In the present invention, using a laser diffraction / scattering type particle size distribution measuring apparatus (“LA950” manufactured by Horiba, Ltd.), water having a refractive index of 1.30 is used as a dispersion medium, the circulation speed is 4, and there is no ultrasonic irradiation. After circulating for a minute, the value of the volume median particle size (D50) as measured is taken as the average composite particle size for the zeolite composite particle group. The average composite particle size of the zeolite composite particles of the present invention is 0.5 μm or more, more preferably 2 μm or more, further preferably 5 μm or more, from the viewpoint of preventing further aggregation of the zeolite composite particles, and a detergent. From the viewpoint of preventing adhesion to an object to be cleaned (clothing, etc.) when blended in the like, it is 10 μm or less, preferably 8 μm or less, and more preferably 6 μm or less. Furthermore, in addition to these average particle diameters, in order to show the particle size distribution situation, D90 by the above measurement method, that is, the particle diameter that becomes 90% on a volume basis is preferably 12 μm or less, more preferably 10 μm or less, and more preferably 8 μm or less. More preferably.

  The zeolite composite particles of the present invention are preferably particles in which the zeolite particles are coated with the polymer of component (b) when observed as a single zeolite composite particle. Ideally, the primary particle zeolite is coated with the polymer. Particles are preferred. However, it is difficult to obtain a particle group composed only of composite particles having a primary particle size as a core, and may be zeolite composite particles in which aggregated particles are coated with a polymer as long as the particle size condition of the present invention is satisfied. The primary particle zeolite may include particles formed by agglomeration of the polymer.

  The coating can be confirmed by the fact that Si, which is a constituent element of zeolite, is not detected on the surface of the composite particle by a surface analysis device such as ESCA.

  However, since the zeolite composite particles of the present invention are too agglomerated depending on the production method, there are cases where the average particle size becomes large or agglomerated particles having a broad particle size distribution may be obtained. Therefore, in order to obtain a zeolite composite particle group satisfying the average particle diameter of the present invention, preferably satisfying the requirements of the average particle diameter and D90, the average particle diameter can be adjusted by classification, pulverization or the like. For example, the pulverizer described in “Chemical Engineering Handbook” (Maruzen, 1988), 5th edition, pages 826-838, edited by the Society of Chemical Engineering, can be used. Wet grinding or dry grinding may be used. Further, the homogenization of the aggregate particle size distribution is also performed by classification. As the classification method, for example, a classification method described in “Chemical Engineering Handbook” (Maruzen, 1988), 5th edition, pages 795 to 809, edited by the Society of Chemical Engineers, can be used. Wet classification or dry classification may be used.

  The zeolite composite particles of the present invention preferably have a bulk density of 400 to 1200 g / L, more preferably 600 to 1000 g / L.

  The particles constituting the zeolite composite particle group of the present invention are the component (b) on the surface of a single zeolite constituting the component (a), preferably a zeolite in which several primary particle zeolites and several primary particle zeolites are aggregated. Individual particles surface-treated with a polycarboxylic acid polymer or agglomerated thereof. Although the component (b) does not necessarily cover the entire surface of the zeolite particles, the effect can be obtained, but from the viewpoint of dispersibility, a state in which the surface of the zeolite particles is completely covered with the component (b) is preferable. In addition, the state coat | covered with (b) component means the state by which Si etc. which are constituent elements of a zeolite are not detected on the surface of the zeolite composite particle finally obtained by surface analysis apparatuses, such as ESCA.

  The zeolite composite particles of the present invention can be obtained by mixing the component (a) with a solution of the component (b), preferably an aqueous solution, and then drying (removing the solvent from the mixture). The drying method is not particularly limited, but thin film drying or spray drying, particularly spray drying is preferable.

  The production method preferably includes a step of crushing the component (a) in a liquid dispersion medium to primary particles in a solution by a pulverizer such as ultrasonic irradiation or a mill to form a fine particle group. In this case, after the component (a) is dispersed in a liquid dispersion medium and subjected to grinding treatment such as ultrasonic irradiation, the component (b) is added and brought into contact, and the component (a) and the component (b) exist simultaneously. There is a method of pulverizing the liquid dispersion medium, but in the case of an aqueous solution, if the pulverization is performed in the presence of the component (a) and the component (b), the dispersibility of the zeolite particles is improved by the component (b). It is preferable to prepare a fine particle suspension by pulverizing in a liquid dispersion medium in the presence of the components (a) and (b). After the treatment, it is preferable to dry the liquid dispersion medium to obtain an aggregate of the zeolite composite, which is dry pulverized to adjust the average particle diameter of the present invention.

  In addition, for drying, the drying apparatus described in Tables 14 and 11-12, Characteristics and Overview of Hot Air Dryers, described in “Chemical Engineering Handbook” (Maruzen, 1999), 6th edition, pages 769-772, is edited. Can be used. Of these, those having a high drying speed, such as a hot air conveying spray type and a non-superheated drum dryer type, are preferred. Also, a drying device using microwaves is preferably used instead of hot air.

  In the zeolite composite particle group of the present invention, the negative charge on the zeolite surface is further increased by coating the zeolite primary particles with a polycarboxylic acid polymer. As a result, for example, when blended in a powder detergent, the electrostatic repulsion force with the cloth is increased in the washing water, and the adhesion of zeolite particles to clothing is suppressed. As a result, the amount of undissolved spots is reduced.

  An example of a preferable production method for obtaining the zeolite composite particle group of the present invention is as follows. 5 parts by mass of the component (b) solution is mixed with 100 parts by mass of the component (a) and dried by spray drying. The method of letting it be mentioned. In this case, the solution of component (b) is preferably an aqueous solution, and the concentration of component (b) in the aqueous solution is set so that the ratio of component (b) to 100 parts by mass of component (a) is 5 parts by mass or more. The When mixing this aqueous solution, it is more preferable that the zeolite particle group satisfies the requirements of D50, particularly the requirements of D50 and D90. In addition, the temperature of the aqueous solution at the time of mixing is not limited, but 5-60 degreeC is preferable. The spray drying temperature is preferably 100 to 300 ° C.

  The zeolite composite particle group of the present invention may contain agents generally used for cleaning agents other than the components (a), (b) and water. Moreover, when it is set as the additive for powder detergent compositions mentioned later, a part of detergent particle | grains may adhere to a zeolite composite particle. Examples thereof include surfactants, nonionic polymers such as polyethylene glycol, fluorescent dyes, pigments, fragrances, and other water-soluble or water-insoluble inorganic salts. The other component is 5 parts by mass or less per 100 parts by mass of the component (a), further 3% by mass or less, and particularly 1% by mass or less. It is preferable to consist of a) component and (b) component.

  The zeolite composite particle group of the present invention can be suitably used as an additive for a powder detergent composition, especially a detergent builder, and further a garment detergent builder, as in the case of ordinary zeolite. Further, since it is a cation exchanger, it has a function of exchanging heavy metals and the like, and therefore can be used for waste water treatment agents, water treatment agents and the like. It can also be used as a carrier or basic catalyst for heavy metal or noble metal catalysts.

<Powder detergent composition>
The powder detergent composition of the present invention contains the zeolite composite particles of the present invention.

  The powder detergent composition of the present invention is obtained by mixing the zeolite composite particles of the present invention with a base detergent containing a surfactant, an alkaline agent, a builder, etc., and from the viewpoint of cleaning performance, 100 parts by mass of the base detergent On the other hand, the zeolite composite particle group of the present invention is preferably mixed in an amount of 1 part by mass or more, more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. Moreover, from a powder physical property and a soluble viewpoint, it is preferable to mix 50 mass parts or less, It is more preferable to mix 30 mass parts or less, It is still more preferable to mix 20 mass parts or less.

  Base detergents are usually added detergent components such as various surfactants, alkali agents (alkali metal carbonates, etc.), builders (other than the zeolite composite particles of the present invention), enzymes, bleaching agents (percarbonate). Salt, perborate, bleach activator, etc.), anti-staining agent (carboxymethyl cellulose, etc.), softener, reducing agent (sulfite, etc.), fluorescent brightener, foam suppressor (silicone, etc.), fragrance Etc. can be contained. However, enzymes and bleaching agents (percarbonate, perborate, bleach activator, etc.) are usually used as separate particles.

  The use of the powder detergent composition of the present invention is not particularly limited, and it is suitably used as a detergent for clothing, dishwashing detergent, residential detergent, automobile detergent, body detergent, tooth paste, metal detergent and the like. In particular, a detergent for clothing is suitable.

  As an example of a composition preferable as a detergent for clothes, the zeolite composite particle group of the present invention is 10 to 50% by mass, the surfactant is 1 to 50% by mass, the sodium carbonate is 1 to 50% by mass, other components (enzymes and the like) What contains 1-5 mass% is mentioned.

  In the following Examples and Comparative Examples, the average composite particle diameter, average particle diameter, and cloth residual amount were measured or calculated by the following methods.

  In addition, whether or not the zeolite particles of the zeolite composite particles were covered with a polymer was confirmed by a surface analyzer such as ESCA.

<Average composite particle size of zeolite composite particles>
Using a laser diffraction / scattering type particle size distribution measuring apparatus ("LA950" manufactured by Horiba, Ltd.), using water with a refractive index of 1.30 as a dispersion medium, circulating at a circulation rate of 4 for 1 minute without ultrasonic irradiation, The value of the volume median particle size (D50) when measured was taken as the average composite particle size of the zeolite composite particle group.

<Average particle diameter of component (a)>
Using a laser diffraction / scattering type particle size distribution measuring apparatus (“LA950” manufactured by Horiba, Ltd.), water with a refractive index of 1.30 is used as a dispersion medium, and the ultrasonic wave is irradiated for 5 minutes at a circulation speed of 4 and an ultrasonic intensity of 7. The value of the volume median particle size (D50) when the subsequent particle size distribution was measured was defined as the average particle size of the zeolite particle group [component (a)].

<Cloth persistence>
(1) Preparation of test cloth Dyeing test material A black cloth-dyed cotton broad 40 (plain weave black cloth) from Tanigami Shoten Co., Ltd. was cut into a circular shape having a diameter of 8 cm to obtain a test cloth. This test cloth is dried at 105 ° C. for 30 minutes with an electric dryer, allowed to stand for 15 minutes in a room temperature and humidity control room (25 ° C., 50% Rh), and then weighed with a precision balance (measurement of initial mass).

(2) Measurement of cloth residual mass of zeolite composite particle group Ion exchange water adjusted to 25 ° C was filled in a 1 liter beaker (inner diameter 105 mm, height 150 mm cylindrical type, for example, manufactured by Iwaki Glass Co., Ltd.) With the water temperature kept constant in a water bath, the swirl depth with respect to the water depth is approximately 1 with a stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, Teflon (registered trademark) round thin type). Stirring was performed at a rotation speed of 1000 rpm (1000 rpm). The zeolite composite particle group weighed so as to be 0.1666 ± 0.0010 g was charged and dispersed in water with stirring, and stirring was continued. Ten minutes after the addition, the dispersion was poured into a test cloth that had been set in a suction filter in advance, and suction filtered. In addition, the suction filtration was performed using a suction bottle with a test cloth previously weighed in a Buchner funnel having a diameter of 90 mm. After suction filtration, the test cloth is dried with an electric dryer at 105 ° C. for 30 minutes, left in a room temperature humidity control room (25 ° C., 50% Rh) for 15 minutes, and then the amount of zeolite composite particles attached to the evaluation cloth Was weighed with a precision balance, and determined from the evaluation fabric mass-initial mass.

(3) Measurement of cloth residual mass of powder detergent composition In the measurement of the cloth residual mass of the zeolite composite particle group, the zeolite composite particle group was replaced with the powder detergent composition. At that time, the powder detergent composition was weighed and added so as to be 0.666 ± 0.0010 g.

(4) Calculation of cloth residual ratio The cloth residual ratio was calculated by the following formula.
Cloth residual ratio (%) = (T / S) × 100
S: input mass (g) of zeolite composite particles or powder detergent composition
T: cloth residual mass (g) of zeolite composite particles or powder detergent composition

Example 1
A 20 mL screw tube was charged with 2 g of a zeolite particle group (average particle size: 4.0 μm (D50), 6.2 μm (D90)) and 8 g of a polyacrylic acid Na aqueous solution having a weight average molecular weight of 50000, and 10 g of a zeolite polymer dispersion. Was made. The concentration of the aqueous polymer solution was adjusted with ion-exchanged water so that the solid content of the polymer was 5.3 parts by mass with respect to 100 parts by mass of the zeolite particle group. Next, the zeolite-polymer dispersion thus prepared was subjected to ultrasonic waves by immersing a screw tube in a water tank of an ultrasonic cleaner, and the fact that the average particle diameter of zeolite was 4.0 μm and D90 was 6.2 μm was confirmed by laser diffraction. / After confirming with a scattering type particle size distribution analyzer (Horiba, Ltd., “LA950”, hereinafter referred to as LA950), a zeolite-polymer dispersion is dropped into an evaporating dish with a diameter of 20 cm, and about 8 g in a microwave oven. The moisture was dried. After drying, the polymer-treated zeolite-containing solid adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.

Example 2
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 170,000, samples were prepared in the same manner as in Example 1, and evaluation was performed in the same manner. The evaluation results are shown in Table 1.

Example 3
The polymer type was changed to acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 50000, a sample was prepared in the same manner as in Example 1, and the evaluation was performed in the same manner. went. The evaluation results are shown in Table 1.

Example 4
Acrylic acid / maleic phosphate copolymer Na (acrylic acid / maleic acid = 50/50 molar ratio) of the weight average molecular weight 70,000 types of polymer to, to prepare a sample in the same manner as in Example 1, evaluated by the same method Went. The evaluation results are shown in Table 1.

Examples 5-9
Samples were prepared in the same manner as in Example 1, except that the amount of polyacrylic acid Na having a weight average molecular weight of 50000 was changed as shown in Table 1 and evaluated by the same method. The evaluation results are shown in Table 1.

Comparative Example 1
A 20 mL screw tube was charged with 2 g of a zeolite particle group (manufactured by Zeobuilder) (average particle size: 4.0 μm, D90: 6.2 μm) and 8 g of ion-exchanged water to prepare 10 g of a zeolite dispersion. Next, the prepared zeolite dispersion was subjected to ultrasonic waves, and it was confirmed by LA950 that the average particle size was 4.0 μm and D90 was 6.2 μm. Then, the zeolite dispersion was dropped into an evaporating dish having a diameter of 20 cm. About 8 g of water was dried in the range. After drying, the zeolite adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.

Comparative Example 2
A 20 mL screw tube was charged with 2 g of a zeolite particle group (manufactured by Zeobuilder) (average particle size: 4.0 μm, D90: 6.2 μm) and 8 g of a polyacrylic acid Na aqueous solution having a weight average molecular weight of 1200. 10 g of zeolite polymer dispersion A liquid was prepared. The concentration of the aqueous polymer solution was adjusted with ion-exchanged water so that the solid content of the polymer was 5.3 parts by mass with respect to 100 parts by mass of the zeolite particle group. Next, the prepared zeolite-polymer dispersion was subjected to ultrasonic waves, and it was confirmed by LA950 that the average particle size was 4.0 μm and D90 was 6.2 μm. Then, the zeolite-polymer dispersion was placed in a 20 cm diameter evaporating dish. It was dripped, and about 8 g of water was dried with a microwave oven. After drying, the polymer-treated zeolite-containing solid adhering to the evaporating dish was scraped with a spatula and pulverized in a mortar so that the average composite particle size was 5.4 μm and D90 was 7.9 μm, to obtain a zeolite composite particle group. Table 1 shows the results of the cloth residue evaluation using this sample.

Comparative Example 3
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 2500, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.

Comparative Example 4
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 3500, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.

Comparative Example 5
The polymer type was changed to polyacrylic acid Na having a weight average molecular weight of 4000, a sample was prepared by the same method as in Comparative Example 1, and evaluation was performed by the same method. The evaluation results are shown in Table 1.

Comparative Example 6
Samples were prepared in the same manner as in Comparative Example 1, and the evaluation was made in the same manner with the polymer type being acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 5000. went. The evaluation results are shown in Table 1.

Comparative Example 7
The polymer type was changed to acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 10,000, a sample was prepared in the same manner as in Comparative Example 1, and the evaluation was performed in the same manner. went. The evaluation results are shown in Table 1.

Comparative Example 8
Samples were prepared in the same manner as in Example 1, except that the amount of polyacrylic acid Na having a weight average molecular weight of 50000 was changed as shown in Table 1 and evaluated by the same method. The evaluation results are shown in Table 1.

Comparative Example 9
A zeolite composite particle group was produced by a method according to Example 1 of JP-A-4-501730. Specifically, 69.5 parts by mass of zeolite (average particle size: 4.0 μm, D90: 6.2 μm) (a ratio in a total of 100 parts by mass of zeolite, polymer, and water) was added to a granulator (5 L Leedige mixer). In the following, the same applies to this example) and a powdery polymer (Socharan CP5, manufactured by BASF, acrylic acid / maleic acid copolymer Na, weight average molecular weight 70,000) at a ratio of 8.8 parts by mass, a total of 300 g was charged, and the spindle rotation speed was 11 Powder mixed for 2 seconds. Next, 21.7 parts by mass of water was added dropwise over 270 seconds, and granulated for 5 minutes while mixing dropwise. After granulation, it was dried at 105 ° C. with an electric dryer until the total mass was reduced by 5%. After drying, about 15% of coarse particles were sieved with a sieve having a mesh size of 1.4 mm. The average composite particle size of the obtained zeolite composite particle group was 571 μm, and D90 was 625 μm. Using this, evaluation was performed in the same manner as in Comparative Example 1. The evaluation results are shown in Table 1.

(Measurement of average particle diameter of Comparative Example 9)
It calculated | required using the sieve prescribed | regulated to JISZ8801. That is, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 355 μm, 250 μm, 180 μm, and 125 μm, a low tap machine (made by HEIKO SEISAKUSHO, tapping: 156 times / minute, rolling: 290 times / minute), 100 g of the sample was shaken for 10 minutes and sieved, and then the pan and each sieve in the order of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm When the weight frequency is accumulated on the top, the opening of the first sieve where the accumulated weight frequency is 50% or more is aμm, and the opening of the sieve that is one step larger than aμm is bμm. C% on the frequency of weight up to the sieve, and on the aμm sieve If the amount frequency was d%, the average particle diameter is calculated by the following equation.
Average particle size = 10 ^A

Example 10
Into a 20 L pail, 4 kg of zeolite particle group (Zeobuilder) (average particle size 4.0 μm, D90 is 6.2 μm) and 16 kg of polyacrylic acid Na aqueous solution with a weight average molecular weight of 50,000 were charged, and 20 kg of zeolite polymer A total of 100 L of five dispersions were prepared. The concentration of the polymer aqueous solution is adjusted with ion-exchanged water so that the solid content of the polymer is 5% by mass with respect to the zeolite, and then using a spray drying apparatus (Sakamoto Giken Co., Ltd., SPRAY DRYER, MODEL TRS-5W2N), The zeolite polymer dispersion is spray-dried under the conditions of an air spray pressure of 0.5 MPa using a two-fluid nozzle, a blowing rate of 9 kg / min, a blowing temperature of 140 ° C., and a feed rate of 7 kg / hr to obtain a powder (granular composition). Obtained. Next, the resulting spray-dried dough was pulverized with an atomizer model E II W 7.5 manufactured by Dalton Co., Ltd., with a hammer peripheral speed of 60 Hz, a feed peripheral speed of 10 Hz, and a screen of 0.7 φ, and then a stainless steel pad. And then shelf-dried with an electric dryer at 105 ° C., and shelf-dried for about 8 hours so that the VL becomes 1% or less, and then pulverized again with an atomizer, the average composite particle size is 4.0 μm, and D90 is 5 A zeolite composite particle group of .8 μm was obtained. Table 2 shows the results of cloth residue evaluation using this sample.

Example 11
The polymer type was acrylic acid / maleic acid copolymer Na (acrylic acid / maleic acid = 50/50, molar ratio) having a weight average molecular weight of 50000, and the average composite particle size was 4.0 μm and D90 in the same manner as in Example 10. Obtained a zeolite composite particle group having a particle size of 5.8 μm. Table 2 shows the results of cloth residue evaluation using this sample.

Example 12
Acrylic acid / maleic phosphate copolymer Na (acrylic acid / maleic acid = 50/50 molar ratio) of the weight average molecular weight 70,000 types of polymer, the average composite particle size 4.0μm in the same manner as in Example 10, A zeolite composite particle group with D90 of 5.8 μm was obtained. Table 2 shows the results of cloth residue evaluation using this sample.

Comparative Example 10
4kg of zeolite particle group (Zeobuilder Co., Ltd.) (average particle size 4.1μm, D90 = 6.2μm) in a 20L pail can and 16kg of ion-exchanged water were weighed and 5 pieces of 20kg zeolite dispersion were prepared to make 100L in total. did. Next, a zeolite composite particle group having an average composite particle size of 4.2 μm and D90 of 6.2 μm was obtained from the prepared zeolite dispersion by the same method as in Example 10. Using this sample, cloth residue evaluation was performed. The results are shown in Table 2.

  In Examples 1 to 12, the presence or absence of coating of the zeolite particles with the polymer was confirmed by the above method, and it was confirmed that the particles were coated. However, in Comparative Examples 1, 8, 9, and 10, when surface analysis was performed by ESCA, Si, which is a component of zeolite, was detected.

Examples 13-15 and Comparative Examples 11-12
Using a Redige mixer FKM-130D (manufactured by Matsubo Co., Ltd.) high-speed mixer, powder detergent compositions having the compositions shown in Table 3 were produced in units of 35 kg. This mixer is equipped with a shearing machine corresponding to a stirring blade and a crushing / dispersing chopper. The operation was performed as follows. Table 3 shows the results of the cloth residue evaluation of the obtained powder detergent composition.

<Powder mixing>
Solid component, sodium carbonate (light ash: manufactured by Central Glass Co., Ltd., average particle size 56.1 μm) 12.03 parts by weight, sodium sulfate (neutral anhydrous sodium sulfate: manufactured by Shikoku Kasei Co., Ltd., average particle size 110 μm) ) 4.10 parts by weight and 0.11 part by weight of the fluorescent dye were measured using a Redige mixer under conditions of stirring blade rotation speed 130 rpm (circumferential speed 3.4 m / s) and shearing machine rotation speed 2850 rpm (circumferential speed 27 m / s). For 1 minute.

<Neutralization>
While operating the mixer under the same conditions as described above, 5.80 parts by weight of LAS-S and 0.40 part by weight of 98% sulfuric acid which had been mixed in advance were added over 4 minutes. During this time, the mixer jacket was cooled by passing water at 25 ° C. At this stage, the temperature reached a maximum of 75 ° C. Throughout this stage, the reaction mixture was granular.

  After addition of LAS-S, the mixer is continuously operated for 1 minute under the same conditions, 0.48 parts by weight of fatty acid (14 to 18 carbon atoms, 40 to 50 ° C.) is added, and the mixer is operated for 1 minute under the same conditions. The neutralization reaction and the granulation operation were completed.

  Further, aeration (300 L / min) was performed immediately after the start of LAS-S addition until the completion of the neutralization reaction.

<Addition of liquid components>
Further, 2.10 parts by weight of a nonionic surfactant (primary alcohol having 12 to 14 carbon atoms added with 6 mol of EO on average) was added, mixed for 1 minute, and then the zeolite composite particles shown in Table 3 8.70 parts by weight were added and the mixer was run for an additional 2 minutes.

<After blend>
Using a rotating drum, 0.18 parts by weight of the enzyme and the detergent composition obtained above were mixed and 0.07 parts by weight of the fragrance was sprayed to obtain a high bulk density powder detergent composition (bulk density 860 g / L). Got.

The components used here are as follows.
LAS-S: acid precursor of linear alkylbenzene sulfonate sodium, “Neopelex GS” manufactured by Kao Corporation
LAS-Na: linear alkylbenzene sulfonate having 12 to 14 carbon atoms in the alkyl group Nonionic surfactant: A mixture of primary alcohols having 12 to 14 carbon atoms with an average of 6 mol of EO.
Fatty acid: Fatty acid having an alkyl group having 14 to 18 carbon atoms, “Lunac P-95” manufactured by Kao Corporation
・ Fatty acid sodium: Fatty acid sodium having an alkyl group having 14 to 18 carbon atoms ・ Fluorescent dye: Ciba Geigy's “Chino Pearl CBS-X” and Sumitomo Chemical Co., Ltd. “Wytex SA” 1/1 (mass ratio) Formulated with: Enzyme: Cellulase K (described in JP-A-63-264699)

The components (partial) in the table are as follows.
LAS-Na: linear alkylbenzene sulfonate having 12 to 14 carbon atoms in alkyl group Fatty acid sodium: sodium salt of fatty acid having an alkyl group having 14 to 18 carbon atoms

Claims (11)

A zeolite particle group (a) having an average particle diameter of 1 to 8 μm is mixed with an aqueous solution of a polycarboxylic acid polymer (b) having a weight average molecular weight of 20,000 to 300,000 and having a monomer structural unit having a carboxylic acid group. Thereafter, a zeolite composite particle group obtained by drying,
Average particle size of 2 10 .mu.m,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more.
Zeolite composite particles. The zeolite composite particle group according to claim 1, wherein the zeolite particle group (a) has a volume basis 90% (D90) particle size of 12 µm or less. The zeolite composite particle group according to claim 1 or 2, wherein the drying is spray drying or thin film drying. The zeolite according to any one of claims 1 to 3, wherein the polycarboxylic acid polymer (b) is a polymer selected from polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and maleic acid, and a sodium salt thereof. Complex particle group. A zeolite composite particle group comprising a zeolite particle group (a) and a polycarboxylic acid-based polymer (b) having a monomer constituent unit having a carboxylic acid group and a weight average molecular weight of 20,000 to 300,000,
Average particle size of 2 10 .mu.m,
The volume diameter of 90% (D90) is 12 μm or less,
The ratio of the polycarboxylic acid polymer (b) to 100 parts by mass of the zeolite particle group (a) is 5 parts by mass or more,
Zeolite particles are coated with a polycarboxylic acid polymer,
Zeolite composite particles. The zeolite composite particle group according to claim 5, wherein the polycarboxylic acid polymer (b) is a polymer selected from polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and maleic acid, and a sodium salt thereof. The powder detergent composition containing the zeolite composite particle group in any one of Claims 1-6 . After mixing the zeolite particle group (a) having an average particle diameter of 1 to 8 μm with an aqueous solution of a polycarboxylic acid polymer (b) having a weight average molecular weight of 20,000 to 300,000 and having a monomer constituent unit having a carboxylic acid group Dry,
Obtaining a zeolite composite particle group having an average particle diameter of 2 to 10 μm and a ratio of the polycarboxylic acid polymer (b) to 5 parts by mass or more with respect to 100 parts by mass of the zeolite particle group (a);
A method for producing a zeolite composite particle group. The production method according to claim 8 , wherein the drying is performed by spray drying or thin film drying. (A) zeolite composite particles The method according to claim 8 or 9 particle size of 12μm or less of the volume-based 90% of the zeolite particles of the component (D90). The zeolite according to any one of claims 8 to 10, wherein the polycarboxylic acid polymer (b) is a polymer selected from polyacrylic acid, polymethacrylic acid, a copolymer of acrylic acid and maleic acid, and a sodium salt thereof. A method for producing a composite particle group.