JP3442753B2 - Manufacturing method of granules for supporting surfactant - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a surfactant-supporting granule group and a method for producing the same. Further, the present invention relates to a high bulk density detergent particle group and a detergent composition using the surfactant-supporting particle group.

[0002]

2. Description of the Related Art As one of the methods for obtaining a high-density detergent, there is a production method including a step of supporting a liquid surfactant on granules for supporting a surfactant. In the production method, the surfactant-supporting granules are required to have a high capability of supporting a liquid surfactant. That is, the supporting ability required for the surfactant-supporting granules is that a large amount of liquid surfactant can be supported (carrying capacity), and the liquid surfactant once absorbed can be strongly retained inside the granules without exuding ( 2)
It consists of two factors. In each case, the carrying capacity is for blending the surfactant in an amount necessary for cleaning performance, and the carrying capacity is for suppressing the fluidity of the powder detergent, caking and It is important in preventing migration of the liquid surfactant to the container and its surface.

The structure required for the surfactant-supporting granules having a high carrying capacity is to increase the carrying capacity by having a sufficient pore volume inside the granules, and to have a high carrying capacity by having a fine pore diameter. A structure having is desirable. Such a structure can be obtained by using fine particles to form a granule for supporting a surfactant while the mutual particles are in contact with each other and maintaining sufficient voids. As a supply source of these fine particles,
Sodium carbonate, a typical water soluble salt in detergent compositions, can be utilized. Sodium carbonate forms monohydrate of sodium carbonate in the preparation liquid, or burkeite which is a double salt with sodium sulfate, but they form fine needle-like crystals, and the inside of the surfactant-supporting granules. Can be a base material that forms an effective supporting site.

As a technique for realizing this, Japanese Patent Laid-Open No. 62-
No. 112697 discloses that crystal growth was controlled by incorporating an effective amount of a crystal growth modifier, which is an organic material having at least three carboxyl groups in the molecule, into a surfactant slurry prior to sodium carbonate. A method is disclosed in which sodium carbonate monohydrate and / or burkeite is formed in a slurry, and then the slurry is spray-dried to obtain a dry powder (surfactant-supporting granules) having a high adsorption capacity.

However, the supporting ability of the surfactant-supporting granules obtained by this method was not sufficient. One of the causes of this is that the amount of fine burkeite dispersed in the slurry before spray drying is insufficient, and the amount of fine crystals of burkeite is not sufficient even in the granules obtained by spray drying. Is mentioned. The fine needle-like crystal burkeite is an effective base for improving the carrying capacity, but the burkeite in the present technology uses the dissolved sodium sulfate and granular sodium carbonate added later to form the granular carbonate. Since it is formed on the surface of sodium or in the vicinity of the surface, most of it exists as a strong aggregate having a large particle size. Therefore, there are few burkeite particles in the form of fine needle-like crystals formed in the slurry, and burkeite particles that can originally become fine needle-like crystals are in agglomerated state with a large particle size in the granules even after spray drying. However, sufficient supporting ability could not be expressed due to the large size. Another cause is that the polycarboxylate polymer has not been sufficiently selected as a crystal growth regulator for burkeite, and therefore has a low effect of precipitating burkeite as fine needle-like crystals.

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a surfactant-supporting granule group excellent in carrying ability (loading capacity / loading power) of a liquid surfactant composition, a method for producing the same, and the surfactant. It is an object of the present invention to provide a detergent particle group using the agent-supporting granules and a detergent composition containing the detergent particle group.

[0007]

[Means for Solving the Problems] That is, according to the present invention, [1] the weight average molecular weight is 3,000 to 100,000, and the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value. The ratio of particles having a particle size on the large particle size side of 32 nm or less and a particle size exceeding 800 nm is 70%.
Hereinafter the acrylic polymer is, spray drying a preparation liquid containing sodium carbonate and sodium sulfate, it viewed including the burkeite, sodium carbonate and sodium sulfate
The total content is 19/1 by weight relative to the polymer content.
- [1/2] is a method of producing granules for supporting a surfactant, and [2] 0.01-3 [mu] measured by a mercury porosimeter.
The mode diameter of the pore volume distribution of m is 1.5 μm or less,
Granules for supporting a surfactant obtained by the production method according to [1], which has a pore volume of 0.01 to 3 μm of 0.3 mL / g or more and a granule strength of 15 MPa or more, [3] weight average molecular weight Is 3,000 to 100,000, and the height of the peak including 10 nm in the light scattering measurement is attenuated to half of its maximum value. The particle size on the large particle size side is 32 nm or less and has a particle size exceeding 800 nm. 70% of particles
The following acrylic acid-based polymer is contained in an amount of 5 to 30% by weight, and sodium carbonate and sodium sulfate are in a weight ratio of 1/1.
0 to 10/1 and the total content of sodium carbonate and sodium sulfate is 19/1 in weight ratio with respect to the polymer content.
To 100 parts by weight of the surfactant-supporting granules according to [2] or [3], the surfactant composition is 10 parts by weight. ~ 1
Detergent particle group supported by 00 parts by weight, [5] Average particle size of 150 to 500 μm, bulk density of 500 containing 50 to 100% by weight of the detergent particle group described in [4] above.
~ 1000 g / L for a detergent composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION 1. Definition of terms The surfactant-supporting granule of the present invention is a granule obtained by spray-drying a preparation liquid containing an acrylic acid polymer and sodium carbonate and sodium sulfate, and the surfactant composition The granules used for supporting the particles are referred to as aggregates, and the aggregate is referred to as the surfactant-supporting granules. The detergent particles are particles containing a surfactant and a builder, which are obtained by supporting the surfactant composition on the surfactant-supporting granules, and the detergent particle group means an aggregate thereof. The detergent composition includes a detergent particle group, and a detergent component (for example, a builder granule, a fluorescent dye, an enzyme, a fragrance, an antifoaming agent, a bleaching agent, and a bleach activator) which is separately added to the detergent particle group if desired. Etc.) is meant. The acrylic acid-based polymer is a polymer and / or copolymer obtained by a polymerization reaction containing acrylic acid and / or a salt thereof as a monomer component. The preparation liquid means a solution or slurry to be subjected to spray drying. Generally, burkeite refers to a double salt composed of sodium carbonate and sodium sulfate in a molar ratio of 1: 2, but the burkeite in the present invention is composed of sodium carbonate and sodium sulfate including other than the above molar ratio. Double salt. The water-soluble salts have a solubility of 0.
It has a molecular weight of 5 g or more and a molecular weight of less than 1,000. The water-soluble polymer has a solubility of 0.5 in 100 g of water at 25 ° C.
It is an organic polymer having a molecular weight of at least g and a molecular weight of at least 1,000. The water-insoluble substance is a solid having a solubility of less than 0.5 g in 100 g of water at 25 ° C. The surfactant composition is a composition containing a liquid and / or paste-like surfactant when loaded on the surfactant-supporting granules.

2. The properties required for the surfactant-supporting granules (hereinafter, also referred to as supporting granules) to exhibit high carrying capacity are as follows.
Having a large amount of space (supporting site) for supporting a liquid and / or paste-like surfactant composition (hereinafter, also referred to as a liquid composition) inside the granules, that is, a liquid having a large pore volume inside the granules It has a large carrying capacity for the composition, a small pore size inside the granules, and a strong carrying ability for the liquid composition. Further, the supporting granules need to have a granule strength that can withstand an operation in manufacturing detergent particles, such as mixing for supporting a liquid composition. Further, from the viewpoint of enhancing the cleaning performance of the detergent particles and the detergent composition, the supporting granules are desired to have a high ability to support a liquid composition and a high builder ability. Here, the builder ability means the ability to enhance or enhance the cleaning performance of the surfactant.

Therefore, since it acts as an alkaline agent exhibiting a suitable pH buffer region in the washing liquid, sodium carbonate used as a typical builder in the detergent composition and / or the ionic strength in the washing liquid is increased to increase the sebum. Since sodium sulfate, which is used as a typical builder in a detergent composition, is suitable for cleaning dirt and the like, studies were conducted to form a structure having many fine spaces inside the granules as described above.

As a result, an acrylic acid-based polymer having specific properties and a preparation liquid containing sodium carbonate and sodium sulfate were prepared, and the preparation liquid was spray-dried to precipitate sodium carbonate in the granules. It was found that a crystal of burkeite, which is a double salt derived from sodium sulfate, becomes fine and a supporting granule group having a fine spatial structure in the above-mentioned granule can be obtained.

Further, the acrylic acid-based polymer is a water-soluble polymer having an action of improving the cleaning performance, and more specifically, it has an action of dispersing solid particle dirt such as mud particles from clothes to a washing bath and a solid substance. It is a builder having an action of preventing particle dirt from reattaching to clothing and an action of trapping metal ions such as calcium ions which inhibit the washing action of a surfactant. Then, the supporting granules obtained by using the acrylic acid-based polymer having both the property of miniaturizing the above-mentioned barkeite and the property of highly enhancing the cleaning performance thereof are excellent supporting properties for the surfactant composition. In addition to the ability, it has an excellent builder ability.

The acrylic acid-based polymer having the above-mentioned specific properties has a property of refining burkeite crystals precipitated in the step of preparing the preparation liquid and the step of spray-drying the preparation liquid, and is high. It has a builder ability. Specifically, the weight average molecular weight measured by the following weight average molecular weight (1) is 3,000 to 100,000, and the height of a peak including 10 nm in the following light scattering measurement (2) is attenuated to half the maximum value. The ratio of particles having a particle size on the large particle size side of 32 nm or less and a particle size of more than 800 nm is 70% or less, and if necessary, the dispersion performance of mud particles according to the following dispersion capacity measurement (3) is 0. Calcium ion trapping ability of 160 mgCa according to the following trapping ability measurement (4).
It is preferable that the stability constant for calcium ion is at least 2.6 by CO ₃ / g or more and the following stability constant measurement (5).

Here, the weight average molecular weight measurement (1), the light scattering measurement (2), the dispersibility measurement (3), the trapping ability measurement (4) and the stability constant measurement (5) will be described in detail and each characteristic will be further described. A preferred embodiment of is described.

Weight average molecular weight measurement (1): For the measurement of the molecular weight of an acrylic acid-based polymer, 1. Conversion standard substance: Polyacrylic acid (AMERICAN STANDAR
DS CORP) 2. Eluent: 0.2 mol / L phosphate buffer / CH ₃ CN:
9/1 (capacity ratio) 3. Column: PWXL + G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation) 4. Detector: RI 5. Sample concentration: 5 mg / mL 6. Injection volume: 0.1 mL 7. Measurement temperature: 40 ° C 8. Flow rate: 1.0 mL / min.

Here, the preferred range of the weight average molecular weight of the acrylic acid-based polymer in the present invention is 3,000 to 100,000, but the weight average molecular weight is increased to increase the granule strength of the supporting granules, and From the viewpoint of enhancing the builder ability by adjusting the weight average molecular weight, more preferably 3,000 to 80,000,
More preferably 40,000 to 60,000, and even more preferably 5,000 to 5
10,000, most preferably 6,000 to 30,000.

Light scattering measurement (2): 40% by weight of solid content in a 50 mL sample tube (hereinafter, solid content is shown in%)
8.0 g of a sample of the acrylic acid-based polymer is weighed and diluted with 20 mL of ion-exchanged water. At this time, when the solid content of the acrylic acid polymer sample is different from 40%,
The amount of the ion-exchanged water is adjusted so that the solid content in the solution becomes equal. 1.0 g of sodium sulfate (anhydrous neutral mirabilite: manufactured by Shikoku Kasei Co., Ltd.) was added to this aqueous solution with stirring in a constant temperature bath adjusted to 50 ° C., followed by sodium carbonate (dense ash: central glass ( KK) 5.
Add 0 g and dissolve. After that, 60 minutes, 50 ℃
After continuing to keep warm at 25 ° C, it is allowed to cool in a room at 25 ° C for 2 hours.

The above sample was filtered with a 0.8 μm filter (SLAA025LS manufactured by Millipore), placed in a cell with an inner diameter of 12 mm, and the temperature was adjusted to 25 ° C., and then DLS-7000DH manufactured by Otsuka Electronics Co., Ltd. was used. The particle size is measured by the dynamic light scattering method. The scattering angle is 90 °,
The light source is an Ar ⁺ laser having a wavelength of 488 nm and an output of 75 mW, and the analysis is performed by fitting using the Markt method to calculate a histogram based on the scattering intensity. As shown in FIG. 1, the histogram has a horizontal axis of particle diameter and a vertical axis of ratio.

Here, the broadening of the peak containing 10 nm of the particle size distribution of the acrylic acid-based polymer measured by light scattering to the large particle size side indicates the degree of association of the polymer molecules. That is, the larger the spread to the large particle size side is, the more the polymer molecules are associated with each other, and the smaller the spread to the large particle size side is, the better the polymer molecules are dispersed. Means As a result of examining the relationship between the spread of the peak containing 10 nm observed in the particle size distribution of the acrylic acid-based polymer to the large particle size side and the crystal growth regulating action on burkeite, the spread to the large particle size side is small. It is considered that the burkeite that precipitates in the preparation process of the preparation liquid and the spray drying process is made fine and acicular.

The extent to which the peak containing 10 nm observed in the particle size distribution obtained by dynamic light scattering measurement of an acrylic acid-based polymer extends toward the large particle size side is 10 nm.
Is defined by the particle size on the large particle size side (hereinafter referred to as the half-valued particle size) at which the height of the peak including is attenuated to half the maximum value (for example, FIG. 1). That is, the larger the half-particle diameter, the larger the spread toward the large particle size, and the smaller the half-particle size, the smaller the spread toward the large particle size.

The preferred half-particle diameter of the acrylic acid-based polymer in the present invention is 32 nm or less, but it acts by the crystals of verkeite which precipitates in the preparation step of the preparation liquid and the spray drying step, and the barkeite is finely divided. From the viewpoint of the above, it is more preferably 30 nm or less, further preferably 28 nm or less, and particularly preferably 26 nm or less,
Most preferably, it is 24 nm or less.

In this measurement, the sample solution was 0.8 μm (80 μm).
Although it is performed after filtering with a filter of 0 nm),
Particle sizes above 800 nm may be observed. It is considered that these are associated with the acrylic acid polymer. As a result of examining the relationship between the ratio of particles having a particle size of more than 800 nm and the absorptivity of the surfactant-supporting granules produced by using the acrylic acid-based polymer to a liquid composition, 8
It has been found that when a high proportion of particles having a particle size of more than 00 nm is used, the absorbability of the supporting granules to the liquid composition is lowered. The ratio of particles having a particle size of more than 800 nm is the same as the increase in the above-mentioned half particle size,
It is considered that the acrylic acid-based polymer exhibits the association property, and there is a concern that the crystal growth regulating action may be lowered, but the acrylic acid-based polymer having a high ratio of particles having a particle size of more than 800 nm has a high film-forming property. Therefore, the properties of the coating film formed on the surface of the surfactant-supporting granules make it difficult for the liquid composition to pass through. That is, it is considered that such an acrylic acid-based polymer deteriorates the absorbability of the surfactant-supporting granules with respect to the liquid composition.

The proportion of particles having a particle size of more than 800 nm in the acrylic acid-based polymer of the present invention is 70% or less, but the absorption property of the surfactant-supporting granules to the liquid composition is increased. From the viewpoint of increasing the loading amount of the liquid composition of the loading granules, it is preferably 60% or less, more preferably 50% or less, still more preferably 40% or less, and most preferably 30% or less.

Further, the acrylic acid-based polymer has the following HPL
It is preferable to have the following discharge pattern in C measurement. The HPLC measurement will be described below.

HPLC measurement: Column made by Tosoh Corporation
Using TSK Gel G2500pwxl, at a measurement temperature of 40 ° C., ion-exchanged water is passed through the mobile phase at 0.5 mL / min, and detection is performed by a differential refractometer (Showa Denko SE-71) at a sampling interval of 50 milliseconds. First, glycerin (special grade, for example, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) of 0.
A 2% aqueous solution is prepared, and 50 μL of the solution is injected into the column to measure the emission pattern of glycerin as a reference substance. In addition, this measurement is performed twice. Next, solids 4
A sample of acrylic acid polymer preliminarily adjusted to 0 ± 1% was diluted 100 times with ion-exchanged water to prepare a sample solution, and 50 μL was injected into the column to discharge the acrylic acid polymer. To measure. This measurement is performed twice.

The difference in the discharge pattern in the HPLC measurement of the acrylic acid type polymer can be confirmed by the relative full width at half maximum described below. First, as shown in FIG. 1, a straight line is drawn from the baseline to the baseline, and a vertical line is drawn from the point where the height has the maximum value at the measured peak, and the half width is obtained. Each half width of the two measured glycerin and glycerin the average value of the half width of each acrylic polymer samples (A ₁₎ and the half-width of the acrylic polymer (A _2), the relative half-width by the following equation Find (B). B = A ₂ / A ₁ Here, the above HP of the acrylic acid-based polymer in the present invention is used.
A preferable relative full width at half maximum of the discharge pattern in the LC measurement is 1.4 or more, more preferably 1.45 or more,
It is more preferably 1.5 or more, and most preferably 1.55 or more.

Further, the acrylic acid-based polymer preferably has a high adsorption property in the adsorption rate measurement (hereinafter referred to as adsorption rate measurement) for barcareite in the following preparation liquid. The adsorption rate measurement will be described below.

Measurement of adsorption rate: 558 g of ion-exchanged water (prepared water) was weighed in a 1 L stainless beaker, and a stirring blade equipped with three 2 × 4 cm propeller blades was placed at 200 r / in a constant temperature bath adjusted to 50 ° C. Rotate at a speed of min and stir. To the ion-exchanged water, 154 g of sodium sulfate (anhydrous neutral Glauber's salt: manufactured by Shikoku Kasei Co., Ltd.) is added and stirred for 10 minutes to dissolve. Then sodium carbonate (dense ash:
158 g of Central Glass Co., Ltd. was added over 15 seconds, and after 5 seconds, 220 g of an aqueous solution sample of an acrylic acid-based polymer, which had been adjusted to a solid content of 40% (concentrated or added with ion-exchanged water), was added over 30 seconds. And add. Part 10
After a minute, sodium chloride (Baked salt S: manufactured by Nippon Salt Co., Ltd.)
Add 51 g over 5 seconds and continue stirring for 60 minutes. Then, about 100 g of a part of the prepared liquid under stirring was weighed in a centrifugal sedimentation tube, and while maintaining the temperature of 50 ° C., a centrifugal separator (manufactured by Domestic Centrifuge Co., Ltd., model H300) was used for 10000 r.
Centrifuge for 5 minutes at pm rpm.

A portion (3 g) of the supernatant liquid is precisely weighed and dried in a dryer (DP32 manufactured by Yamato) at 130 ° C. for 10 hours to quantify the water content (solid content) in the supernatant liquid.

In order to quantify the amount of inorganic ions dissolved in the supernatant liquid, 3 g of the supernatant liquid was precisely weighed to 100 m.
The solution is made up to 1 to give a solution for quantifying inorganic ions. 5 ml of this solution is sampled with a whole pipette, and a 100 ml volumetric flask is filled up to prepare a sample solution for measuring CO ₃ ^2- ions. Further, 3 ml of this solution is sampled with a whole pipette, and a 50 ml volumetric flask is filled with the solution to prepare a sample solution for measuring Cl ⁻ and SO ₄ ²⁻ ions. In addition, ion exchange water is used for measuring up.

The quantitative determination of each inorganic ion is carried out by a calibration curve method using an ion chromatography method.

Measurement conditions (SERIES4500I manufactured by DIONEX Japan) (CO ₃ ^2- ion quantification) Column: ICE-AS1 Eluent: 0.1 mM octanesulfonic acid-containing aqueous solution flow rate: 1.0 mL / min Suppressor column: AMMS-ICE Removal solution: Detection of 5 mM TBAOH, 50 mM boric acid-containing aqueous solution: Electrical conductivity Sample injection amount: 25 μL

(Quantification of Cl ⁻ and SO ₄ ²⁻ ions) Column: AS9-HC4 eluent: 5 mM NaHCO ₃ , 12 mM Na ₂ CO ₃ -containing aqueous solution flow rate: 1.0 mL / min Suppressor column: AMMS-II removing solution: 25mN sulfuric acid aqueous solution detection: electrical conductivity Sample injection volume: 25μL

The ion concentration (mg / L) in the supernatant was determined, and the weights of Na ₂ SO ₄ , Na ₂ CO ₃ and NaCl in ₃ g of the supernatant were calculated.

On the other hand, the quantification of the acrylic acid-based polymer in the supernatant is determined by gel permeation chromatography (GP
C) method using a calibration curve method. The sample solution used for the ion chromatography measurement is used.

Measurement conditions Column: G4000PWXL + G25000PWXL Eluent: 0.2M phosphate buffer solution / CH ₃ CN = 9/1 (volume ratio) Flow rate: 1.0 mL / min Column temperature: 40 ° C. Detector: Differential refractometer sample injection Volume: 100 μL

From the ratio conversion of the weight of water in 3 g of the supernatant obtained by the above drying method to the total weight of water in the preparation liquid (weight of water charged + weight of water of the charged acrylic acid polymer aqueous solution),
Dissolved Na ₂ SO ₄ and Na ₂ C on the preparation scale
The weights of O ₃ , NaCl and acrylic acid based polymer are determined. Therefore, the weight of the precipitated and / or undissolved substance (hereinafter referred to as the weight of the deposit) for each component is determined by the following formula. Precipitate weight = Charged weight-Dissolved weight

However, NaCl was completely dissolved in this preparation liquid. If the dissolved weight exceeds the charged weight, the total dissolution is taken.

Assuming that the weight of the acrylic acid polymer precipitate is A, the weight of the Na ₂ SO ₄ precipitate is B, and the weight of the Na ₂ CO ₃ precipitate is C, the acrylic acid polymer becomes barkeite. The adsorption rate of is calculated by the following formula. Adsorption rate (%) = A / (B + C) × 100

Here, the preferred adsorption rate of the acrylic acid-based polymer in the present invention to burkeite is 2.5% or more. Further, from the viewpoint of further miniaturizing the burkeite by the action of the acrylic acid-based polymer on the crystal of the burkeite precipitated in the preparation step of the preparation liquid and the spray drying step, more preferably 3% or more, further preferably 4 % Or more, preferably 5% or more, and most preferably 6% or more. Further, when a preparation liquid containing an acrylic acid polymer is spray-dried, the obtained granules have a structure covered with a coating film containing the polymer, and the absorption of the liquid composition from the surface tends to be delayed, It was also found that the use of the above acrylic acid-based polymer having a high adsorption rate to burkeite improves the absorbability.

Here, the high adsorption rate of the acrylic acid-based polymer to the burkeite measured by the above-mentioned adsorption rate measurement means that the acrylic acid-based polymer has a high interaction with the burkeite as described above. That is, it means that the crystal growth regulating effect on burkeite is strong. When an acrylic acid-based polymer having a high adsorption rate to burkeite is used, the resulting supporting granules have a small pore size and a high supporting capacity for a liquid composition and a high granule strength. or,
When an acrylic acid-based polymer having a high adsorption rate to burkeite is used, a phenomenon in which fine burkeite crystals are precipitated can be confirmed in the preparation liquid prepared by the above adsorption rate measurement.

As the confirmation method, for example, the following in-line type particle droplet monitoring system (LASENT) is used.
"TSUB-TEC M100" manufactured by EC) can be used.
The confirmation method will be exemplified below. A preparation liquid is prepared in the same stainless beaker as in the above adsorption rate measurement by the same method and procedure. At this time, an in-line type particle monitoring system (TSUB-TEC M100) manufactured by LASENTEC Co., Ltd. is infiltrated at an angle of 45 ° with respect to the liquid surface of the stationary preparation liquid, and attached at a position 3 cm below the liquid surface. This allows
The particles always collide with the window surface when stirred.
The software is "Control Interface for FBRM Ver5.4.
Build 58b "(manufactured by LASENTEC) is used, and the focus position is set to a position in which a focus is placed inside by 0.02 mm from the window surface. One measurement time (Me
asurement Duration is 14.5 seconds, moving average (Averag
ing) is 10 and the count number (count number / second) and particle size distribution (code length distribution) are measured. The phenomenon in which fine burkeite crystals are precipitated can be confirmed by comparing the measured value immediately before the addition of sodium chloride (a) with the measured value at the time point 60 minutes after the addition of sodium chloride (b). . That is, the finer barkite precipitated by the addition of sodium chloride means that the count number increases and / or the average particle size of the precipitate (median code: particle size when the cumulative value of the number of particles is 50%). ) Can be confirmed by being smaller. Here, the average particle size of the precipitate is the average particle size obtained from the particle size distribution obtained by subtracting the particle size distribution at time point (a) from the particle size distribution at time point (b).

From the viewpoint that the loading ability of the loading granules is improved by using an acrylic acid polymer having the effect of producing fine barkeite in the preparation liquid, the acrylic acid polymer is The count number obtained by subtracting the count number at the time point (a) from the count number in (b) is preferably 1000 counts / second or more, more preferably 1 count.
The acrylic acid-based polymer has a count of 250 counts / second or more, more preferably 1500 counts / second or more, and most preferably 1750 counts / second or more. In addition, the acrylic acid-based polymer has an average particle size of precipitates in the adsorption rate measurement of preferably 40 μm or less, more preferably 35 μm.
Or less, more preferably 30 μm or less, and most preferably 2
It is an acrylic acid-based polymer having a thickness of 7.5 μm or less.

The characteristics of the acrylic acid-based polymer as described above, that is, the ratio of the half particle size to the large particle size in the light scattering measurement, the half-value width in the HPLC measurement, and the adsorption rate to burkeite are as follows. Derived from the type of end groups and the structure of the main chain of the united body.

As the terminal group, those having a high polarity are desirable, for example, those having a sulfonic acid group are suitable.
Depending on the structure of the main chain, which will be described later, sufficient performance may be exhibited even with a low-polarity terminal group, and it is not generally specified.

The structure of the main chain means the number of branches and the number of head-to-head or tail-to-tail structures.
The polymer having less disordered structure is suitable for the present invention. Such a polymer can be obtained by carrying out the polymerization under mild conditions, paying attention to the points described below.

The head-to-head or tail-to-tail structure is caused by a decrease in the selectivity of the reaction site in the growth reaction during polymerization. It is desirable to lower the temperature in order to obtain a polymer suitable for the present invention. At this time, it is also effective to carry out the polymerization by a redox method from the viewpoint of carrying out the polymerization at a relatively low temperature. In addition, as the polymerization by the redox method, COMPREHENSIVE POL
YMER SCIENCE, Volume 3Chai
n Polymerization Part 1,1
23-139, PERGAMON PRESS, 1
989 or Japanese Examined Patent Publication No. 2-24283.

Since branching occurs when α hydrogen of the main chain is abstracted by a radical, it is important to suppress the activity of the radical in order to obtain a polymer suitable for the present invention. Specifically, it is desirable to lower the temperature during polymerization or lower the initiator concentration. From the viewpoint of lowering the polymerization temperature, it is effective to carry out the polymerization by the redox method here as well. Care should be taken that the initiator concentration does not become too high not only for the whole but also locally, so that the dropping is carried out at a low concentration, the stirring is sufficiently performed, and at any stage of the reaction. However, it is desirable to design the process so that the concentration of the initiator does not become too high temporarily. From the viewpoint of not raising the radical concentration, it is desirable to adopt a stirring method or process that does not cause a local or temporary rise in the temperature as well as the initiator concentration. As the type of initiator, an azo-based initiator is more preferable than a persulfate from the viewpoint that the α-hydrogen abstraction ability is low.

When the molecular weight becomes larger than the target by reducing the concentration of the initiator, it is effective to use a chain transfer agent in combination. Examples of chain transfer agents include sulfurous acid, hypophosphorous acid, phosphorous acid, and mercaptan-based chain transfer agents.

The degree of branching of the actually obtained acrylic acid-based polymer can be measured by the following method.

Branching degree measuring method: GPC equipped with a triple detector (differential refraction, viscosity, light scattering) is measured and calculated by the Jim Stockmeier method. The procedure will be described in detail below. As the Jim Stockmeier method, gel permeation chromatography (Maruzen, 1976) 159
Pp. 161, written by Tsugio Takeuchi and Sadao Mori.

1. GPC condition device: Model 300 T manufactured by Viscotek
DA column: TSK gel G (4000,250 manufactured by Tosoh Corporation)
0) PWxl, temperature: 35 ° C, mobile phase: 0.05 mol
/ L Na ₂ SO ₄ /10% CH ₃ CN, flow rate: 0.8
mL / min

2. Instrument Calibration: Standard Polyethylene Oxide (Viscotek PolyCAL ™)
Inject 0.2 mL of a 1.5 mg / mL solution of PEO (50K) (the solvent is the same as that of the mobile phase described above) into GPC,
From the obtained chromatogram, the refractive index of the solvent is 1.3.
3, weight average molecular weight 51,500, intrinsic viscosity 0.62
The device constant is calculated assuming that 1 (unit is 10 ² cm ³ · g ⁻¹ ) and dn / dc (increase in refractive index) is 0.132.

3. 0.2 mL of a sample solution having a polymer concentration of 3 mg / mL (the solvent is the above-mentioned mobile phase) was injected, and the weight average molecular weight (M
w _b ) and the intrinsic viscosity ([η] _b ) are determined. However, the sample concentration is recalculated assuming that dn / dc of the sample is 0.148.

4. The viscosity constants α and K of the linear polymer are 0.847 and 6.84 × 10 ⁻⁵ , respectively, and [η] _l (intrinsic viscosity of the linear polymer) corresponding to the sample is calculated from the following formula.

[0056]

[Equation 1]

The viscosity constant of the linear polymer is a value calculated from the polymer of Experimental Example 1, assuming that the polymer of Experimental Example 1 described later is linear.

[0058]

[Equation 2]

7. The branching degree (λ) is calculated by the following formula. However, R is 47,000 (= monomer molecular weight / 2 × 100
0). Therefore, λ is 100 carbon atoms in the main chain.
It is the weight average number of branch points per 0. λ = R · Bn / Mw _b

Here, the preferred value of the degree of branching (λ) of the acrylic acid polymer according to the present invention by the above-mentioned measuring method is 9 or less, more preferably 5 or less, and further preferably 2.
It is 5 or less.

Dispersing power measurement (3): First, 71.2 mgC
aCO ₃ / L hardness (using calcium chloride), pH 1
A 0.02 M NH ₄ Cl—NH ₄ OH buffer solution adjusted to 0 is used to prepare an aqueous solution of 5.0 × 10 ⁻⁴ wt% acrylic acid polymer. Next, 50 mL of the aqueous solution is added to 50
Place in a shaker tube (sedimentation tube) of mL, 150 mesh (1
Add 0.05 g of Kanuma Akatamachi (for example, Sakamoto Shoten Co., Ltd.) for horticultural use of 100 μm pass. After shaking vigorously for 30 seconds, ultrasonic irradiation is performed for 5 minutes. The shaking tube (sedimentation tube) was allowed to stand for 2 hours in an environment of 25 ° C., and then the supernatant was collected from a position 3 cm below the liquid surface, using a spectrophotometer for 575 n.
Turbidity is evaluated by measuring the absorbance at the wavelength of m, and the value is taken as the dispersion performance of mud particles. Therefore, the larger the measured value of this absorbance, the higher the dispersion performance of the mud particles.

Here, the preferable dispersion performance of the mud particles of the acrylic acid-based polymer in the present invention is 0.5 or more, but the mud particle dirt is separated from the laundry clothes and uniformly dispersed in the washing bath. From the viewpoint of preventing particles from redepositing on laundry clothes, the particle size is more preferably 0.6 or more, further preferably 0.7 or more, and most preferably 0.8 or more.

Measurement of capture ability (4): First, 0.1M-NH
The potential of the standard calcium ion solution was measured using an ion analyzer (model 920A, manufactured by Orion Co., Ltd.) equipped with a standard calcium ion electrode using ₄ Cl-NH ₄ OH buffer (pH 10), and the calcium ion as shown in FIG. A calibration curve showing the relationship between the logarithm of the concentration and the potential is prepared. Next, 0.1 g of acrylic acid-based polymer (in terms of solid content) is weighed in a 100 ml volumetric flask, and the volume is raised with the above buffer solution. To this, a CaCl ₂ solution (pH 10) corresponding to 20000 ppm (calculated as CaCO ₃ ) is dropped from a buret (a blank is also measured). CaC is dropped
performed by adding l ₂ solution by 0.1-0.2, read the potential at that time, obtaining the calcium ion concentration from the calibration curve of FIG. The calcium ion concentration at the dropped amount A of the sample in FIG. 4 is the calcium ion trapping ability of the sample.

The calcium ion-capturing ability shows how much the acrylic acid-based polymer captures calcium ions in water which lowers the activity of the surfactant. The higher the calcium ion-capturing ability is, the more the supporting granules have the excellent builder ability to suppress the activity reduction of the surfactant.

Here, the preferred calcium ion-capturing ability of the acrylic acid-based polymer of the present invention is 160 mgC
aCO ₃ / g or more, but more preferably 180 m from the viewpoint of exhibiting higher cleaning performance by capturing more calcium ions present in the washing bath.
gCaCO ₃ / g or more, more preferably 190 mgCa
CO ₃ / g or more, most preferably 200 mg CaCO ₃
/ G or more.

Stability constant measurement (5): Numerical values obtained under the following measurement conditions are substituted into the following formula to obtain. 0.001 mol / L, 0.002 mol / L, 0.
003 mol / L, 0.004 mol / L, 0.005
mol / L, 0.006 mol / L, 0.007 mol
/ L, 0.008 mol / L, 0.009 mol / L,
0.01 mol / L calcium ion solution _{0.1M-NH 4 Cl-NH 4} OH buffer at each concentration of (pH 10)
(Using CaCl ₂ ) and add 50 g to a 100 ml beaker. Acrylic acid polymer 50 mg (solid content conversion) is added. Adjust pH to 10. 0.15 g of sodium chloride is added as a calcium ion electrode stabilizer.

Free calcium ion concentration is measured using a calcium ion electrode. Free calcium ion concentration: [Ca] Immobilized calcium ion concentration: [CaS] Free chelate site: [S] Number of chelate sites: [SO] Stability constant: logK, [Ca] × [S] / [CaS] = 1 / K, [S]
= [SO]-[CaS]. Therefore, [Ca] /
[CaS] = 1 / ([SO] × [Ca]) + 1 / [S
O] × 1 / K. Therefore, [Ca] / [CaS] is plotted on the vertical axis and [Ca] is plotted on the horizontal axis, and [SO], K, and logK are calculated from the slope and intercept.

The stability constant for calcium ions is
It shows the degree to which the concentration of calcium ions in the wash water is lowered, and also shows the degree to which calcium ions existing in dirt and the like adhering to laundry clothes are extracted. Then, the higher the stability constant of the acrylic acid polymer is, the more strongly calcium ions can be extracted from the dirt attached to the laundry clothes, and the dirt is easily removed. As described above, the use of the acrylic acid-based polymer having a high stability constant with respect to calcium ions makes the supporting granules have excellent builder ability.

The preferred stability constant of the acrylic acid-based polymer for the present invention with respect to calcium ions is
It is 2.6 or more, but more preferably 2.7 or more, further preferably 2.8 or more, among them, from the viewpoint of exhibiting higher cleaning performance by capturing more calcium ions present in the washing bath. It is preferably 2.9 or more, and most preferably 3.0 or more.

The internal structure of the surfactant-supporting granules of the present invention can be confirmed by using a mercury porosimeter as the pore volume distribution of the supporting granules. Mercury porosimeter (for example, "Poresizer 932" manufactured by Shimadzu Corporation)
0 ”), the distribution of pore volume per pore diameter inside the supporting granules (hereinafter referred to as pore volume distribution)
The larger the pore volume, the larger the carrying capacity of the liquid composition, and the smaller the pore size, the ability to retain the liquid composition once absorbed by the capillarity (supporting capacity).
Will be higher. Therefore, when the pore volume is larger and the pore diameter is smaller, the ability to carry the surfactant is higher,
It is possible to support a large amount of the liquid composition and suppress the spotting of the liquid composition. Therefore, the surfactant-supporting granules of the present invention suitable for supporting a liquid composition have a mode diameter of pore volume distribution (in the obtained pore volume distribution, a pore diameter having the maximum pore volume). It is preferably 1.5 μm or less, more preferably 1.3 μm or less, and 1.1 μm
The following is more preferable, 1.0 μm or less is particularly preferable, and 0.9 μm or less is preferable among them, and 0.8 μm
The following is particularly preferable. The pore volume of the surfactant-supporting granules of the present invention is 0.01
To 3.0 μm, the pore volume is preferably 0.3 mL / g or more, and the pore volume of 0.01 to 2.5 μm is more preferably 0.3 mL / g or more. The pore volume of 0.01 to 2.0 μm is more preferably 0.3 mL / g or more, and the pore diameter is 0.01 to 1.5.
The pore volume of μm is preferably 0.3 mL / g or more, and the pore volume of 0.01 to 1.0 μm is particularly preferably 0.3 mL / g or more.

It has also been found that the smaller the pore size of the supporting granules, that is, the finer the crystals inside the particles and the more points of contact between the crystals, the higher the strength of the granules. The preferred granule strength of the supporting granules is 1 from the viewpoint of preventing the granules from collapsing and reducing the carrying capacity when the liquid surfactant composition is added to the granules.
It is 5 MPa or more, preferably 20 MPa or more, more preferably 25 MPa or more, further preferably 30 MPa or more, and preferably 100 MPa or less, more preferably 80 MP from the viewpoint of securing the carrying capacity of the supporting granules.
a or less, more preferably 70 MPa or less, most preferably 60 MPa or less.

In addition, a quinone generally used as a polymerization inhibitor in an acrylic acid monomer raw material used when synthesizing an acrylic acid-based polymer, for example, p-methoxyphenol (hereinafter also referred to as methquinone) is used as a preparation liquid. When it is contained, the surfactant-supporting granules obtained by spray drying may become pink and the hue may deteriorate. From the viewpoint of improving the hue of the surfactant-supporting granules obtained by spray-drying the preparation liquid, it is preferable to reduce the quinone content when the acrylic acid polymer is blended in the preparation liquid. . That is, the acrylic acid polymer has a quinone content of 6
It is preferably in the form of an aqueous solution of not more than ppm,
More preferably 4 ppm or less, further preferably 2 ppm
Below, most preferably, it is substantially free of quinones (1
(less than ppm) preferably in the form of an aqueous solution.

As a method for reducing quinones, it is possible to reduce the content of quinones in the acrylic acid monomer raw material when the acrylic acid polymer is synthesized. Further, it is possible to oxidize quinones contained in the acrylic acid-based polymer aqueous solution by adding an oxidizing agent such as hydrogen peroxide or sodium hypochlorite to the acrylic acid-based polymer aqueous solution. . As a preferable oxidation method, p
It is possible to exemplify the treatment with H of 10 or more and hydrogen peroxide in an equimolar amount or more of quinones. The oxidizing agent added at this time and the auxiliary agent (sodium hydroxide aqueous solution) for improving the effect thereof may be added continuously or batchwise.

As a method for detecting quinones, methquinone will be exemplified below. The amount of methaquinone in the aqueous solution of acrylic acid-based polymer is quantified by high performance liquid chromatography under the following measurement conditions.

Measurement condition column: ODS column (for example, TSK-manufactured by Tosoh Corporation)
GEL ODS-80TS (4.6mmφ x 250m
m) Eluent: 0.02M KH ₂ PO ₄ / acetonitrile = 80/20 (vol / vol) (pH of 2.
5) Measurement: UV (210 nm) Column temperature: 30 ° C. Flow rate: 1.0 ml / min Sample: Polymer aqueous solution (40%) is diluted 100 times with ion-exchanged water or eluent, and this sample is measured as it is. To do.

3. Composition of Surfactant-Supporting Granules The supporting granules of the present invention contain an acrylic acid-based polymer that is a water-soluble polymer, and sodium carbonate and sodium sulfate that are water-soluble salts. Acrylic acid-based polymers and sodium carbonate and sodium sulfate are important in forming the loading sites for the liquid surfactant composition.
Further, the acrylic acid-based polymer has a function of imparting strength to the granules.

The acrylic acid-based polymer used in the supporting granules of the present invention is a homopolymer and / or a copolymer obtained by a polymerization reaction containing acrylic acid and / or a salt thereof as a monomer component. . The acrylic acid-based polymer has a weight-average molecular weight, a half-particle size by light scattering, a ratio of particles having a particle size of more than 800 nm, and if necessary, mud particle dispersion performance, calcium ion trapping ability, and stability to calcium ions. It suffices if the constant is within the range specified above. Here, examples of the monomer component other than acrylic acid and / or its salt contained in the acrylic acid-based polymer include unsaturated monocarboxylic acids represented by methacrylic acid, α-hydroxyacrylic acid, crotonic acid, and the like. Unsaturated salts of maleic acid, methylmaleic acid, fumaric acid, itaconic acid, aconitic acid and the like, and salts thereof, unsaturated sulfonic acids represented by allylsulfonic acid, styrenesulfonic acid, etc. And a water-soluble ethylenically unsaturated monomer component exemplified by salts thereof and the like.
The acrylic acid-based polymer may contain one or more kinds of the water-soluble ethylenically unsaturated monomer component in addition to acrylic acid and its salt.

From the viewpoint of acting on the crystals of burkeite precipitated in the preparation step of the preparation liquid and the spray drying step to adjust the crystals of the burkeite into finer particles, acrylic acid-based polymers include acrylic acid and It is preferable that the amount of the monomer component other than the salt is 1 / 2.5 or less, more preferably 1/3 or less, and still more preferably the molar ratio with respect to the amount of acrylic acid and / or the salt. Is 1 /
It is 5 or less, preferably 1/10 or less, and most preferably substantially consisting of acrylic acid and / or its salt.

The content of the acrylic acid-based polymer in the surfactant-supporting granules of the present invention is preferably 5 to 30% by weight, more preferably 6 to 28% by weight, and further preferably 7 to 26% by weight. 8 to 24% by weight is particularly preferable,
Most preferred is 10 to 22% by weight. When the content is within this range, the ability to support the liquid composition is high and the granule strength is satisfactory.

The surfactant-supporting granules of the present invention may contain a water-soluble polymer other than the acrylic acid-based polymer together with the acrylic acid-based polymer. Carboxylic acid-based polymers other than acrylic acid-based polymers, for example, polymers such as polyglyoxylate salts, cellulose derivatives such as carboxymethyl cellulose and aminocarboxylic acid-based polymers such as polyaspartate salts also sequestering ability, It can be used as a material having dispersibility and anti-redeposition ability.

In addition, polyvinylpyrrolidone (PV
P), polyethylene glycol (PEG), polypropylene glycol (PPG) and the like. PVP is
It is preferable as a color transfer preventing agent, and PEG and PPG having a molecular weight of about 1,000 to 20,000 are preferable because they improve the paste viscosity characteristics generated when the powder detergent contains water.

The surfactant-supporting granules of the present invention contain water-soluble salts sodium carbonate and sodium sulfate. Sodium carbonate and sodium sulfate serve as a base for forming a supporting site for the liquid composition in the supporting granules, and sodium carbonate precipitated in the step of preparing the preparation liquid and the step of spray-drying the preparation liquid, and The size and shape of burkeite, which is a double salt of sodium sulfate, is important for enhancing the carrying capacity of the supporting granules. That is, in order to improve the loading ability of the loading granules, it is preferable to generate a large number of fine and acicular burkeites that have been acted by the acrylic acid-based polymer inside the loading granules. From this viewpoint, the total content of sodium carbonate and sodium sulfate in the surfactant-supporting granules is 19/1 to the polymer content in a weight ratio.
It is preferably 1/2, more preferably 17/1
To 1/1, more preferably 15/1 to 2/1, among them preferably 13/1 to 3/1, most preferably 11 /
It is 1 to 4/1. From the viewpoint of efficiently producing burkeite in the supporting granules, the content ratio of sodium carbonate and sodium sulfate in the surfactant supporting granules is preferably 1/10 to 10/1 by weight. . More preferably 1/8 to 8/1, still more preferably 1
/ 6 to 6/1, of which 1/4 to 4/1 is preferable,
Among them, 1/3 to 3/1 is more preferable, and 1/2 to 2/1 is most preferable.

Other water-soluble salts that can be contained in the surfactant-supporting granules of the present invention include water-soluble inorganic salts having a carbonate group, a sulfate group, a hydrogen carbonate group, a sulfite group, a hydrogen sulfate group, a phosphate group and the like. Salts (eg alkali metal salts, ammonium salts, or amine salts) can be mentioned. Further, examples thereof include chlorides such as alkali metals (for example, sodium or potassium) and alkaline earth metals (for example, calcium or magnesium), and halides such as bromides, iodides, and fluorides.

Of these, potassium carbonate, potassium sulfate, sodium sulfite and potassium sulfite are preferred.
Potassium carbonate is preferred as an alkaline agent exhibiting a suitable pH buffer region in the washing liquid, and sulfite reduces hypochlorite ion contained in tap water, and hypochlorous acid of detergent components such as enzymes and perfumes. It has an effect of preventing oxidative deterioration due to ions.

Sodium tripolyphosphate can also be used as the water-soluble salt. Also, when an alkali metal halide such as sodium chloride is added to a preparation solution containing sodium carbonate and sodium sulfate, it dissolves itself and instead precipitates fine crystals of a double salt of sodium carbonate and sodium sulfate. Since it has the effect of making it act, it effectively acts on the formation of the supporting site of the supporting granules. Furthermore, these alkali metal halides also have an action of partially suppressing the formation of a surface coating in the drying process, and also have an action of increasing the loading rate of the liquid composition of the loading granules. Is especially important from.

Examples of the water-soluble salts that can be contained in the surfactant-supporting granules of the present invention include low-molecular-weight water-soluble organic acid salts such as carboxylic acid salts such as citrate and fumarate. Is mentioned. From the viewpoint of detergency, methyliminodiacetate, iminodisuccinate, ethylenediaminedisuccinate, taurine diacetate, hydroxyethyliminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate Salts, glutamic acid diacetates, asparagine diacetates, serine diacetates and the like are preferred.

The total content of water-soluble salts including sodium carbonate and sodium sulfate in the surfactant-supporting granules is preferably 20 to 95% by weight, more preferably 25 to 90% by weight, and 30 to 85% by weight. Is more preferable,
35-80% by weight is particularly preferable, 40-75% by weight
Is most preferred. Within these ranges, the supporting granules have sufficiently high granule strength, and are also preferable from the viewpoint of solubility of the detergent particle group.

Further, the surfactant-supporting granules of the present invention may contain a water-insoluble substance. As the water-insoluble substance, crystalline aluminosilicates, amorphous aluminosilicates, silicon dioxide, hydrated silicic acid compounds, clay compounds such as perlite and bentonite, etc. can be used. The crystalline aluminosilicate and the amorphous aluminosilicate are preferred for the reason that they do not accelerate the generation of undissolved residue and the contribution of the above. The average particle size of the aluminosilicate is preferably 0.1 to 10 μm, and 0.5 to 5 μm.
m is more preferred.

Suitable crystalline aluminosilicates are A type zeolites (for example, trade name: "Toyo Builder"; manufactured by Tosoh Corporation, trade name: "synthetic zeolite";
Made by Nippon Builder Co., Ltd., product name: "VALFOR10
0 ”; PQ CHEMICALS (Thailand)
Ltd, product name: "VEGOBOND"; CONDEA
Company name: "ZEOBUILDER"; ZEOBU
ILDER Ltd, product name: "VEGOBOND
A ”; OMAN CHEMICAL INDUSTR
ES Ltd, trade name: "Zeolite"; THAI
SILICATE CHEMICALS Ltd), which is also preferable in terms of sequestration ability and economic efficiency.
Here, the value of the oil absorption capacity of the A-type zeolite according to the JIS K 5101 method is preferably 40 to 50 mL / 100 g. In addition, P type (for example, trade name "Douci
l A24 ”,“ ZSE064 ”, etc .; Crossfield
Manufactured by the company; oil absorption capacity 60 to 150 mL / 100 g) and X type (for example, trade name: "Wessasalith XD"; Degus
sa company; oil absorption capacity 80 to 100 mL / 100 g). The hybrid zeolite described in WO9842622 is also mentioned as a suitable crystalline aluminosilicate.

Further, amorphous aluminosilicate, amorphous silica and the like, which have a low sequestering ability but have a high oil absorption ability, can be used as the water-insoluble substance. For example, JP-A-6
2-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (in particular, the initial temperature is preferably in the range of 15 to 60 ° C.), JP-A-62-191419, page 2. Amorphous aluminosilicates described in lower right column, line 20 to page 5, lower left column, line 11 (in particular, oil absorption is preferably 170 mL / 100 g), and JP-A No. 9-132794, No. 17
Column line 46 to column 18 line 38, JP-A-7-10526
No. 3, column 3, line 3 to column 5, line 9, JP-A-6-227.
No. 811, column 2, line 15 to column 5, line 2, JP-A-8
No. 119622, column 2, line 18 to column 3, line 47, amorphous aluminosilicate (oil absorption capacity 285
mL / 100 g) and the like. For example,
"Tokushiru NR" (manufactured by Tokuyama Soda Co., Ltd .: oil absorption capacity 21)
0-270mL / 100g), "Fluorite" (the same:
Oil absorption capacity 400-600mL / 100g), "TIXOL
EX25 "(Korean French Chemical Company: Oil absorption capacity 220-270mL
/ 100 g), "Silopure" (manufactured by Fuji Divison Co., Ltd .: oil absorption capacity 240 to 280 mL / 100 g), and the like can be used. In particular, as an oil-absorbing carrier, JP-A-6-179899, column 12, line 12 to line 1
Those described in column 3, line 1 and column 17, line 34 to column 19, line 17 are preferable.

The water-insoluble substance may be composed of a single component or a plurality of components. When the water-insoluble substance is contained, its content in the supporting granules is preferably 49% by weight or less, more preferably 45% by weight or less, and 40% by weight or less.
The following is more preferable, 35% by weight or less is particularly preferable, and 30% by weight or less is most preferable. Within this range, a surfactant-supporting granule group having excellent granule strength and solubility can be obtained.

As the other component, it is possible to add a surfactant to the supporting granules, but when a supporting liquid-containing preparation liquid is spray-dried to produce the supporting granules, it is obtained. Since a coating film tends to be formed on the surface of the supporting granules, the absorption rate of the supporting granules with respect to the liquid surfactant composition tends to decrease. Therefore, from this viewpoint, it is preferable that the content of the surfactant in the supporting granules is smaller, and it is more preferable that the surfactant is not present. From the above, the content of the surfactant in the supporting granules is preferably 0 to 5% by weight, more preferably 0 to 3% by weight, further preferably 0 to 2% by weight, and 0 to 1% by weight. Among them, it is preferable, and among them, it is most preferable not to contain them.

As an example of the surfactant, the same liquid surfactant composition as that to be loaded on the loading granules described later can be used.

The amorphous silicate has the function of increasing the granular strength of the supporting granules, but when aluminosilicate is used as the water-insoluble substance contained in the supporting granules, the amorphous silicate is Is not included in the supporting granules of the present invention, since it forms an aggregate that becomes difficult to dissolve in water over time when it is mixed with the preparation liquid for preparing the supporting granules. Is preferred. Since the crystalline silicate also dissolves in the preparation liquid and becomes amorphous, it is preferable not to mix it with the preparation liquid like the amorphous silicate. Further, even when the aluminosilicate is not used, when the silicate is blended in the preparation liquid, the dissolution rate of the supporting granules obtained after spray drying tends to decrease. ,
It is preferably 10% by weight or less, more preferably 5% by weight or less, still more preferably 3% by weight or less, and most preferably 2% by weight, based on the water-soluble salts excluding silicate contained in the supporting granules. Hereafter, it is preferably 1% by weight or less, and most preferably substantially not contained.

Further, the supporting granules may contain auxiliary components such as fluorescent dyes, pigments, dyes and enzymes. The content of the auxiliary component is preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 2% by weight or less in the supporting granules.

4. Method for Producing Surfactant-Supporting Granules The surfactant-supporting granules of the present invention can be prepared by a production method including the steps (a) and (b) described below. Step (a): As a first step, a step of preparing a preparation liquid containing an acrylic acid polymer and sodium carbonate and sodium sulfate. Step (b): A step of spray-drying the preparation liquid of step (a).

The step (b) is a step of drying the preparation liquid obtained in the step (a) to obtain a surfactant-supporting granule group.
With respect to the drying method, any drying method, for example, freeze-drying, reduced-pressure drying or the like can be used, but from the viewpoint of precipitating finer burkeite to effectively act for supporting the liquid composition, the preparation liquid Is preferably instantaneously dried, and a particularly preferable drying method is a spray drying method.
The spray drying tower may be either a countercurrent tower or a cocurrent tower, but a countercurrent tower is preferable from the viewpoint of productivity. Further, a pulse shock wave dryer using a pulse combustor as a heat source of the spray drying tower is also exemplified as one of preferable drying devices. In the pulse shock wave dryer, the droplets of the preparation liquid are dried in the high-temperature combustion gas accompanied by the shock wave, so that the droplets are dried at a high speed. An example of the pulse shock wave dryer is PALCON (made by Osaka Fuji Industry Co., Ltd.). The step (a) will be described in detail below.

4-1. The micronization step (a) of producing, adding and pulverizing fine burkeite in the preparation liquid is a step of preparing a preparation liquid containing an acrylic acid-based polymer and sodium carbonate and sodium sulfate. From the viewpoint of further improving the carrying ability of the surfactant-supporting granules by precipitating a larger amount of burkeite, at least one and / or fine burkeite precipitation steps (I) to (III) described below are performed. It is preferable that step (a) includes a step (IV) of adding burkeite to the preparation liquid and / or a step (V) of pulverizing burkeite in the preparation liquid. here,
Steps (I) to (III) are steps of precipitating fine burkeite from sodium carbonate and sodium sulfate dissolved in the preparation liquid. Berkeite that precipitates in the process is
The fine particles are produced from the liquid phase of the preparation liquid and are acted on by the acrylic acid polymer. In addition, the step (IV) exhibits the same effect as when fine burkeite is precipitated in the preparation liquid by adding fine burkeite to the preparation liquid. In the step (V), coarse burkeite in the preparation liquid, for example, burkeite produced by using sodium carbonate particles as a nucleus, is pulverized to be finer or finer burkeite.

The preparation liquid before carrying out steps (I) to (V) is prepared by a known method, and the acrylic acid polymer and sodium carbonate and sodium sulfate may be blended in any order. I do not care. However, when the blended sodium carbonate and sodium sulfate are not completely dissolved in the preparation liquid, it is preferable to blend sodium sulfate before blending sodium carbonate from the viewpoint of efficiently producing burkeite. Further, in the case of adding a crystal depositing agent and fine burkeite described later, it is preferable to add the crystal depositing agent after the acrylic acid-based polymer and sodium carbonate and sodium sulfate. When blending a water-insoluble substance, from the viewpoint of suppressing the viscosity increase of the preparation liquid due to precipitation and addition and pulverization of burkeite, a water-insoluble substance may be blended before precipitation and addition and pulverization of fine burkeite, From the viewpoint of increasing the production efficiency of the preparation liquid, it may be added later. Steps (I) to (V) in step (a) will be described.

4-1-1. Step (I) Precipitation by Crystal Precipitating Agent As a result of investigating a method for precipitating fine burkeite in a preparation liquid, a method for precipitating by a crystal precipitating agent was found. That is, by adding a crystal precipitating agent having the effect of precipitating fine burkeite dissolved in the solution of the preparation liquid, the fine burkeite can be precipitated from the sodium carbonate and sodium sulfate dissolved in the preparation liquid. The precipitation method using a crystal precipitation agent will be described in more detail.

The crystal precipitant is a substance other than sodium carbonate and sodium sulfate contained in the preparation liquid before the addition of the precipitant, and having the effect of precipitating burkeite when added to the preparation liquid. Is.

First, in the case where the crystallizing agent is a water-soluble substance, when the preparation liquid before adding the crystallizing agent contains sodium carbonate and sodium sulfate, the crystallizing agent was added to the crystallizing agent. Its solubility at temperature is higher than that of burkeite, which is a double salt of sodium carbonate and sodium sulfate. The dissolution strength as used herein means the ease of dissolution. The substance that can be used as the crystal depositing agent is determined by the following method. For example, when sodium chloride is added to a saturated solution containing an acrylic acid-based polymer and sodium carbonate and sodium sulfate, sodium chloride is dissolved and fine needle-like crystals of burkeite, which is a double salt of sodium carbonate and sodium sulfate, are generated. Precipitates without agglomeration. In this case, sodium chloride is the preferred crystallizer for the preparations containing sodium carbonate and sodium sulfate.

The burkeite precipitated in the preparation liquid by the crystallizing agent is fine. Regarding the size of the crystals precipitated in the preparation liquid, the in-line type particle droplet monitoring system described above (“TSUB-TEC M
100 ") can be used for measurement.

Further, the effect of precipitating fine crystals by the crystal precipitating agent can be confirmed as an increase in the number of particles with time observed after the precipitating agent is added by the in-line type particle droplet monitoring system.

A method for confirming the fine crystal precipitation effect of the crystal precipitation agent will be illustrated. First, a saturated solution containing both sodium sulfate and sodium carbonate is prepared by the following method. Deionized water 1500 adjusted to the preparation temperature of the preparation liquid
g to sodium sulfate (anhydrous neutral sodium sulfate, Shikoku Kasei Co., Ltd.)
400 g), and sufficiently dissolve for 20 minutes in a constant temperature bath at the preparation temperature of the preparation liquid to dissolve. 400 g of sodium carbonate (Dense ash, manufactured by Central Glass Co., Ltd.)
Add and prepare suspension by stirring for 30 minutes. A saturated solution of sodium sulfate / sodium carbonate is prepared by a method of collecting the supernatant after allowing the suspension to stand or a method of filtering the suspension. The preparation temperature of the preparation liquid here means any temperature in the temperature range of 30 to 80 ° C.

1000 g of a saturated sodium sulfate / sodium carbonate solution prepared by any one of the above methods was weighed in a 1 L stainless beaker, and three propeller blades of 2 × 4 cm were placed in a thermostat at a preparation temperature of slurry or the like. The stirring blade is rotated at a speed of 200 r / min to stir. Add 100 g of the test sample within 30 seconds and continue stirring for 60 minutes. If burkeite crystals precipitate after 60 minutes, the sample under test is a crystallization precipitant for sodium carbonate and sodium sulfate. The precipitate is identified by performing analysis such as X-ray diffraction and elemental analysis.

Examples of the crystal depositing agent include salts having high solubility such as chlorides of sodium, potassium, calcium, magnesium, halides such as bromide, iodide and fluoride. In addition, a solvent that is compatible with water, such as ethanol, methanol, and acetone, and a substance having a high hydration power such as (anhydrous) zeolite among water-insoluble substances can also be used as the crystallizing agent.

From the viewpoint of dissolution strength, bromide and iodide are preferable, but from the viewpoint of storage stability of detergent particles, etc.,
Chlorides are preferred, and alkali metal salts are preferred because of their effect on cleaning performance. Among them, sodium chloride is particularly preferable from the economical point of view.

The content of the crystal-precipitating agent in the surfactant-supporting granules is from the viewpoint of exhibiting a sufficient crystal-precipitating effect and maintaining the cleaning performance when the detergent composition is prepared.
0.2 to 35% by weight is preferable, 0.5 to 30% by weight is more preferable, 1 to 25% by weight is further preferable, 1.5
-20 wt% is especially preferable, and 2-15 wt% is particularly preferable.

Further, the dissolution rate of the water-soluble crystal-precipitating agent in the preparation liquid is such that a larger number of precipitates are generated by dissolving more in the solution portion of the preparation liquid to form a liquid of the supporting granules obtained after spray drying. From the viewpoint of making the supporting site for the composition a more preferable structure, the higher one is preferable. The dissolution rate of the crystallizing agent is preferably 75% by weight or more, more preferably 80% by weight or more, further preferably 85% by weight or more, particularly preferably 90% by weight or more, and among them, preferably 95% by weight or more, most preferably Is to dissolve completely.

The dissolution rate of the crystallizing agent in the prepared liquid can be measured by combining known analytical techniques. For example, the prepared liquid is filtered under reduced pressure to obtain a water concentration P in the filtrate.
₁ (%) of far-infrared heater type moisture meter (manufactured by Shimadzu Corporation
Manufactured). Further, the concentration S of the crystal precipitation agent in the filtrate is
Calculate ₁ (%) by ion chromatography. When the water content of the preparation liquid is Q ₁ (%) and the content of the crystallizing agent in the preparation liquid is T ₁ (%), the dissolution rate of the crystallizing agent is calculated by the following formula. However, when the calculated dissolution rate exceeds 100%, the dissolution rate is 100%. Dissolution rate (%) = (100 × S ₁ × Q ₁ ) / (P ₁ × T ₁ ) (1)

Regarding the procedure for compounding sodium carbonate and sodium sulfate in the preparation liquid, it is preferable to dissolve sodium sulfate sufficiently and then add sodium carbonate from the viewpoint of enhancing the carrying ability of the supporting granules.

The water content of the preparation liquid is more preferably 35 to 65 from the viewpoint of reducing coarse burkeite particles having an average particle diameter of 40 μm or more which are formed by using sodium carbonate particles as nuclei and sufficiently expressing the effect of the crystal precipitating agent. weight%,
Most preferred is 40-60% by weight. The temperature of the preparation liquid is preferably 30 to 80 ° C., more preferably 35, from the viewpoint of the amount of water-soluble salts dissolved and pumpability.
~ 75 ° C.

As a method of preparing the preparation liquid, for example, all or almost all of the mixed water is first added to the mixing tank, and preferably after the water temperature almost reaches the set temperature, other components are sequentially added. The preferred order of addition is to first add the liquid component and sodium sulfate, sodium carbonate and the like. In addition, water-insoluble substances such as zeolite and small amounts of auxiliary components such as dyes can be added. However, the crystallizing agent is added after the solution portion of the preparation liquid is saturated or the solution portion is saturated when the crystallizing agent is dissolved. The water-insoluble substance may be added before the crystallizing agent, after the crystallizing agent, or separately before and after. In order to finally obtain a homogeneous preparation liquid, preferably 10 minutes or more, more preferably 2 minutes after adding all components to the preparation liquid.
Mix for 0 minutes or more, more preferably for 30 minutes or more.

4-1-2. Step (II) Precipitation by Concentration of Preparation Liquid As a result of investigating a method of precipitating fine burkeite, a method of precipitating by concentrating the preparation liquid was found. That is, a large number of fine crystals can be generated in the preparation liquid by performing an operation of precipitating burkeite from sodium carbonate and sodium sulfate in a dissolved state in the presence of an acrylic acid polymer by concentration.
The precipitation method by concentrating the prepared liquid will be described in more detail.

First, the preparation liquid before concentration may be prepared by a known method, and the acrylic acid polymer and sodium carbonate and sodium sulfate may be mixed in any order. However, when sodium carbonate and sodium sulfate in the preparation liquid are not completely dissolved, it is preferable to add sodium sulfate before sodium carbonate.
When the above-mentioned crystal depositing agent is added, it is preferable to add it after adding the acrylic acid polymer and sodium carbonate and sodium sulfate, and may be added after the concentration operation of the preparation liquid. When a water-insoluble substance is added, it may be added before or after the preparation liquid is concentrated.

The smaller the amount of coarse burkeite present in the pre-concentration preparation liquid (however, when the crystallizing agent is blended, the pre-blending preparation liquid), the smaller the amount of the supporting granules obtained after spray drying is. Noh is high. Therefore, the total dissolution rate of sodium carbonate and sodium sulfate in the preparation liquid before concentration is preferably 50 to 100% by weight, and 70 to 10% by weight.
0 wt% is more preferable, and 90 to 100 wt% is particularly preferable. When the dissolution rate is less than 100% by weight, it is also a preferred embodiment to pulverize the prepared liquid by using a wet pulverizer to be described later to make the undissolved substance fine. The wet pulverization of the prepared liquid may be performed on the concentrated slurry. The total dissolution rate of sodium carbonate and sodium sulfate is measured by the following method.

The total content T ₂ (%) of sodium carbonate and sodium sulfate in the prepared liquid is determined by ion chromatography or the like. Further, the prepared liquid is filtered under reduced pressure, and the water concentration P ₂ (%) in the filtrate is measured with a far infrared heater type water meter (manufactured by Shimadzu Corporation) or the like. Further, the total concentration S ₂ (%) of sodium carbonate and sodium sulfate in the filtrate is determined by ion chromatography or the like. Q of the water content of the prepared liquid
₂ (%) and the total content of sodium carbonate and sodium sulfate in the preparation liquid is T ₂ (%), the total dissolution rate of sodium carbonate and sodium sulfate is calculated by the following formula. However, the calculated dissolution rate is 100
When it exceeds%, the dissolution rate is 100%. Dissolution rate (%) = (100 × S ₂ × Q ₂ ) / (P ₂ × T ₂ ) (2)

Next, the preparation liquid is concentrated to precipitate water-soluble salts dissolved in the preparation liquid. As a device for concentration, any device may be used as long as it is a widely used concentration device. For example, there is a natural circulation type evaporation can in which the liquid rises while boiling inside the heating pipe inside the evaporation can, then collects in the concentrated liquid collecting pipe in the center and falls and naturally circulates, or a circulation pump between the evaporation can and the heating can. The liquid is circulated at a high speed using an external heating forced circulation type evaporation can to evaporate the water in the evaporation can or the liquid is introduced from the upper part of the vertical heating can, and flows down as a uniform liquid film on the inner wall of the heating pipe. There are thin-film flow-through type evaporators in which evaporation and concentration are performed, and these may be used alone or may be used for multiple effects. A flash-type evaporation device that evaporates water by injecting a liquid heated above the boiling point into a depressurized evaporation can is also effective.

Since the preparation liquid used in the present invention produces crystals of water-soluble salts as it is concentrated, the scale is likely to adhere to the concentration device. Therefore, it is more preferable to use a concentrating device having a function of removing the attached scale or a concentrating device having a structure in which the scale does not easily attach. As the former device, there is a device provided with the above-mentioned thin film flow down type evaporation can equipped with stirring blades for scraping scales, for example, Wiplen (manufactured by Shinko Pantec Co., Ltd.). As the latter device, there is a Roscoe evaporator (manufactured by Sumitomo Heavy Industries, Ltd.) which has a plate-type heating element inside the evaporator and concentrates the solution by flowing a liquid on the surface of this heating element under reduced pressure.

4-1-3. Step (III) Precipitation by adjusting the temperature of the preparation liquid As a result of investigating the method of precipitating fine burkeite, a method of changing the temperature of the preparation liquid so that the amount of sodium carbonate and sodium sulfate dissolved in the preparation liquid is decreased I found it. That is, the temperature of the preparation liquid is adjusted so that the dissolved amounts of sodium carbonate and sodium sulfate are reduced, and sodium carbonate and sodium sulfate in a dissolved state are precipitated in the presence of the acrylic acid-based polymer to prepare a preparation liquid. A large number of fine barkeite can be generated. The precipitation method by adjusting the temperature of the prepared liquid will be described in more detail.

First, the preparation liquid before the temperature change operation may be prepared by a known method. When the above-mentioned crystallization precipitant is blended, after the acrylic acid polymer and sodium carbonate and sodium sulfate are blended, It is preferable to add the crystallization precipitant after the temperature change operation of the preparation liquid. When a water-insoluble substance is added, it may be added before the temperature change operation of the preparation liquid or the like, or after the temperature change operation. Further, a part of the acrylic acid polymer may be added to the preparation liquid after the operation. Thereby, the size of the precipitated water-soluble salt crystals can be adjusted.

The smaller the amount of coarse burkeite present in the preparation liquid before the temperature change operation, the higher the carrying capacity of the obtained surfactant-supporting granules. Therefore, the total dissolution rate of sodium carbonate and sodium sulfate in the preparation liquid before the temperature change operation is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, and 90 to 100% by weight.
Weight percent is particularly preferred. When the dissolution rate is less than 100% by weight, it is also a preferred embodiment to pulverize the prepared liquid by using a wet pulverizer described later to finely pulverize coarse burkeite. The wet pulverization of the preparation liquid may be performed on the preparation liquid after the temperature change operation. The total dissolution rate of sodium carbonate and sodium sulfate is measured by the method described above.

Next, by changing the temperature of the preparation liquid, a part of the dissolved sodium carbonate and sodium sulfate is precipitated as burkeite. Examples of the method of changing the temperature of the preparation liquid include a method of using an apparatus equipped with an outer jacket, an internal coil, and the like when preparing the preparation liquid, and heating / cooling them.

The temperature of the preparation liquid before the temperature change operation is
It is preferable to set the dissolution rate of sodium carbonate and sodium sulfate contained in the preparation liquid to be high.

The temperature of the preparation liquid after the temperature change operation is set so that the dissolution rate of sodium carbonate and sodium sulfate in the preparation liquid is low, but sodium carbonate and sodium sulfate have the maximum dissolution amount at 30 to 40 ° C. Therefore, when using these raw materials, the prepared liquid before the temperature change operation should be
Adjust the temperature to about 0 ° C and adjust the temperature of the prepared solution after the temperature change operation to 5
It is preferable to adjust the temperature to 0 to 70 ° C.

By changing the temperature of the preparation liquid, for example, by performing flash concentration on the preparation liquid,
It is also a preferred embodiment to promote the precipitation of dissolved water-soluble salts.

4-1-4. Step (IV) Addition of fine burkeite particles to the preparation liquid As a result of investigating a method of exhibiting the same effect as that of precipitating fine burkeite in the preparation liquid, a method of adding fine particles of burkeite to the preparation liquid was found.

The preparation liquid before the addition of the fine particles is prepared by a known method, but the acrylic acid polymer and sodium carbonate and sodium sulfate may be mixed in any order. However, when sodium carbonate and sodium sulfate in the preparation liquid are not completely dissolved, it is preferable to add sodium sulfate before sodium carbonate.
When the above-mentioned crystal precipitating agent is added, it is preferable to add the crystal precipitating agent after the acrylic acid polymer and sodium carbonate and sodium sulfate. When a water-insoluble substance is added, the water-insoluble substance may be added before or after the fine particles of burkeite are added to the preparation liquid.

As a method for producing fine particles of burkeite, it is possible to pulverize a commercially available substance, but it is more preferable to carry out fine crystallization in the presence of a water-soluble polymer. Specifically, sodium carbonate and sodium sulfate are dissolved in water together with an acrylic acid-based polymer, crystallized by spray drying or the like, and finely divided by a pulverizer to obtain barcareite fine particles. The fine crusher includes a roller mill, a ball mill, an impact type crusher, etc., and the roller mill includes a USV mill (manufactured by Ube Industries, Ltd.), an MRS mill (manufactured by Mitsubishi Heavy Industries, Ltd.), and an SH mill (manufactured by IHI). There are dynamic mills (manufactured by Mitsui Miike Kakoki Co., Ltd.) and vibration mills (manufactured by Chuo Kakoki Shoji Co., Ltd.) as ball mills, and atomizers and palperizers (both are Fuji Manufactured by Paudal Co., Ltd., etc.

Further, the smaller the average particle size of the burkeite particles, the greater the effect of improving the carrying capacity of the surfactant-supporting granules obtained by spray drying in the step (b). From this viewpoint, the average particle size of the fine particles is preferably 40 μm or less, more preferably 35 μm or less, and 30
μm or less is more preferable, 25 μm or less is particularly preferable, and 20 μm or less is also preferable, and 1
It is more preferable that the thickness is 5 μm or less, and 10 is preferable.
It is particularly preferable that the thickness is less than or equal to μm. The average particle size is measured by the following method.

Ethanol 1 in a 1 L stainless beaker
Weighing 000g, 2x4cm 3 in a 20 ° C thermostat
A stirring blade equipped with a single propeller blade is rotated at a speed of 200 r / min for stirring. Subsequently, 20
g. The particle size distribution at the time of measurement for 10 minutes is measured by the same method using the above-described LASENTEC in-line particle monitoring system (TSUB-TEC M100).
The median code (particle size when the cumulative value of the number of particles is 50%) is defined as the average particle size.

4-1-5. Step (V) Wet pulverization of preparation liquid As a result of studying a method for exhibiting the same effect as when fine burkeite is precipitated in the preparation liquid, a method of wet pulverizing the preparation liquid was found. By the method of wet pulverizing the prepared liquid, coarse burkeite produced by using sodium carbonate particles as nuclei in the prepared liquid can be made finer, and further fine burkeite can be made finer.
The preparation liquid before wet pulverization is prepared by a known method, but the acrylic acid polymer and sodium carbonate and sodium sulfate may be mixed in any order. When a water-insoluble substance is blended, it may be blended before wet-milling the preparation liquid, or may be blended after wet-milling, but from the viewpoint of crushing aggregates of the water-insoluble substance and uniformly dispersing them. It is preferable to mix them before wet grinding. For example, a crystalline aluminosilicate, which is a water-insoluble substance, can improve the calcium exchange rate by blending it before wet grinding.

Further, the more finely pulverized the burkeite contained in the preparation liquid, the greater the effect of improving the carrying capacity of the surfactant-supporting granules obtained by spray drying in the step (b). The wet pulverization of the preparation liquid makes it possible to utilize the burkeite for forming supporting sites in the supporting granules obtained by spray-drying by pulverizing the burkeite present in the preparation liquid. For example, when barkerite is formed in the preparation liquid by adding sodium carbonate to the acrylic acid-based polymer and sodium sulfate, the barkerite is a coarse particle formed on the surface of sodium carbonate to which most of the barkite is added. Exists as. Burkeite can hardly contribute to the formation of the supporting site of the supporting granules if it exists as such coarse particles,
By pulverizing by wet pulverization, it is effectively used for forming a supporting site in the supporting granules, and the supporting ability of the granules is improved.

The crushing device may be any generally known wet crushing device. As a commonly used wet crushing device, there are (i) a device for finely crushing using a crushing medium, and (ii) a device for finely crushing in a gap between a crushing blade and a stator.

As (i), while stirring the medium in the vertical cylindrical vessel with a stirring blade or a stirring disk, the processing liquid is supplied from the lower part of the vessel to pulverize by the shearing force generated by the difference in the flow velocity of the medium. There is a device for performing the treatment and discharging the treatment liquid from the upper portion of the vessel. There are sand grinders (made by Igarashi Kikai Seisakusho Co., Ltd.) and universal mills (made by Mitsui Miike Seisakusho Co., Ltd.) as continuous types of such devices, and an aquamizer (made by Hosokawa Micron Corp.) as a batch type. . As a horizontal continuous type having a similar structure, there is Dyno-Mill (manufactured by WAB). or,
A diamond fine mill (manufactured by Mitsubishi Heavy Industries, Ltd.), which consists of a cylindrical rotor and an annular casing that encloses it, and crushes the processing liquid supplied from the lower center of the rotor by the high-speed rotational force of the media, Coball Mill (Shinko Pantech Co., Ltd.) is available.

(Ii) is a colloid mill (Shinko Pantec Co., Ltd.) which is composed of a rotor having a grinding tooth and a stator, and which grinds by repeatedly applying a shearing force when the treatment liquid passes through this gap. Manufactured by Mitsui Miike Kakoki Co., Ltd.). Glow mill (made by Glow Engineering Co., Ltd.), which has the same crushing mechanism as the rotor and stator are grindstones, mass colloider (made by Masuyuki Sangyo Co., Ltd.), and corundum mill (made by Shinko Pantec Co., Ltd.) . Further, there is a homomic line mill (manufactured by Tokushu Kika Kogyo Co., Ltd.) that performs coarse crushing with a first turbine and a stator and fine crushing with a second rotor and a stator. Furthermore, with a wet emulsion disperser that also has the functions of emulsion dispersion, uniform mixing, and atomization, a specially shaped rotor that rotates at high speed,
There is Cavitron (manufactured by Taiheiyo Kiko Co., Ltd.) that can give a powerful impact in megahertz to the liquid with a stator that meshes with it and obtain a dispersion effect equivalent to that of a high pressure homogenizer.

5. Physical Properties of Granules for Supporting Surfactant The bulk density of the granules for supporting the present invention is from the viewpoint of securing the carrying capacity of the liquid surfactant composition and the bulk density after supporting the liquid surfactant composition. From the viewpoint of
000 g / L is preferable, 350 to 800 g / L is more preferable, 400 to 700 g / L is further preferable, 45
0 to 600 g / L is particularly preferable.

The average particle size of the supporting granules is also considered from the viewpoint of powderiness and solubility when a detergent composition containing a detergent particle group in which a liquid surfactant composition is supported on the supporting granules is used. The diameter is preferably 140 to 600 μm, and is 160
˜500 μm is more preferable, and 180 to 400 μm is still more preferable.

The amount of water in the supporting granules measured by an infrared moisture meter is preferably as small as possible from the viewpoint of increasing the carrying capacity of the liquid surfactant composition in the granules, and preferably 14
It is not more than 10% by weight, more preferably not more than 10% by weight, further preferably not more than 6% by weight, most preferably not more than 2%.

The above-mentioned bulk density, average particle size and water content can be measured by the methods described in the methods for measuring physical properties described later.

6. Composition and Physical Properties of Detergent Particle Group The detergent particle group of the present invention comprises the above-mentioned supporting granule group and a surfactant composition supported thereon.

In the surfactant composition, the anionic surfactant and the nonionic surfactant may be used alone, but it is more preferable to use both as a mixture. In particular, when using a nonionic surfactant having a melting point of 30 ° C. or lower, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1,000 to 30,000, which acts to increase the melting point of the surfactant. It is preferable to use a compound (hereinafter referred to as a melting point raising agent) or an aqueous solution thereof together. Examples of the melting point raising agent that can be used in the present invention include polyethylene glycol and polypropylene glycol. Further, an amphoteric surfactant or a cationic surfactant can be used together depending on the purpose. Further, by adding an anionic surfactant such as an alkylbenzene sulfonate to the detergent particle group in an amount of 5 to 25% by weight, the effect of improving the dispersibility of the detergent particle group in low temperature water is exhibited.

As the surfactant composition, for example, one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants are used. be able to. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or its ester, alkyl or alkenyl ether carboxylate, amino acid type surfactant. , N-acyl amino acid type surfactants and the like. Particularly, straight chain alkylbenzene sulfonate having 10 to 14 carbon atoms, alkyl sulfate or alkyl ether sulfate having 10 to 18 carbon atoms can be mentioned, and as counterion, alkali metal such as sodium and potassium, monoethanolamine, diethanolamine and the like. Are preferred.

Further, a fatty acid salt may be used in combination for obtaining a defoaming effect. Preferred fatty acid has 12 carbon atoms
~ 18.

As the nonionic surfactant, polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl or alkenyl phenyl ether,
Polyoxyethylene polyoxypropylene alkyl or alkenyl ether, polyoxyethylene polyoxypropylene glycol represented by trademark Pluronic, polyoxyethylene alkylamine, higher fatty acid alkanolamide, alkyl glucoside, alkyl glucose amide, alkyl amine oxide, etc. . Among them, those having a high hydrophilicity and those having a low ability to form liquid crystals formed when mixed with water or those which do not form liquid crystals are preferable, and polyoxyalkylene alkyl or alkenyl ethers are particularly preferable. Preferably, the carbon number is 10 to 18,
Ethylene oxide (hereinafter referred to as EO) addition of an alcohol having an average addition mole number of preferably 12 to 14 and more preferably 5 to 30, more preferably 7 to 30, still more preferably 9 to 30 and particularly preferably 11 to 30. In addition to these, EO adducts of alcohols having 8 to 18 carbon atoms and propylene oxide (hereinafter PO) adducts are preferable. As the order of addition, it is possible to use the one in which PO is added after adding EO, the one in which EO is added after adding PO, or the one in which EO and PO are randomly added, but those having a particularly preferable addition order For example, after adding EO, block addition of PO, and then E
General formula with block addition of O: R-O- (EO) _X- (PO) _Y- (EO) _Z- H [In the formula, R is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group or an alkenyl group. A group, EO is an oxyethylene group, PO is an oxypropylene group, and X, Y and Z are average addition mole numbers, respectively. ] The most preferable average addition mole number among them is X> 0, Z> 0, X + Y + Z = 6 to 14,
+ Z = 5 to 12 and Y = 1 to 4.

Examples of the cationic surface active agent include quaternary ammonium salts such as alkyl trimethyl ammonium salts.

Examples of the amphoteric surfactant include carbobetaine type and sulfobetaine type.

The content of the anionic surfactant is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, and particularly preferably 30 to 180 parts by weight, based on 100 parts by weight of the nonionic surfactant. Is. The blending amount of the melting point increasing agent of the nonionic surfactant is 1
The amount is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 00 parts by weight. In this range, the surfactant composition has a viscosity of 10 Pa · s or less, preferably 5 Pa · s at a temperature of the pour point of the composition or higher.
In the following, it is particularly preferable that the composition has a temperature range of 2 Pa · s or less and has a penetration hardness of 10 kPa or more, preferably in a temperature range lower than the pour point of the composition and higher than the melting point of the nonionic surfactant. Has a temperature range of 30 kPa or more, particularly preferably 50 kPa or more,
It is preferable because the composition and the detergent particle group can be easily handled during production and the nonionic surfactant can be prevented from being spotted during storage of the detergent particle group.

The physical properties of the surfactant composition can be measured by the following methods. The pour point is JIS K22
69 method. Melting point is FP
800 METTLER FP81 (Met)
Teller Instrument AG)
It is measured at a temperature rising rate of 0.2 ° C./min. The viscosity is a B-type viscometer (“DVM-B” manufactured by TOKYO KEIKI).
Type ”), rotor No. It is determined by measuring under the condition of 3, 60 r / min. When the measured value under the condition exceeds 2 Pa · s and the measurement becomes impossible, the rotor No. 3, 12r
Measured under the condition of / min. Ingress hardness is measured by rheometer ("NRM-3002D", manufactured by Fudo Kogyo Co., Ltd.)
And a circular adapter (No. 3, 8φ) having a diameter of 8 mm and a bottom area of 0.5 cm ² , the load when the adapter enters the surfactant composition at a penetration rate of 20 mm / min for 20 mm is applied to the bottom of the circular adapter. It is the value divided by the area.

From the viewpoint of detergency and solubility, the amount of the surfactant composition added is preferably in the range of 10 to 100 parts by weight, preferably 20 to 80 parts by weight, relative to 100 parts by weight of the supporting granules.
The range of parts by weight is more preferable, and the range of 30 to 60 parts by weight is particularly preferable. The amount of the surfactant composition added here does not include the amount of the surfactant added, even if the surfactant is added to the preparation liquid.

When the surfactant composition and the supporting granules are mixed, if desired, powder raw materials other than the granules may be added, and the addition amount is based on 100 parts by weight of the granules. Therefore, 0 to 150 parts by weight is preferable. Examples of the powder raw material include crystalline silicates such as aluminosilicate and SKS-6 (manufactured by Clariant).

Further, the detergent particle group may contain, as a component other than the above-mentioned surfactant composition, a water-soluble polymer, a water-soluble salt, a water-insoluble substance and other components exemplified in the supporting granules. When a water-insoluble substance is used, it may contain a crystalline silicate described later.

When a detergent particle group is produced using a powder raw material and a component such as a surfactant which can serve as a binder,
In some cases, the detergent particles are covered with an aggregating layer of the components, and the physical properties of the supporting particles cannot be confirmed only from the appearance. In this case, one of the methods for confirming the physical properties of the supporting granules is to extract the organic solvent-soluble component from the detergent particle group and separate the supporting granules for confirmation. Further, the type of organic solvent used for extraction is appropriately selected depending on the type of binder substance that binds each constituent unit of the detergent particles.

The method for confirming the physical properties and the like of the surfactant-supporting granules by solvent extraction will be illustrated below. 15 g of the detergent particles that have been shrunk and weighed are refluxed for 1 hour with 300 mL of 95% ethanol heated in a water bath, and then ethanol-insoluble matter is gradually filtered off by suction filtration while sufficiently washing with hot ethanol. Separate the separated ethanol insoluble matter
After drying under reduced pressure for 4 hours, it is carefully collected so as not to destroy the granular structure of the insoluble matter. This operation is repeated several times to obtain 100 g of ethanol-insoluble matter. The ethanol-insoluble matter thus obtained was subjected to 1 using a JIS Z 8801 standard sieve.
After vibrating for 0 minutes, the weight on each sieve was measured and the granules classified by the above-mentioned sieves were observed and analyzed to determine whether the obtained granules are the supporting granules of the present invention. And the presence or absence of the ethanol insoluble matter added in the subsequent step. When ethanol-insoluble matter added in the post-process to the supporting granules in the ethanol-insoluble matter is confirmed, the effect on the particle size distribution due to the post-process addition is removed to obtain the average particle size of the supporting granules. . That is, by performing a separation operation of a solvent-insoluble matter with a properly selected solvent or a combination thereof, after removing the surfactant composition and components added in the subsequent step, the physical properties of the supporting granules, etc. You can check.

The preferred physical properties of the detergent particle group according to the present invention are as follows. The bulk density is preferably 500 to
1000 g / L, more preferably 600-1000 g / L
L, particularly preferably 650 to 850 g / L. The average particle diameter is preferably 150 to 500 μm, more preferably 180 to 400 μm.

7. Method for Producing Detergent Particle Group A suitable method for obtaining a detergent particle group comprises the following step (I), and may further include step (II) if necessary. Step (I): A step in which the surfactant composition is mixed with the surfactant-supporting granules obtained by the production method of the present invention under a liquid condition. Step (II): A step of mixing the mixture obtained in step (I) with a surface coating agent and coating the surface of the powder detergent particles with the surface coating agent. However, the step (II) also includes the case where crushing proceeds simultaneously.

<Step (I)> As a method for supporting the surfactant composition on the supporting granules, for example, a batch type or a continuous mixer is used to carry the supporting granules and the surfactant composition. And a method of mixing with. Here, when performing in a batch system, as a charging method to the mixer, (1) first charging the supporting granules to the mixer, and then adding the surfactant composition, (2) to the mixer Charge the supporting granules and the surfactant composition little by little. (3) Charge a part of the supporting granules in the mixer, and then add the remaining supporting granules and the surfactant composition little by little. A method such as charging can be used.

Among the surfactant compositions, those which are present in a solid or paste form even if the temperature is raised within a practical temperature range, for example, 50 to 90 ° C. An ionic surfactant, a nonionic surfactant aqueous solution or water is dispersed or dissolved to prepare a mixed solution or aqueous solution of the surfactant composition, and the mixed solution or aqueous solution is added to the supporting granules in the form of the mixed solution or aqueous solution. Just do it. By this method, a surfactant composition existing in a solid or paste state can be easily added to the supporting granules. The mixing ratio of the low-viscosity surfactant composition or water to the solid or pasty surfactant composition is preferably within a viscosity range in which the resulting mixed liquid or aqueous solution can be sprayed.

The above-mentioned mixed solution can be prepared, for example, by adding a solid or pasty surfactant composition to a low-viscosity surfactant or water and mixing them, or in a low-viscosity surfactant or in water. The acid precursor of the surfactant, for example, the acid precursor of the anionic surfactant is neutralized with an alkaline agent (for example, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide) to prepare a mixed solution of the surfactant composition. You may prepare.

In addition, in this step, before the addition of the surfactant composition, at the same time as the addition of the surfactant composition, during the addition of the surfactant composition, or after the addition of the surfactant composition, the anionic surfactant is added. It is also possible to add an acid precursor of the agent. By adding an acid precursor of an anionic surfactant, the surfactant is highly blended, the carrying capacity of the supporting granules, the carrying capacity is controlled, and the stain generation of the nonionic surfactant of the detergent particles is suppressed. It is possible to improve physical properties and quality such as fluidity.

Examples of the acid precursor of the anionic surfactant which can be used in the present invention include alkylbenzene sulfonic acid, alkyl or alkenyl ether sulfuric acid,
Examples thereof include alkyl or alkenyl sulfuric acid, α-olefin sulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, and fatty acid. From the viewpoint of improving the fluidity of the detergent particles, it is particularly preferable to add the fatty acid after adding the surfactant.

The amount of the acid precursor of the anionic surfactant to be used is preferably 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, and 1 to 100 parts by weight of the supporting granules.
10 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable. The amount of the acid precursor used is not included in the amount of the surfactant composition in the present invention. Further, as a method of adding the acid precursor of the anionic surfactant, it is preferable to spray and supply a liquid one at room temperature, and a solid one at room temperature may be added as a powder or melted. You may supply after spraying. However, when the powder is added, it is preferable to raise the temperature of the detergent particle group in the mixer to a temperature at which the powder melts.

Specific examples of preferable mixing devices include the following. In case of batch method, (1) ~
The thing of (3) is preferable. (1) Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), high-speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Powrex Co., Ltd.), Loedige mixer (manufactured by Matsuzaka Giken Co., Ltd.) , Proshare mixer (Pacific Machine Engineering Co., Ltd.)
Manufactured), JP-A-10-296064, JP-A-10-26064
(2) Ribbon mixer (manufactured by Hiwa Machinery Co., Ltd.), batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), ribocorn (manufactured by Okawara Seisakusho Co., Ltd.), etc. ( 3) Nauta mixer (manufactured by Hosokawa Micron Co., Ltd.), SV mixer (Shinko Pantech Co., Ltd.)
Manufactured) etc. Among the above mixers, a Loedige mixer, a Proshare mixer, and JP-A-10-29 are preferable.
There are mixing devices and the like described in JP-A No. 6064 and JP-A No. 10-296065, and step (II) described below can be performed by the same device, which is preferable from the viewpoint of simplification of equipment. Among them, the mixing devices described in JP-A-10-296064 and JP-A-10-296065 are preferable because they can control the moisture content and temperature of the mixture by aeration and suppress the disintegration of the surfactant-supporting granules. Further, a mixing device such as a Nauter mixer, an SV mixer or a ribbon mixer capable of mixing the powder and the liquid without giving a strong shearing force is preferable from the viewpoint of suppressing the collapse of the surfactant-supporting granules.

Further, the supporting granules and the surfactant composition may be mixed using a continuous type device of the above mixer.
Examples of continuous mixers other than those mentioned above include a flexomix type (manufactured by Powrex Co., Ltd.) and a turbulizer (manufactured by Hosokawa Micron Co., Ltd.).

When a nonionic surfactant is used in this step, it has a melting point of 45 to 100 ° C. and a molecular weight of 1,000 to 100, which has a function of increasing the melting point of the surfactant.
30,000 water-soluble nonionic organic compound (hereinafter, melting point raising agent) or this aqueous solution, before the addition of the surfactant composition, simultaneously with the addition of the surfactant composition, during the addition of the surfactant composition, Alternatively, it is preferable to add it after the surfactant composition is added, or after being mixed in advance with the surfactant composition. By adding a melting point raising agent, the caking property of the detergent particle group,
The stain release property of the surfactant in the detergent particle group can be suppressed. As the melting point raising agent, the same ones as those exemplified in the melting point raising agent having the composition of the detergent particles can be used. The amount of the melting point raising agent used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and 1 to 100 parts by weight of the supporting granules.
Most preferred is 3 parts by weight. This range is the suppression of aggregation between detergent particles contained in the detergent particle group, high-speed solubility,
In addition, it is preferable from the viewpoint of suppressing stain generation and caking properties. As a method of adding the melting point raising agent, it is possible to add it by mixing it with a surfactant in advance by an arbitrary method, or to add the melting point raising agent after the addition of the surfactant in order to prevent stain generation or caking property of the detergent particles. It is advantageous for suppression.

It is more preferable that the temperature in the mixer in this step is raised to a temperature not lower than the pour point of the surfactant composition for mixing. The pour point of the surfactant composition is JIS
It is measured by the method specified in K2269. Here, the temperature to be raised may be higher than the pour point of the surfactant composition added to promote the loading of the surfactant composition, but in a practical range, it may exceed the pour point. A temperature of 50 ° C. above the pour point is preferable, and a temperature of 10 ° C. to 30 ° C. above the pour point is more preferable. Further, when the acid precursor of the anionic surfactant is added in this step, it is more preferable that the temperature is raised to a temperature at which the acid precursor of the anionic surfactant can react and mixing is performed.

The batch mixing time for obtaining a suitable detergent particle group, and the average residence time in continuous mixing are 1
It is preferably -20 minutes, more preferably 2-10 minutes.

Further, when an aqueous solution of a surfactant or an aqueous solution of a water-soluble nonionic organic compound is added as a surfactant composition, there is a step of drying excess water during mixing and / or after mixing. Good.

It is also possible to add the powdered surfactant and / or the powder builder before, simultaneously with, or during the addition of the surfactant composition. By adding the powder builder, the particle size of the detergent particle group can be controlled, and the cleaning power can be improved. Particularly when an acid precursor of an anionic surfactant is added, it is effective to add a powder builder exhibiting alkalinity before adding the acid precursor from the viewpoint of promoting the neutralization reaction. The powder builder mentioned here is
Other than a surfactant, it means a powder detergency enhancer, specifically, a base having sequestering ability such as zeolite or citrate, or a base having alkaline ability such as sodium carbonate or potassium carbonate. Agents, bases having both sequestering ability and alkalinity of crystalline silicates, etc., and other bases for increasing ionic strength such as sodium sulfate.

Here, as the crystalline silicate, Japanese Patent Laid-Open No. 5-2 is used.
79013 gazette, column 3, line 17 (in particular, 500 to 10)
What was crystallized by firing at 00 ° C is preferable. ), JP-A-7-89712, column 2, line 45, JP-A-60.
-227895 publication, page 2, lower right column, line 18 (especially second
The listed silicates are preferred. The crystalline silicate described in 1) can be used as a preferred powder builder. here,
The alkali metal silicate having SiO ₂ / M ₂ O (where M represents an alkali metal) of 0.5 to 3.2, preferably 1.5 to 2.6 is more preferably used.

The amount of the powder builder used is preferably 0.5 to 12 parts by weight, more preferably 1 to 6 parts by weight, based on 100 parts by weight of the supporting granules. When the amount of the powder builder for a detergent used is within this range, a powder having good solubility can be obtained.

Further, after the step (I), it is preferable to add a step (II) for surface-modifying the detergent particle group.

<Step (II)> In the present invention, in order to modify the particle surface of the detergent particles supporting the surfactant in the step (I), the following (1) fine powder is added as a form of addition. The body, (2) the step (II) of adding various surface coating agents such as liquid may be carried out one or more steps.

When the particle surface of the detergent particle group of the present invention is coated, the fluidity and the caking resistance of the detergent particle group tend to be improved, so that it is preferable to provide the surface modification step.
The apparatus used in the step (II) is preferably, for example, the mixer illustrated in the step (I), which is equipped with both a stirring blade and a crushing blade. Each of the surface coating agents will be described below.

(1) Fine powder As the fine powder, the average particle diameter of the primary particles is preferably 10 μm or less, and more preferably 0.1 to 10 μm. When the average particle size is in this range, the coverage of the particle surface of the detergent particle group is improved, and it is suitable from the viewpoint of improving the fluidity and the caking resistance of the detergent particle group. The average particle diameter of the fine powder is measured by a method utilizing light scattering, for example, a particle analyzer (manufactured by Horiba, Ltd.) or measurement by microscopic observation. Further, it is preferable from the viewpoint of cleaning that the fine powder has a high ion exchange ability and a high alkali ability.

The fine powder is preferably an aluminosilicate, which may be crystalline or amorphous. In addition to aluminosilicates, fine powders such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, silicic acid compounds such as amorphous silica derivatives and crystalline silicic acid compounds are also preferable. In addition, metal soap having primary particles of 0.1 to 10 μm, powdered surfactant (eg, alkyl sulfate, etc.)
Similarly, a water-soluble organic salt can be used. When the crystalline silicic acid compound is used, it is preferably mixed with fine powder other than the crystalline silicic acid compound for the purpose of preventing deterioration due to aggregation of the crystalline silicic acid compound due to moisture absorption or carbon dioxide absorption.

The amount of the fine powder used is the detergent particle group 10
0.5 to 40 parts by weight is preferable with respect to 0 parts by weight, and 1 to
30 parts by weight is more preferable, and 2 to 20 parts by weight is particularly preferable. When the amount of the fine powder used is within this range, the fluidity is improved and the consumer feels good.

(2) Liquid Material Examples of the liquid material include water-soluble polymers and fatty acids, which can be added in an aqueous solution or a molten state.

(2-1) Water-Soluble Polymer Examples of the water-soluble polymer include carboxymethyl cellulose, polyethylene glycol, polyacrylic acid or a salt thereof, a polycarboxylic acid salt such as a copolymer of acrylic acid and maleic acid or a salt thereof, and the like. Can be mentioned. The amount of the water-soluble polymer used is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 2 to 6 parts by weight, based on 100 parts by weight of the detergent particle group. When the amount of the water-soluble polymer used is within this range, it is possible to obtain a detergent particle group exhibiting good solubility, good fluidity, and anti-caking property.

(2-2) Fatty acids Examples of fatty acids include fatty acids having 10 to 22 carbon atoms. The amount of the fatty acid used is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the detergent particle group,
0.5 to 3 parts by weight is particularly preferred. In the case of a solid substance at room temperature, it is preferable to spray and supply after heating to a temperature at which it has fluidity.

8. Detergent composition The detergent composition of the present invention is a composition containing the above-mentioned detergent particle group, and a detergent component separately added other than the detergent particle group (for example, builder granules, fluorescent dye, enzyme, A fragrance, an antifoaming agent, a bleaching agent, a bleaching activator, etc.).

From the viewpoint of detergency, the content of the detergent particles in the detergent composition is preferably 50% by weight or more, more preferably 60% by weight or more, further preferably 70% by weight or more,
It is particularly preferably 80% by weight or more and 100% by weight or less.

The content of the detergent component other than the detergent particles in the detergent composition is preferably 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less, particularly preferably 20% by weight or less. .

9. Physical Properties of Detergent Composition Preferred physical properties of the detergent composition according to the present invention are as follows. The average particle size is preferably 150 to 500 μm,
More preferably, it is 180 to 400 μm. The bulk density is
Preferably 500-1000 g / L, more preferably 6
00-1000 g / L, particularly preferably 650-850
It is g / L.

10. Method for Producing Detergent Composition The method for producing the detergent composition is not particularly limited, and examples thereof include a method of mixing the detergent particle group and a separately added detergent component. Since the detergent composition thus obtained contains detergent particles having a large amount of the surfactant loaded, it can exhibit a sufficient cleaning effect even in a small amount.
The application of the detergent composition is not particularly limited as long as it is an application using a powder detergent, for example, a powder detergent for clothes,
Examples include automatic dishwashing detergent.

11. Physical Property Measuring Method The physical property values in the present specification refer to those measured by the following methods. (Bulk density): Measured by the method specified by JIS K3362. (Average particle diameter): Determined using a sieve specified in JIS Z8801. For example, the aperture is 2000μm, 1400μ
m, 1000 μm, 710 μm, 500 μm, 355 μ
m, 250 μm, 180 μm, 125 μm, 9 stages of sieves and pans, and low tap machine (HEIKO SEISAK
USHO, tapping: 156 times / min, rolling: 29
(0 times / minute), 100 g of sample was vibrated for 10 minutes to perform sieving, and then, a saucer, 125 μm, 180
μm, 250 μm, 355 μm, 500 μm, 710 μm
m, 1000 μm, 1400 μm, 2000 μm in order of accumulating the weight frequency on the pan and each sieve, the first sieve opening with which the accumulated weight frequency is 50% or more is αμ.
m, and the opening of the sieve, which is one step larger than αμm, is βμm.
When the cumulative weight frequency from the pan to the αμm sieve is γ% and the weight frequency on the αμm sieve is θ%,

[0188]

[Equation 3]

It can be obtained according to

(Granular strength): 20 g of the sample was placed in a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapped 30 times (Tsutsui Rikagaku Kikai Co., Ltd., TVP1 type tapping type dense packing bulk density measuring instrument, tapping conditions; 36 cycles / minute,
Free fall from a height of 60 mm is performed, and the sample height at that time (initial sample height) is measured. After that, the entire upper end surface of the sample held in the container by a pressure tester is 10 mm / m.
Pressurize at a speed of in to obtain a load-displacement curve. The gradient in the straight line portion when the displacement rate is 5% or less is multiplied by the initial sample height, and the value is divided by the pressing area to obtain the granule strength.

(Water content): The water content of the granules is measured by the infrared moisture meter method. That is, 3 g of a sample is weighed on a sample dish of known weight, and the sample is heated for 3 minutes by an infrared moisture meter (Ket Scientific Laboratory Co., Ltd. (infrared lamp 185W)).
Dry. After drying, weigh the sample dish and dried sample. The difference in weight between the sample before and after drying and the sample obtained by the above operation is divided by the amount of the sample weighed and multiplied by 100 to calculate the amount of water in the sample.

(Pore volume distribution): The pore volume of the surfactant-supporting granules can be measured by "SHIMAD Co., Ltd."
Using the ZU Pore Sizer 9320 ", the procedure is as follows based on the instruction manual. That is, the surfactant-supporting granules are put into a cell, and the mercury to be press-fitted is supplied to the low pressure portion (0-14.2 psi).
Separately measure into a) and the high pressure part (14.2 to 30000 psia). Measurement data is smoothed by taking a moving average of two data before and after, and a mode diameter in the range of 0.01 μm to 3 μm and a pore volume of 0.01 μm to 3 μm are obtained.

(Fluidity): Flow time is JIS K 3
From the hopper for bulk density measurement defined by 362,
Let the time required for 100 mL of powder to flow out.
(Loading capacity of liquid surfactant composition): 100 g of granules are placed in a cylindrical mixing tank having an inner diameter of 5 cm and a height of 15 cm equipped with a stirring blade, and the mixture is stirred at 350 rpm at 30 ° C.
And polyoxyethylene alkyl ether [C ₁₂ / C ₁₄ =
6/4 (molar ratio), EO = 7.7, melting point = 25 ° C.]
Drop at a rate of 0 mL / min and measure the change over time in the stirring power. The amount of polyoxyethylene alkyl ether added when the stirring power became the highest was adjusted to the weight of the granules (10
The value divided by 0 g) is taken as the carrying capacity (mL / g) of the granule group.

(Staining property): Vertical × horizontal × height = 10 cm × 6 using a two-type filter paper defined in JIS P 3801 (for example, “Qualitative No2 filter paper” manufactured by Toyo Roshi Kaisha, Ltd.)
Make a container with an open top of cm x 4 cm. An oil-based marker (“Magic Ink M700-T1” manufactured by Uchida Yoko Co., Ltd.) is used to draw a line having a line width of 0.5 to 1.0 mm in a diagonal direction on the sample filling surface on the bottom surface of the container. Sample 1 in the container
00 g is filled, and the total weight of acrylic resin plate and lead plate (or iron plate) 15 g + 250 g is placed on it. By placing this in a moisture-proof container, leaving it in a thermostat at a temperature of 30 ° C., and visually observing the degree of bleeding of the oily marker after 7 days,
Determine the appearance of spots. The criteria are as follows. Rank 5: Bleed width of oil marker is 2 cm or more Rank 4: Bleed width of oil marker is 1 cm or more Rank 3: Bleed width of oil marker is 0.5 cm or more Rank 2: Bleed of oil marker is slightly recognized Rank 1: No bleeding on oily marker.

(Washing performance): An artificial stain liquid having the following composition is attached to a cloth to prepare an artificial stain cloth. The attachment of the artificial contamination liquid to the cloth is performed by printing the artificial contamination liquid on the cloth according to Japanese Patent Laid-Open No. 7-270395. The step of producing the artificially contaminated cloth by attaching the artificially contaminated liquid to the cloth is as follows. The cell volume of the gravure roll is 58 cm ³ / cm ² , and the coating speed is 1.0 m / mi.
n, the drying temperature is 100 ° C., and the drying time is 1 minute. As the cloth, cotton cloth 2003 cloth (made by Yazu Shoten) is used.

The composition of the artificial pollutant was 0.44 lauric acid.
% By weight, myristic acid 3.09% by weight, pentadecanoic acid 2.31% by weight, palmitic acid 6.18% by weight, heptadecanoic acid 0.44% by weight, stearic acid 1.57% by weight, oleic acid 7.75% by weight Trioleic acid 13.
06 wt%, n-hexadecyl palmitate 2.18 wt%, squalene 6.53 wt%, egg yolk lecithin liquid crystal 1.94 wt%, Kanuma red clay 8.11 wt%, carbon black 0.01 wt%, tap water Is the balance amount.

The cleaning performance is evaluated by the following method.
2.2 kg of clothes (8/2 weight ratio of underwear and Y-shirt) to Matsushita Electric Industrial washing machine "Aizuma-go NA-F70AP"
And the 10 cm × 10 cm artificially contaminated cloth 10 prepared above
3 pieces of 35 cm x 30 cm cotton base cloth are sewn evenly, and 22 g of the evaluation sample is put on the clothes in a collective state, and water is poured so that the evaluation sample does not come into direct contact with water,
Wash on standard course. The washing conditions are as follows.
Washing course: standard course, detergent concentration 0.067% by weight, wash water 71.2 mg CaCO ₃ / L, hard water with Ca / Mg molar ratio 7/3, water temperature 20 ° C., bath ratio 15 L / kg.

The cleaning performance was determined by measuring the reflectance of the unfabricated raw cloth and the contaminated cloth before and after washing at 550 nm with a self-recording colorimeter (manufactured by Shimadzu Corporation), and the cleaning rate was calculated by the following formula: 10 sheets The measured average value of is shown as the cleaning performance. The reflectance after cleaning is A, the reflectance before cleaning is B, and the reflectance C of the original cloth is C. Cleaning rate (%) = (A−B) / (C−B) × 100

[0199]

EXAMPLES In this experimental example, the following raw materials were used unless otherwise specified. Sodium Sulfate: Anhydrous Neutral Glauber's salt (manufactured by Shikoku Kasei Co., Ltd.) Sodium sulfite: Sodium sulfite (manufactured by Mitsui Chemicals, Inc.) Fluorescent dye: Chinopearl CBS-X (manufactured by Ciba Specialty Chemicals) Sodium carbonate: Dense ash (average particle size) Diameter: 290 μm, Central Glass Co., Ltd. Sodium chloride: Baked salt S (manufactured by Japan Salt Co., Ltd.) Crystalline sodium aluminosilicate (zeolite): Zeobuilder (4A type, average particle size: 3.5 μm), Zeobuilder ) Polyoxyethylene alkyl ether: Emulgen 10
8KM (average number of moles of ethylene oxide added: 8.5,
Carbon number of alkyl chain: 12 to 14, manufactured by Kao Corporation) Polyethylene glycol: K-PEG6000 (weight average molecular weight: 8500, manufactured by Kao Corporation)

Experimental Example 1 453 parts by weight of water was placed in a jacketed mixing tank equipped with a stirrer, and after the water temperature reached 37 ° C., 110 parts by weight of sodium sulfate, 5 parts by weight of sodium sulfite, and 2 parts by weight of fluorescent dye were added. Add and stir for 10 minutes. 125 parts by weight of sodium carbonate was added, 175 parts by weight of the following acrylic acid-based polymer aqueous solution was added, and the mixture was stirred for 10 minutes. 40 parts by weight of sodium chloride was added as a crystallizing agent, and the mixture was stirred for 60 minutes. Further, 143 parts by weight of zeolite was added and stirred for 30 minutes to obtain a preparation liquid. The water content of this preparation is 5
The final temperature of the preparation was 50 ° C.

As the above acrylic acid-based polymer aqueous solution, a sodium polyacrylate aqueous solution produced by the following method was used.

The sodium polyacrylate aqueous solution was produced according to the method described in the example of Japanese Patent Publication No. 2-24283. The reaction has a degree of neutralization of 95% and a concentration of 37.7% by weight.
An aqueous sodium acrylate solution of 3.11 kg / h is supplied, a sodium bisulfite aqueous solution having a concentration of 35% by weight is supplied at 0.13 kg / h, the air supply amount is 3 m ³ / h, and the average temperature of the jacket is 20 ° C. I did it in. 1000 parts by weight of the obtained sodium acrylate polymer aqueous solution was charged, and a 48 wt% sodium hydroxide aqueous solution was added to adjust the pH to 12. The pH-adjusted sodium acrylate polymer aqueous solution was kept at 40 ° C. and 8.57 parts by weight of 35 wt% hydrogen peroxide solution (3000 mg / k relative to the sodium acrylate polymer aqueous solution charged as hydrogen peroxide).
g) was added dropwise and the mixture was stirred at 40 ° C. for 24 hours. Subsequently, in order to remove the residual hydrogen peroxide, 5.54 parts by weight of a 35 wt% sodium hydrogensulfite aqueous solution was added, and the mixture was further stirred at 40 ° C. for 24 hours to obtain a desired acrylic acid polymer aqueous solution (solid content: 40 wt%). %) Was obtained. The weight average molecular weight of the resulting acrylic acid polymer 1 was 10,000. The sodium polyacrylate was mildly synthesized by realizing a low temperature condition of 20 ° C. by adopting a redox polymerization method. Further, the acrylic acid-based polymer 1
As a result of measuring the characteristic value of,
The particle size on the large particle size side at which the height of the peak including is attenuated to half of its maximum value is 21.3 nm, the ratio of particles having a particle size exceeding 800 nm is 24.7%, and the relative half width in HPLC measurement is 1. 68, adsorption rate to burkeite is 9.6%, branching degree is 0.0, mud particle dispersing ability is 0.83, calcium ion capturing ability is 211 mgCaCO ₃ / g, and stability constant for calcium ion is 3.2. Met. In addition, the content of methquinone in the 40% by weight acrylic acid-based polymer aqueous solution was measured, and it was not detected.

Sampling was performed from the preparation liquid 10 minutes after the addition of the acrylic acid polymer aqueous solution (before the addition of sodium chloride) and the preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite) to obtain TSUB-TEC M100. The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before addition of sodium chloride was 503 / s, and the average particle size (on a number basis) was 65.3 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 6021 particles / s, and the average particle diameter was 35.7 μm. From these measurement results, the number of water-soluble salts was 55 due to the addition of sodium chloride.
The number of burkeite particles increased by 18 particles / s, and the average particle diameter of the increased burkeite particles was 27.5 μm.

The prepared liquid was supplied to a spray drying tower (countercurrent type) by a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. The high temperature gas supplied to the spray drying tower was supplied at a temperature of 218 ° C. from the lower part of the tower and discharged at 100 ° C. from the top of the tower. The water content of the obtained surfactant-supporting granule group 1 was 1% by weight.

The composition and physical properties of the surfactant-supporting granules 1 are shown in Table 1 (in the table, the surfactant-supporting granules are abbreviated as "granules"). The hue of the obtained surfactant-supporting granule group 1 was particularly good. The hue was visually confirmed and evaluated according to the following criteria. Particularly good: No pink particles are observed. Good: A slight pinking is confirmed in a very small part of the particles. Pinking: Clearly pinked particles are confirmed.

Detergent particle group 1 was produced by the following method using the surfactant-supporting granule group 1. Palmitic acid equivalent to 1.6 parts by weight of polyethylene glycol and 4 parts by weight of sodium palmitate (21 parts by weight of polyoxyethylene alkyl ether under mixing at 80 ° C. (Lunack P
-95, manufactured by Kao Co., Ltd., an alkylbenzene sulfonic acid precursor corresponding to 25 parts by weight of sodium alkylbenzene sulfonate (Neoperex GS, manufactured by Kao Co., Ltd.), and a sodium hydroxide aqueous solution of 11% by weight. % Hydrous surfactant composition was prepared.

Next, a Lodige mixer (Matsuzaka Giken Co., Ltd.)
100 parts by weight of the obtained granules 1 for supporting a surfactant are put into a product (capacity 130 L, with a jacket), and stirring of a main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s) is started. did. In addition, warm water of 80 ℃ to the jacket 10L /
Shed in minutes. 58 parts by weight of the above-mentioned surfactant composition was added thereto in 2 minutes, and then stirred for 5 minutes. Furthermore,
Crystalline sodium silicate ((Clariant Tokuyama,
22 parts by weight of an average particle size of 120 μm) crushed by a roller mill (average particle size of 8 μm) and 12 parts by weight of zeolite as the minimum amount that the stain exudation property of the detergent particle group becomes 1, and the main shaft (rotation) Number: 120 rpm, peripheral speed: 3.
1 m / s) and a chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) are stirred for 1 minute, and the detergent particle group 1-
1 was discharged. It should be noted that, here, the spotting property of the detergent particles is 1
The smaller the minimum amount of zeolite, the better the ability of the surfactant-supporting granules to support the liquid composition. The composition and physical property values of the detergent particle group 1-1 are shown in Table 2 (in the table, the detergent particle group is abbreviated as "particle group"). In addition, the cleaning performance of the above detergent particle group 1-1 was evaluated. The results are shown in Tables 2 and 3.

Experimental Example 2 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the acrylic acid polymer aqueous solution, a sodium polyacrylate aqueous solution produced according to the following method was used. Water 80.3
kg and ferrous sulfate heptahydrate 0.54 g (1.94 mm)
ol) was charged and the temperature was raised to 100 ° C. 190kg of 80% by weight acrylic acid aqueous solution while keeping the temperature at 100 ℃
(2.1 kmol) and 98 wt% 2-mercaptoethanol aqueous solution 3.9 kg (48.6 mol) over 5 hours, and 30 wt% sodium persulfate aqueous solution 5.0 kg
(6.3 mol) was added dropwise at a constant rate over 6 hours to carry out polymerization. Also, for deodorization, 35% hydrogen peroxide solution 1
5.7 kg (161.3 mol) was added dropwise over 1 hour from the end of the dropwise polymerization, and the mixture was aged for 4 hours and cooled.
After adding 167 kg (2 kmol) of 48 wt% sodium hydroxide aqueous solution at an internal temperature of 40 ° C. or lower, as a reducing agent, 35 wt% sodium bisulfite aqueous solution 5.7 kg
(19.2 mol) was added and reacted for 1 hour. afterwards,
Water was added to adjust the concentration to obtain a desired acrylic acid-based polymer aqueous solution (solid content: 40% by weight). The resulting acrylic acid polymer 2 had a weight average molecular weight of 10,000. Although this sodium polyacrylate is synthesized at a temperature of 100 ° C., by using 2-mercaptoethanol which is a chain transfer agent, the amount of the aqueous solution of sodium persulfate which is an initiator is suppressed, and under mild conditions. It is a composite.

Further, as a result of measuring the characteristic value of the acrylic acid-based polymer 2, the particle size on the large particle size side where the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value is 17. The ratio of particles having a particle size of 1 nm or more than 800 nm is 0%, and the relative half width in HPLC measurement is 1.5.
5, the adsorption rate to burkeite is 6.5%, and the degree of branching is 3.
9, the mud particle dispersibility was 0.82, the calcium ion trapping ability was 213 mgCaCO ₃ / g, and the stability constant for calcium ions was 3.3. In addition, as a result of measuring the methquinone content in the acrylic acid-based polymer aqueous solution,
Not detected.

Sampling was carried out from the preparation liquid 10 minutes after the addition of the acrylic acid polymer aqueous solution (before the addition of sodium chloride) and the preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite) to obtain TSUB-TEC M100. The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before addition of sodium chloride was 1375 / s, and the average particle size (on a number basis) was 77.0 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 3550 / s, and the average particle diameter was 24.5 μm. From these measurement results, the number of water-soluble salts was 21 by addition of sodium chloride.
The number of particles increased by 75 particles / s, and the average particle size of the increased burkeite was 11.6 μm.

[0211] In the same manner as in Experimental Example 1, a surfactant-supporting granule group 2 was obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 2. The hue of the resulting surfactant-supporting granule group 2 was particularly good.

A detergent particle group 2-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting particle group 2. 12 parts by weight of zeolite was added as the minimum amount so that the stain release property of the detergent particle group becomes 1. Table 2 shows the composition and physical property values of the detergent particle group 2-1. In addition, the above-mentioned detergent particle group 2-1
The cleaning performance was evaluated. The results are shown in Tables 2 and 3.

Experimental Example 3 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the acrylic acid polymer aqueous solution, a sodium polyacrylate aqueous solution produced according to the following method was used. The sodium polyacrylate aqueous solution was manufactured according to the method described in the example of Japanese Patent Publication No. 2-24283. The reaction was performed by supplying an aqueous sodium acrylate solution having a neutralization degree of 95% and a concentration of 37.7% by weight at 3.11 kg / h, and an aqueous sodium hydrogen sulfite solution having a concentration of 35% by weight at 0.13 kg / h, and air. The supply amount was 3 m ³ / h, and the average temperature of the jacket was 20 ° C. 1000 parts by weight of the obtained aqueous sodium acrylate polymer solution was charged, and 8.57 parts by weight of 35% by weight hydrogen peroxide solution (3000 mg based on the aqueous sodium acrylate polymer solution charged as hydrogen peroxide) was added.
/ Kg), and the mixture was stirred at 40 ° C. for 24 hours.
Subsequently, in order to remove the residual hydrogen peroxide, 5.54 parts by weight of a 35 wt% sodium hydrogensulfite aqueous solution was added, and the mixture was further stirred at 40 ° C. for 24 hours to obtain a desired acrylic acid polymer aqueous solution (solid content: 40 wt%). %) Was obtained. The weight average molecular weight of the resulting acrylic acid polymer 3 was 10,000. The sodium polyacrylate was mildly synthesized by realizing a low temperature condition of 20 ° C. by adopting a redox polymerization method. In addition, as a result of measuring the characteristic value of the acrylic acid-based polymer 3, 10
The height of the peak including nm is reduced to half of its maximum value, the particle size on the large particle size side is 18.9 nm, the ratio of particles having a particle size exceeding 800 nm is 16.5%, and the relative half width in HPLC measurement. Is 1.70, the adsorption rate on burkeite is 9.1%, the degree of branching is 0.0, and the dispersibility of mud particles is 0.8.
3. Calcium ion capture capacity is 212mgCaCO ₃ /
The stability constant for g and calcium ions was 3.3. In addition, as a result of measuring the methquinone content in the 40% acrylic acid polymer aqueous solution, 6 ppm of methquinone was contained.

Sampling was carried out from a preparation liquid 10 minutes after the addition of a 40% by weight aqueous acrylic acid polymer solution (before the addition of sodium chloride) and a preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite) to obtain TSUB-TEC M100.
The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before addition of sodium chloride was 501 particles / s, and the average particle size (on a number basis) was 65.1 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 5293 particles / s, and the average particle diameter was 34.7 μm. From these measurement results, the number of water-soluble salts was 47 by addition of sodium chloride.
The number of particles increased by 92 particles / s, and the average particle size of the increased burkeite was 26.8 μm.

In the same manner as in Experimental Example 1, a surfactant-supporting granule group 3 was obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granule group 3. The hue of the resulting surfactant-supporting granule group 3 was good.

A detergent particle group 3-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting granule group 3. 12 parts by weight of zeolite was added as the minimum amount so that the stain release property of the detergent particle group becomes 1. Table 2 shows the composition and physical property values of the detergent particle group 3-1. In addition, the above-mentioned detergent particle group 3-1
The cleaning performance was evaluated. The results are shown in Tables 2 and 3.

Experimental Example 4 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the sodium polyacrylate aqueous solution, Aron A20UN (solid content 41.3% by weight) manufactured by Toagosei Co., Ltd. was used, and the water content of the preparation liquid was adjusted by the amount of water initially charged into the mixing tank. In addition, this Aron A20UN is not used for a general detergent, but is used as a pigment dispersant for paper processing, a dyeing auxiliary agent, and the like.

Further, as a result of measuring the characteristic value of the acrylic acid polymer 4, the particle size on the large particle size side where the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value is 16. The ratio of particles having a particle size of 2 nm or more than 800 nm is 14.8%, the relative half width in HPLC measurement is 1.81, the adsorption rate to burkeite is 7.4%, the dispersibility of mud particles is 0.82, Calcium ion capture capacity is 207
The stability constant for mgCaCO ₃ / g and calcium ion was 3.7. Moreover, as a result of measuring the methquinone content in the acrylic acid-based polymer aqueous solution, it was not detected.

Sampling was performed from the preparation liquid 10 minutes after the addition of the acrylic acid-based polymer aqueous solution (before the addition of sodium chloride) and the preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite), and the sample was prepared with TSUB-TEC M100. The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before the addition of sodium chloride was 625 / s, and the average particle size (on a number basis) was 79.5 μm. Sodium chloride addition 60
The number of particles in the prepared liquid after the separation was 2780 particles / s, and the average particle size was 25.5 μm. From these measurement results, the number of water-soluble salts was 2155 /
The average particle size of burkeite is 21.0
was μm.

In the same manner as in Experimental Example 1, a surfactant-supporting granule group 4 was obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 4. The hue of the obtained surfactant-supporting granule group 4 was particularly good.

A detergent particle group 4-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting granule group 4. 12 parts by weight of zeolite was added as the minimum amount so that the stain release property of the detergent particle group becomes 1. Table 2 shows the composition and physical property values of the detergent particle group 4-1. In addition, the above-mentioned detergent particle group 4-1
The cleaning performance was evaluated. The results are shown in Tables 2 and 3.

Experimental Example 5 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the acrylic acid polymer aqueous solution, a sodium polyacrylate aqueous solution produced according to the following method was used. The sodium polyacrylate aqueous solution was manufactured according to the method described in the example of Japanese Patent Publication No. 2-24283. The reaction was performed by supplying an aqueous sodium acrylate solution having a neutralization degree of 95% and a concentration of 37.7% by weight at 3.11 kg / h, and an aqueous sodium hydrogen sulfite solution having a concentration of 35% by weight at 0.13 kg / h, and air. The supply amount was 3 m ³ / h and the average temperature of the jacket was 20 ° C. to obtain the desired acrylic acid polymer aqueous solution (solid content 40% by weight). The weight average molecular weight of the resulting acrylic acid polymer 5 was 10,000. The sodium polyacrylate was mildly synthesized by realizing a low temperature condition of 20 ° C. by adopting a redox polymerization method. Further, as a result of measuring the characteristic value of the acrylic acid-based polymer 5, the particle size on the large particle size side where the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value is 16.1 nm and 800 nm. The ratio of particles having a particle size of over 9.3%, the relative half width in HPLC measurement is 1.69, the adsorption rate to burkeite is 9.3%, the branching degree is 0.0, and the dispersibility of mud particles is The calcium ion-capturing ability was 0.83, the calcium ion-capturing ability was 212 mgCaCO ₃ / g, and the stability constant for calcium ions was 3.3. Further, as a result of measuring the methquinone content in the 40% by weight acrylic acid polymer aqueous solution, 40 ppm of methquinone was contained.

Sampling was performed from the preparation liquid 10 minutes after addition of the 40% by weight acrylic acid-based polymer aqueous solution (before sodium chloride addition) and the preparation liquid 60 minutes after addition of sodium chloride (before addition of zeolite) to obtain TSUB-TEC M100.
The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before addition of sodium chloride was 640 particles / s, and the average particle size (on a number basis) was 81.1 μm. The number of particles in the prepared liquid 60 minutes after the addition of sodium chloride was 2459 / s, and the average particle size was 23.6 μm. From these measurement results, the number of water-soluble salts was 18 by addition of sodium chloride.
The number of particles increased by 19 particles / s, and the average particle size of the increased burkeite was 14.2 μm.

[0224] In the same manner as in Experimental Example 1, a surfactant-supporting granule group 5 was obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 5. The hue of the obtained surfactant-supporting granules 5 was pink.

Detergent particle group 5-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting granule group 5. 12 parts by weight of zeolite was added as the minimum amount so that the stain release property of the detergent particle group becomes 1. Table 2 shows the composition and physical property values of the detergent particle group 5-1. Also, the above-mentioned detergent particle group 5-1
The cleaning performance was evaluated. The results are shown in Tables 2 and 3.

Experimental Example 6 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the acrylic acid polymer aqueous solution, BASF sodium polyacrylate aqueous solution: Socalan PA-30CL (solid content 46.8% by weight) was used, and the water content of the preparation liquid was the water initially charged to the mixing tank. The amount was adjusted. In addition, this Sokaran PA
-30CL is commercially available for use in detergent builders, and is used in general detergents.

Further, the characteristic value of the acrylic acid polymer 6 is
As a result of the measurement, the peak including 10 nm in the light scattering measurement
The particle size on the large particle size side where the height of the peak decreases to half of its maximum value
Of 33.7 nm and particles with a particle size exceeding 800 nm
The ratio is 0%, and the relative half width in HPLC measurement is 1.3.
2. Adsorption rate to burkeite is 2.3%, branching degree is 1.
0, mud particle dispersion capacity 0.79, calcium ion capture
Noh is 206 mg CaCO ₃/ G, for calcium ion
The stability constant was 0.8. Also, the 46.8-fold
Amount of methaquinone in the acrylic acid polymer aqueous solution
As a result of the measurement, it contained 15 ppm of methquinone.
It was

Sampling was performed from the preparation liquid 10 minutes after the addition of the aqueous solution of the acrylic acid polymer (before the addition of sodium chloride) and the preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite) to obtain TSUB-TEC. M100
The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before the addition of sodium chloride was 632 / s, and the average particle size (on a number basis) was 66.5 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 851 / s, and the average particle size was 67.2 μm. From these measurement results, the number of water-soluble salts increased by the addition of sodium chloride was 219 / s.

In the same manner as in Experimental Example 1, a surfactant-supporting granule group 6 was obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 6. The hue of the obtained surfactant-supporting granules 6 was pink.

Detergent particle group 6-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting granule group 6. The amount of zeolite added was 52 parts by weight as the minimum amount at which the stain release property of the detergent particle group became 1. Table 2 shows the composition, physical property values, and cleaning performance of the detergent particle group 6-1.

Further, as in Experimental Examples 1 to 5, a detergent particle group 6-2 having a zeolite amount of 12 parts by weight was prepared and the cleaning performance was evaluated. The results are shown in Table 3.

Experimental Example 7 A preparation liquid was obtained in the same manner as in Experimental Example 1. As the acrylic acid-based polymer aqueous solution, an aqueous solution of sodium salt of acrylic acid-maleic acid copolymer (solid content 40% by weight, molar ratio of maleic acid and acrylic acid is 3/7) prepared according to the following method is used. I was there.

A glass reactor equipped with a stirrer, a thermometer, a reflux condenser, an inlet for dropping a monomer solution and an initiator solution, and a heating jacket (hereinafter referred to as a reactor) is a raw material supply tank for the monomer solution and the initiator solution. (Hereinafter, also referred to as a monomer supply tank and an initiator supply tank)
In advance, 175 kg of a 40% by weight aqueous solution of a maleic acid salt partially neutralized with a 48% by weight sodium hydroxide aqueous solution at a neutralization degree of 40% is charged in a reactor, and 125 kg of an 80% by weight acrylic acid aqueous solution is charged in a monomer supply tank. . Also, 35
20 kg of weight% hydrogen peroxide water was charged into the initiator supply tank. Warm water is passed through the jacket of the reactor so that the polymerization temperature is 10
Adjust to 0 ± 3 ° C. An 80% by weight acrylic acid aqueous solution and a 35% by weight aqueous hydrogen peroxide solution were continuously added dropwise through the inlet and stirred. Drip in 6 hours, then 2
Let it stay for a time. At this time, although some heat was generated, the polymerization temperature was maintained at 100 ± 3 ° C. while adjusting the jacket warm water. By performing these series of operations, an acrylic acid polymer 7 having a polymerization rate of acrylic acid and maleic acid of 95% or more and a weight average molecular weight of 70,000 was obtained. The acrylic acid-based polymer 7
Was adjusted to pH 7 and a concentration of 40% by weight using a 48% by weight aqueous solution of sodium hydroxide to obtain an aqueous sodium salt solution. This acrylic acid-based polymer 7 was synthesized under a hard condition in which a large amount of hydrogen peroxide was used to generate many radicals, and a chain transfer agent or the like was not used in the synthesis. Further, as a result of measuring the characteristic value of the acrylic acid-based polymer 7, the particle diameters on the large particle diameter side where the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value are 423.3 nm and 800 nm. The ratio of particles with a particle size exceeding 29.1%, the adsorption rate to barkeite is 2.3
%, The mud particle dispersibility was 0.3, the calcium ion trapping ability was 380 mgCaCO ₃ / g, and the stability constant for calcium ions was 4.0. Further, as a result of measuring the content of methoquinone in the 40 wt% acrylic acid-based polymer aqueous solution, methoquinone was not detected.

Sampling was performed from the preparation liquid 10 minutes after the addition of the aqueous solution of the acrylic acid polymer (before the addition of sodium chloride) and the preparation liquid 60 minutes after the addition of sodium chloride (before the addition of zeolite) to obtain TSUB-TEC. M100
The number of particles and the particle size distribution were measured. The number of particles in the preparation liquid before addition of sodium chloride was 589 / s, and the average particle size (on a number basis) was 65.4 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 601 particles / s, and the average particle diameter was 65.5 μm. From these measurement results, the number of water-soluble salts increased by the addition of sodium chloride was 12 / s.

In the same manner as in Experimental Example 1, surfactant-supporting granules 7 were obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 7. The hue of the resulting surfactant-supporting granules 7 was particularly good.

Detergent particle group 7-1 was produced in the same manner as in Experimental Example 1 using the surfactant-supporting granule group 7. The amount of zeolite added was 43 parts by weight, which was the minimum amount at which the stain release property of the detergent particle group became 1. Table 2 shows the composition, physical properties, and cleaning performance of the detergent particle group 7-1. In addition, Experimental Examples 1 to
In the same manner as in No. 5, a detergent particle group 7-2 having a zeolite amount of 12 parts by weight was prepared, and the cleaning performance was evaluated. The results are shown in Table 3.

[0237]

[Table 1]

[0238]

[Table 2]

[0239]

[Table 3]

In the experimental examples of the present invention, by using an acrylic acid type polymer having specific properties, the bar kerite precipitated in the preparation process of the preparation liquid and the spray drying process becomes fine. Therefore, the surfactant-supporting granule groups 1 to 5 are
The mode diameter of the pore volume distribution is smaller than that of the surfactant-supporting granule group 6 or 7, and the pore volume is larger, so that the capability of supporting the liquid composition is enhanced. As a result, the detergent particle group of the present invention (detergent particle group 1-
1 to 5-1) can significantly reduce the necessary amount of zeolite added afterwards in order to maintain the quality (staining resistance) (Table 2). Further, the detergent particle groups 1-1 to 5 of the present invention
-1 is a detergent particle group 6-2 or 7 having the same amount of zeolite
A cleaning performance higher than −2 can be expressed (Table 3). In addition, the detergent particle group 6-2 or 7-2 was an agglomerate exuding the surfactant composition, and the dispersion solubility at the time of evaluating the cleaning performance was lowered. That is, by using the surfactant-supporting granules 1 to 5 having a high carrying ability of the present invention, the surfactant-supporting granules 6 or 7 (both of which have a peak height of 10 nm in light scattering measurement) It is possible to obtain a detergent particle group having higher quality and higher cleaning performance than using a detergent particle group in which the particle diameter on the large particle diameter side that attenuates to half the maximum value exceeds 32 nm). In addition, detergent particles having excellent hue can be obtained by using the particles 1 to 4 for supporting the surfactant.

[0241]

EFFECTS OF THE INVENTION According to the present invention, a group of granules for supporting a surfactant having an excellent carrying ability (loading capacity / loading power) of a surfactant composition, high quality and high cleaning performance, and also an excellent hue There is also provided a detergent particle group, and a detergent composition containing the detergent particle group.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a histogram of a light scattering measurement.

FIG. 2 is a graph showing an asymmetry coefficient (A) of an acrylic acid-based polymer.
FIG. 3 is a schematic diagram of the HPLC emission pattern used to measure s).

FIG. 3 is a schematic diagram of a calibration curve showing the relationship between the logarithm of the calcium ion concentration and the potential used for measuring the calcium ion trapping ability of an acrylic acid polymer.

FIG. 4 is a schematic diagram showing a relationship of calcium ion concentration in a dropping amount A of a CaCl ₂ solution of a sample used for measuring a calcium ion capturing ability of an acrylic acid polymer.

[Explanation of symbols]

h Peak height Ve Elution time W _1/2 Half width

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C11D 17/06 C11D 17/06 (72) Inventor Masatsugu Tanaka 1334 Minato Minato, Wakayama Kao Corporation Research Institute (72) Inventor Yoshimura Chutoku 1334 Minato Minato, Wakayama City Kao Co., Ltd. (72) Inventor Hitoshi Takatani 1334 Minato Minato Wakayama City, Kao Co., Ltd. (56) Reference JP 62-112697 (JP, A) JP 63-282371 (JP, A) JP 2000-186300 (JP, A) JP 62-121705 (JP, A) JP 11-35989 (JP, A) WO 00/039265 (WO, A1) WO 96 / 018714 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 1/00-17/08

Claims (11)

(57) [Claims] 1. A particle size on the large particle size side where the weight average molecular weight is 3,000 to 100,000 and the height of a peak containing 10 nm in light scattering measurement is attenuated to half the maximum value, and the particle size on the large particle size side is 32 nm.
Acrylic acid polymer ratio of particles having a particle size greater than the are and 800nm or less is 70% or less, preparation and spray drying containing sodium carbonate and sodium sulfate, viewed including the burkeite, sodium carbonate and Sodium sulfate
The total content of thorium is the weight ratio to the content of the polymer.
The method for producing a group of granules for supporting a surfactant, which is 19/1 to 1/2 . 2. The method for producing surfactant-supporting granules according to claim 1, wherein the acrylic acid-based polymer has a calcium ion-trapping capacity of 160 mgCaCO ₃ / g or more and a stability constant for calcium ions of 2.6 or more. . Wherein the particles for supporting a surfactant is, according to claim 1, the acrylic polymer containing 5-30 wt%, charcoal sodium and sodium sulfate in a weight ratio of 1 / 10-10 / 1 containing Alternatively, the method for producing the granules for supporting a surfactant according to item 2. 4. The method for producing granules for supporting a surfactant according to claim 1, wherein the acrylic acid-based polymer blended in the preparation liquid is in the form of an aqueous solution having a quinone content of 6 ppm or less. 5. The acrylic acid polymer is acrylic acid and / or
Alternatively, the amount of the monomer component other than the salt is acrylic acid and / or
Is less than 1 / 2.5 in molar ratio to the amount of salt
The granules for supporting a surfactant according to any one of claims 1 to 4.
How to make a group. 6. 0.0 measured by mercury porosimeter
The mode diameter of the pore volume distribution of 1 to 3 μm is 1.5 μm or less, and the pore volume of 0.01 to 3 μm is 0.3 mL / g.
It is above, and the granule strength is 15 MPa or more.
5. A group of granules for supporting a surfactant obtained by the method according to any one of 5 to 6 . 7. The particle size on the large particle size side where the weight average molecular weight is 3,000 to 100,000 and the height of the peak including 10 nm in the light scattering measurement is attenuated to half the maximum value, and the particle size on the large particle size side is 32 nm.
It contains 5 to 30% by weight of an acrylic acid-based polymer in which the ratio of particles having a particle size of 800 nm or less is 70% or less, and sodium carbonate and sodium sulfate are contained in a weight ratio of 1/10 to 10 /. 1. A group of surfactant-containing granules containing burkeite, wherein the total content of sodium carbonate and sodium sulfate is 19/1 to 1/2 with respect to the polymer content. 8. The acrylic acid-based polymer has a calcium ion-capturing ability of 160 mgCaCO ₃ / g or more and a stability constant for calcium ions of 2.6 or more.
7. A group of granules for supporting a surfactant according to 7 . 9. The acrylic acid polymer is acrylic acid and / or
Alternatively, the amount of the monomer component other than the salt is acrylic acid and / or
Is less than 1 / 2.5 in molar ratio to the amount of salt
A group of granules for supporting a surfactant according to claim 7 or 8. 10. A detergent particle group in which 10 to 100 parts by weight of a surfactant composition is supported with respect to 100 parts by weight of the surfactant-supporting granule group according to any one of claims 6 to 9 . 11. The detergent particle group according to claim 10 is 50 to 50.
A detergent composition containing 100% by weight and having an average particle size of 150 to 500 μm and a bulk density of 500 to 1000 g / L.