JP2002114995A - Method for manufacturing granule group to carry surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a group of granules to carry a surfactant which excels in the capacity of carrying a liquid surfactant composition, its manufacturing method, a group of detergent particles using the group of granules to carry a surfactant, and a detergent composition comprising the group of detergent particles. SOLUTION: The method for manufacturing a group of granules to carry a surfactant containing a burkeite comprises subjecting a preparation fluid containing an acrylic acid based polymer having a weight average molecular weight of 3,000-100,000, a particle diameter in the side of larger particles where the peak height including 10 nm in the light scattering measurement is damped to the half of the maximum value of <=32 nm, and a ratio of particles having a particle diameter of >800 nm of <=70%, and sodium carbonate and sodium sulfate to spray drying. The group of granules to carry a surfactant comprises 5-30 wt.% acrylic acid based polymer and a burkeite containing sodium carbonate and sodium sulfate at a weight ratio of 1/10 to 10/1 and, simultaneously, at a weight ratio of the total content of the sodium carbonate and the sodium sulfate to the content of the above polymer of 19/1 to 1/2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to particles for supporting a surfactant 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 granules.

[0002]

2. Description of the Related Art As one method for obtaining a high-density detergent, there is a production method including a step of supporting a liquid surfactant on particles for supporting a surfactant. In the production method, the particles for supporting a surfactant are required to have a high ability to support a liquid surfactant. That is, the supporting ability required for the particles for supporting a surfactant is such that a large amount of the liquid surfactant can be supported (capacity) and that the liquid surfactant once absorbed can be strongly retained inside the granules without exuding ( 2)
Consists of two factors. In each case, the loading capacity is determined by blending an amount of surfactant necessary for cleaning performance, and the loading capacity is reduced by suppressing the bleeding of the liquid surfactant, thereby lowering the fluidity of the powder detergent, caking and This is important in preventing the transfer of the liquid surfactant to the container and its surface.

[0003] The structure required for a surfactant-supporting granule group having a high loading capacity is to increase the loading capacity by having a sufficient pore volume inside the granule, and to increase the loading capacity by having a fine pore diameter. Is desirable. Such a structure can be obtained by using fine particles to constitute surfactant-supporting granules while maintaining mutual contact between particles and sufficient voids. As a source of these fine particles,
Sodium carbonate, a representative water soluble salt in detergent compositions, can be used. Sodium carbonate forms monohydrate of sodium carbonate and burkeite, which is a double salt with sodium sulfate, in the preparation solution, and they form fine needle-like crystals, which are formed inside the granules for supporting the surfactant. Can be a base for forming an effective carrier site.

As a technique for realizing this, Japanese Patent Laid-Open No.
Japanese Patent No. 112697 discloses that crystal growth was adjusted by mixing an effective amount of a crystal growth modifier, which is an organic substance having at least three carboxyl groups in a molecule, into a surfactant slurry before 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 (particles for supporting a surfactant) having a high adsorption capacity.

However, the supporting ability of the particles for supporting a surfactant obtained by this method was not sufficient. One of the causes is that the amount of fine burkeite dispersed in the slurry before spray drying is insufficient, and the amount of fine burkeite crystals in the granules obtained by spray drying is not sufficient. Is mentioned. Although burkeite in the form of fine needle crystals is an effective base for improving the loading capacity, burkeite in the present technology is based on the presence of dissolved sodium sulfate and granular sodium carbonate added later, and the granular carbonic acid is used as the base. Most of them are formed as strong and large-sized aggregates because they are formed on or near the surface of sodium. Therefore, the burkeite in the form of fine needle-like crystals generated in the slurry is small, and burkeite, which can be originally fine needle-like crystals, is in a state of aggregation with a large particle diameter in the granules even after spray drying, and the pore volume and the pore diameter are small. Was not able to express sufficient supporting ability. Another cause is that the polycarboxylate polymer is not sufficiently selected as a crystal growth regulator for burkeite, and thus has a low effect of precipitating burkeite as fine needle-like crystals.

[0006]

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

[0007]

That is, the present invention provides [1]
The weight average molecular weight is from 3,000 to 100,000, the particle size on the large particle size side where the height of a peak including 10 nm in light scattering measurement is attenuated to a half of the maximum value is 32 nm or less, and 8
Method for producing surfactant-containing granules containing burkeite by spray-drying a preparation solution containing an acrylic acid polymer in which the ratio of particles having a particle size exceeding 00 nm is 70% or less and sodium carbonate and sodium sulfate [2] a mode diameter of a pore volume distribution of 0.01 to 3 μm measured by a mercury porosimeter of 1.5 μm or less;
The particles for supporting a surfactant obtained by the production method according to the above [1], wherein the pore volume of μm is 0.3 mL / g or more and the granule strength is 15 MPa or more; [3] The weight average molecular weight is 3
1,000 to 100,000, and the particle size on the large particle size side where the height of a peak including 10 nm in light scattering measurement attenuates to half of its maximum value is 32 nm or less and a particle having a particle size exceeding 800 nm. It contains 5 to 30% by weight of an acrylic acid polymer having a ratio of 70% or less, and contains sodium carbonate and sodium sulfate in a weight ratio of 1/10 to 10/1 and a total content of sodium carbonate and sodium sulfate. Surfactant-supporting granules containing burkeite containing 19/1 to 1/2 by weight relative to the polymer content, [4] above [2]
Or a detergent particle group comprising 10 to 100 parts by weight of a surfactant composition per 100 parts by weight of the surfactant-supporting granule group according to [3]; [5] a detergent particle group according to [4]. Is 50 to 100% by weight, and the average particle size is 150 to 50.
The present invention relates to a detergent composition having 0 μm and a bulk density of 500 to 1000 g / L.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Definition of terms The surfactant-supporting granules of the present invention are granules obtained by spray-drying a preparation solution containing an acrylic acid polymer and sodium carbonate and sodium sulfate, and a surfactant composition. Refers to granules used for supporting the particles, and the aggregate thereof is referred to as a group of particles for supporting a surfactant. The detergent particles are particles containing a surfactant, a builder, and the like obtained by supporting a surfactant composition on granules for supporting a surfactant, and the detergent particles mean an aggregate thereof. The detergent composition is a detergent composition containing 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, a bleaching activator) which is separately added in addition to the detergent particle if desired. Etc.). The acrylic acid 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. In general, burkeite refers to a double salt composed of sodium carbonate and sodium sulfate in a molar ratio of 1: 2. However, 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 in water of 100 g at 25 ° C. of 0.1 g.
It has a molecular weight of 5 g or more and less than 1,000. The water-soluble polymer has a solubility in water of 100 g at 25 ° C of 0.5.
g or more and an organic polymer having a molecular weight of 1,000 or more. The water-insoluble substance is a solid having a solubility in 100 g of water at 25 ° C. of less than 0.5 g. The surfactant composition is a composition containing a surfactant that is in a liquid and / or paste form when loaded on the particles for supporting a surfactant.

[0009] 2. The properties required for the surfactant-supporting granules (hereinafter, also referred to as “supporting granules”) to exhibit a high supporting ability include:
The granules have a lot of spaces (supporting sites) for supporting a liquid and / or paste-like surfactant composition (hereinafter, also referred to as a liquid composition), that is, the pore volume inside the granules is large and the That is, the supporting capacity for the composition is large, and the pore size inside the granule is small, and the supporting force for the liquid composition is strong. Further, the supporting granules need to have a granular strength that can withstand the operation at the time of producing the detergent particles, such as being mixed to support the liquid composition. Further, from the viewpoint of enhancing the cleaning performance of the detergent particles and the detergent composition, it is desired that the supporting granules have a high supporting ability to the liquid composition and a high builder ability. Here, the builder ability means an ability to enhance or enhance the cleaning performance by the surfactant.

In view of the above, since it acts as an alkaline agent showing a suitable pH buffer region in the washing liquid, sodium carbonate used as a typical builder in detergent compositions and / or ionic strength in the washing liquid is increased to increase sebum. Since it suitably acts on dirt washing and the like, a study was conducted to form a structure having many fine spaces inside the above-mentioned granules using sodium sulfate used as a typical builder in a detergent composition.

As a result, a preparation solution containing an acrylic acid polymer having specific properties and sodium carbonate and sodium sulfate is prepared, and the preparation solution is spray-dried to remove sodium carbonate precipitated in granules. The present inventors have found that particles of burkeite, which is a double salt derived from sodium sulfate and having fine crystals, can be obtained as a support granule having a fine spatial structure in the above-mentioned granules.

The acrylic acid polymer is a water-soluble polymer having an effect of improving the washing performance, and specifically, an effect of dispersing solid particle dirt such as mud particles from clothes into a washing bath and a solid polymer. It is a builder that has the effect of preventing particulate soil from re-adhering to clothing, and the function of trapping metal ions such as calcium ions that inhibit the cleaning action of surfactants. The supporting granules obtained by using an acrylic acid polymer having both the above-mentioned property of refining burkeite and having a high property of improving the cleaning performance of the burkeite are excellent in supporting a surfactant composition. In addition to having builder ability, it has excellent builder ability.

The acrylic acid polymer having the above-mentioned specific properties is characterized in that it has a property of refining burkeite crystals precipitated in the step of preparing the preparation and in the step of spray-drying the preparation, and has a high property. It has builder ability. Specifically, the weight average molecular weight measured by the following weight average molecular weight measurement (1) is 3,000 to 100,000, and the height of a peak including 10 nm in the light scattering measurement (2) described below is attenuated to a half value of the maximum value. The ratio of particles having a particle size of 32 nm or less and a particle size exceeding 800 nm on the large particle size side is 70% or less, and if necessary, the dispersibility of mud particles by the following dispersibility measurement (3) is 0%. 0.5 or more, the calcium ion capturing ability by the following capturing ability measurement (4) was 160 mg Ca
Those having a stability constant of not less than CO ₃ / g and a calcium ion of not less than 2.6 by the following stability constant measurement (5) are preferred.

Here, the weight average molecular weight measurement (1), light scattering measurement (2), dispersion ability measurement (3), trapping ability measurement (4) and stability constant measurement (5) will be described in detail, and furthermore, each characteristic will be described. Preferred embodiments for are described.

Weight average molecular weight measurement (1): The molecular weight measurement of the acrylic acid-based polymer includes: Conversion standard material: polyacrylic acid (AMERICAN STANDAR
DS CORP) 2. Eluent: 0.2 mol / L phosphate buffer / CH ₃ CN:
9/1 (volume ratio) Column: PWXL + G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation) Detector: RI5. 5. Sample concentration: 5 mg / mL 6. Injection volume: 0.1 mL Measurement temperature: 40 ° C8. Flow rate: 1.0 mL / min.

Here, the preferred range of the weight average molecular weight of the acrylic acid polymer in the present invention is from 3,000 to 100,000, but it is necessary to increase the weight average molecular weight to increase the granule strength of the supporting granules. From the viewpoint of adjusting the weight average molecular weight to enhance the builder ability, more preferably 30,000 to 80,000,
More preferably 4,000 to 60,000, and particularly preferably 5,000 to 5
And most preferably from 6,000 to 30,000.

Light scattering measurement (2): solid content of 40% by weight in a 50 mL sample tube (hereinafter, solid content is indicated by%)
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 sample of the acrylic acid polymer 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 sodium sulfate: manufactured by Shikoku Chemicals Co., Ltd.) was added to the aqueous solution while stirring in a thermostat adjusted to 50 ° C., followed by sodium carbonate (dense ash: central glass ( Co., Ltd.) 5.
Add 0 g and dissolve. Then, at 50 ° C for 60 minutes
, And then allowed to cool in a room at 25 ° C for 2 hours.

The above sample was filtered through a 0.8 μm filter (SLAA025LS manufactured by Millipore), placed in a cell having an inner diameter of 12 mm, adjusted to a temperature of 25 ° C., and treated with DLS-7000DH manufactured by Otsuka Electronics Co., Ltd. And particle size measurement by 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. The analysis calculates a histogram based on the scattering intensity using fitting by the Marquardt method. As shown in FIG. 1, the histogram shows the particle diameter on the horizontal axis and the ratio on the vertical axis.

Here, the broadening of the peak containing 10 nm of the particle size distribution of the acrylic acid polymer measured by light scattering toward the larger particle size indicates the degree of association of the polymer molecules. That is, the larger the spread to the large particle size side, the more the polymer molecules are associated, and the smaller the spread to the large particle size side, the better the polymer molecules are dispersed. Means As a result of examining the relationship between the broadening of the peak including 10 nm observed in the particle size distribution of the acrylic acid-based polymer to the large particle size side and the effect of regulating the crystal growth on burkeite, it was found that the spread to the large particle size side was small. It is considered that burkeite precipitated in the preparation step of the preparation liquid and the spray drying step becomes finer and more needle-like.

The extent to which the peak including 10 nm observed in the particle size distribution obtained by the dynamic light scattering measurement of the acrylic acid polymer toward the large particle size is, here, 10 nm
The height of the peak containing the peak value is defined by the particle size on the large particle size side (hereinafter, the half-reduced particle size) at which the peak value attenuates to a half value of the maximum value (for example, FIG. 1). That is, the larger the half-reduced particle size, the larger the spread to the large particle size side, and the smaller the half-reduced particle size, the smaller the spread to the large particle size side.

The preferred half-reduced particle size of the acrylic acid polymer in the present invention is 32 nm or less, but it acts on burkeite crystals precipitated in the step of preparing the preparation solution and in the step of spray-drying to make the burkeite fine. In light of the above, more preferably 30 nm or less, still more 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).
0nm) after filtering through a filter.
Particle sizes above 800 nm may be observed. It is considered that these were associated with the acrylic acid polymer. As a result of examining the relationship between the ratio of particles having a particle diameter exceeding 800 nm and the absorbability of the surfactant-supporting granules produced using the acrylic acid-based polymer in the liquid composition, it was found that 8
It has been found that when particles having a high ratio of particles having a particle size exceeding 00 nm are used, the absorbability of the supporting granules to the liquid composition is reduced. The proportion of particles having a particle size of more than 800 nm is similar to the increase of the half-value particle size described above.
It is thought that the polymer exhibits an associative property of the acrylic acid polymer, and there is a concern that the crystal growth adjusting effect may be reduced. However, an acrylic acid polymer having a high ratio of particles having a particle size exceeding 800 nm has a high film forming property Therefore, the properties of the film formed on the surface of the surfactant-supporting granules become difficult to pass through the liquid composition. That is, it is considered that such an acrylic acid-based polymer deteriorates the absorbability of the particles for supporting a surfactant in the liquid composition.

In the present invention, the proportion of particles having a particle size exceeding 800 nm of the acrylic acid polymer in the present invention is 70% or less. From the viewpoint of increasing the amount of the liquid composition supported by the supporting granules, the content is preferably 60% or less, more preferably 50% or less, further preferably 40% or less, and most preferably 30% or less.

The acrylic acid polymer is the following HPL
It is preferable to have the following discharge pattern in the C measurement. The HPLC measurement is described below.

HPLC measurement: The column was manufactured by Tosoh Corporation
Using TSK Gel G2500pwxl, at a measurement temperature of 40 ° C., ion-exchanged water is allowed to flow through the mobile phase at a rate of 0.5 mL / min, and detection is performed with a differential refractometer (Showa Denko SE-71) at a sampling interval of 50 ms. First, 0.1% of glycerin (special grade, for example, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.).
A 2% aqueous solution is prepared, and 50 μL is injected into the column to measure the glycerin discharge pattern as a reference substance. In addition, this measurement is performed twice. Next, solid content 4
A sample of the acrylic acid polymer, which was previously adjusted to 0 ± 1%, was diluted 100 times with ion-exchanged water to prepare a sample solution, and 50 μL of the sample solution was injected into the column to thereby discharge the acrylic acid polymer. Is measured. This measurement is performed twice.

The difference in the discharge pattern of the acrylic acid polymer in the HPLC measurement can be confirmed by the relative half width described below. First, as shown in FIG. 1, a straight line is drawn from the base line to the base line, and a perpendicular line is drawn from the point where the height is the maximum value at the measured peak to obtain a half width. 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 (B) is obtained. B = A ₂ / A ₁ Here, the above-mentioned HP of the acrylic acid polymer of the present invention is used.
A preferable relative half width of the discharge pattern in the LC measurement is 1.4 or more, more preferably 1.45 or more,
It is more preferably at least 1.5, most preferably at least 1.55.

The acrylic acid polymer preferably has high adsorption characteristics in the measurement of the adsorption rate of burkeite in the following preparation liquid (hereinafter referred to as adsorption rate measurement). The adsorption rate measurement will be described below.

Adsorption rate measurement: 558 g of ion-exchanged water (charged water) was weighed and placed in a 1 L stainless beaker, and a stirring blade equipped with three propeller blades of 2 × 4 cm at a temperature of 50 ° C. was set to 200 rpm. Rotate at a speed of min and stir. 154 g of sodium sulfate (anhydrous neutral sodium sulfate: manufactured by Shikoku Chemicals Co., Ltd.) is added to the ion-exchanged water and stirred for 10 minutes to dissolve. Subsequently, 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 of an acrylic acid polymer previously adjusted to a solid content of 40% (concentration or addition of ion-exchanged water) was applied over 30 seconds. And add. Part 10
Minutes later, 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 solution under stirring was weighed in a centrifugal sedimentation tube, and kept at a temperature of 50 ° C. with a centrifuge (manufactured by Domestic Centrifuge Co., Model H300) at 10,000 r.
Centrifuge for 5 minutes at rpm.

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

Further, in order to determine the amount of inorganic ions dissolved in the supernatant, 3 g of the supernatant was precisely weighed and measured for 100 m.
1 to make a solution for the determination of inorganic ions. This 5ml of solution was filled up to the measuring flask collected 100ml a whole pipette and CO ₃ ^2- ion measurement sample solution. Further, 3 ml of this solution is collected with a whole pipette, and the volume is increased to a 50 ml volumetric flask to obtain a sample solution for measuring Cl ⁻ and SO ₄ ²⁻ ions. In addition, ion exchange water is used for measuring up.

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

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

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

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

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

Measurement conditions Column: G4000PWXL + G25000PWXL Eluent: 0.2 M 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

The ratio 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 charged water + weight of water of the charged aqueous solution of the acrylic acid polymer) was calculated as follows.
Na ₂ SO ₄ , Na ₂ C dissolved in charge scale
The weight of O ₃ , NaCl and acrylic acid-based polymer is determined. Therefore, the weight of the precipitated and / or undissolved material (hereinafter referred to as the weight of the precipitate) for each component is determined by the following equation. Deposit weight = Charged weight-Dissolved weight

However, in this preparation, all NaCl is dissolved. If the dissolution weight exceeds the charged weight, the total dissolution is determined.

Here, assuming that the weight of the precipitate of the acrylic acid polymer is A, the weight of the precipitate of Na ₂ SO ₄ is B, and the weight of the precipitate of Na ₂ CO ₃ is C, the weight of the acrylic acid polymer is burkeite. Is determined by the following equation. Adsorption rate (%) = A / (B + C) × 100

Here, the preferred adsorption rate of the acrylic acid polymer to burkeite in the present invention is 2.5% or more. In addition, from the viewpoint of making the burkeite finer by the acrylic acid-based polymer acting more on the burkeite crystals precipitated in the preparation step of the preparation liquid and the spray drying step, the burkeite is more preferably 3% or more, and still more preferably 4% or more. %, Particularly preferably 5% or more, most preferably 6% or more. Also, when spray-drying a preparation liquid containing an acrylic acid polymer, the obtained granules have a structure covered with a film containing the polymer and tend to delay absorption of the liquid composition from the surface, It was also found that the use of an acrylic acid polymer having a high adsorption rate to burkeite improved the absorbability.

Here, the high adsorption rate of the acrylic acid polymer to burkeite measured by the above-mentioned adsorption rate measurement means that the acrylic acid 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 polymer having a high adsorption rate to burkeite is used, the resulting supporting granules have a small pore size and a high supporting ability to a liquid composition and a high granule strength. or,
When an acrylic acid 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 solution prepared by the above-described adsorption rate measurement.

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

From the viewpoint that the use of an acrylic acid polymer having an effect of forming fine burkeite in the preparation solution improves the ability to support the supporting granules, the acrylic acid polymer is not 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, and more preferably 1 count.
The acrylic polymer is 250 counts / second or more, more preferably 1500 counts / second or more, and most preferably 1750 counts / second or more. Further, the acrylic acid polymer, the average particle size of the precipitate in the adsorption rate measurement is preferably 40μm or less, more preferably 35μm
Or less, more preferably 30 μm or less, and most preferably 2 μm or less.
It is an acrylic acid polymer having a size of 7.5 μm or less.

The characteristics of the acrylic acid polymer as described above, that is, the ratio of the half-reduced particle diameter to the large particle diameter in the light scattering measurement, the half value width in the HPLC measurement, and the adsorption rate to burkeite are determined by the acrylic acid-based polymer. It is derived from the type of terminal group and the structure of the main chain of the merging.

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

The structure of the main chain means the number of branches and the number of head-to-head or tail-to-tail structures.
A polymer having less of these disordered structures is a polymer suitable for the present invention. Such a polymer can be obtained by performing polymerization under mild conditions while keeping the following points in mind.

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 for obtaining a polymer suitable for the present invention. At this time, from the viewpoint of polymerizing at a relatively low temperature, it is also effective to perform polymerization by a redox method. The polymerization by the redox method includes COMPREHENSIVE POL
YMER SCIENCE, Volume 3Chai
n Polymerization Part 1,1
23-139, PERGAMON PRESS, 1
989 or Japanese Patent Publication No. 2-24283.

Since the branching occurs when α-hydrogen in the main chain is extracted 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 and to lower the concentration of the initiator. From the viewpoint of lowering the polymerization temperature, it is also effective here to carry out the polymerization by the redox method. In order to prevent the initiator concentration from becoming too high not only for the whole but also locally, pay attention to the point of dropping at a low concentration, sufficiently stirring, etc., and at any stage of the reaction. Also, it is desirable to design the process in consideration of preventing the concentration of the initiator from becoming too high temporarily. From the viewpoint of not increasing the radical concentration, it is desirable to employ a stirring method or process that does not cause a local or temporary increase in the temperature as in the case of the initiator concentration. As the type of the initiator, an azo-based initiator is more preferable than a persulfate, from the viewpoint of low α-hydrogen abstraction ability.

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

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

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

1. GPC conditions Apparatus: Model 300 T manufactured by Viscotek
DA column: Tosoh TSKgel G (4000,250
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 (PolyCAL ™ from Viscotek)
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) was injected into GPC,
From the obtained chromatogram, the refractive index of the solvent was 1.3.
3, the weight average molecular weight is 51500, the intrinsic viscosity is 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 intrinsic viscosity ([η] _b ). However, the sample concentration is recalculated with dn / dc of the sample being 0.148.

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

[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 below is linear.

[0058]

(Equation 2)

7. The branching degree (λ) is obtained by the following equation. However, R is 47000 (= monomer molecular weight ÷ 2 × 100
0). As a result, λ is 100 carbon atoms in the main chain.
It becomes the weight average number of branch points per 0 pieces. λ = R · Bn / Mw _b

The preferred value of the degree of branching (λ) of the acrylic acid polymer in the present invention is 9 or less, more preferably 5 or less, and still more preferably 2.
5 or less.

Dispersibility measurement (3): First, 71.2 mgC
aCO ₃ / L hardness (using calcium chloride), pH1
Using a 0.02 M NH ₄ Cl—NH ₄ OH buffer adjusted to 0, an aqueous solution of 5.0 × 10 ⁻⁴ wt% acrylic acid-based polymer is prepared. Next, 50 mL of the aqueous solution was added to 50 mL.
into a shaker tube (sedimentation tube) of 150 mL and 150 mesh (1
(00 μm) Add 0.05 g of Kanuma Akadama clay for horticultural use (for example, manufactured by Sakamoto Shoten). After shaking vigorously for 30 seconds, ultrasonic irradiation is performed for 5 minutes. After the shaker tube (sedimentation tube) was allowed to stand at 25 ° C. for 2 hours, the supernatant was collected from a place 3 cm below the liquid surface, and 575 n using a spectrophotometer.
The turbidity is evaluated by measuring the absorbance at a wavelength of m, and the value is used as the dispersion performance of the mud particles. Therefore, the larger the measured value of the absorbance, the higher the dispersibility of the mud particles.

Here, the preferable dispersing performance of the acrylic acid polymer in the present invention is 0.5 or more, but the dirt particles are separated from the laundry clothes and dispersed uniformly in the washing bath. From the viewpoint of preventing the particles from re-adhering to the laundry clothes, it 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, 0.1 M-NH
The potential of the standard calcium ion solution was measured using an ion analyzer (model 920A, manufactured by Orion) equipped with a standard calcium ion electrode using a 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 created. Next, 0.1 g of an acrylic acid-based polymer (in terms of solid content) is weighed in a 100 ml volumetric flask, and the volume is increased with the above buffer solution. A CaCl ₂ solution (pH 10) corresponding to 20,000 ppm (calculated as CaCO ₃ ) is dropped from the burette (blanks are also measured). The drop is CaC
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 dropping amount A of the sample in FIG. 4 is the calcium ion trapping ability of the sample.

The calcium ion-capturing ability indicates how much the acrylic acid polymer captures calcium ions in water that lower the activity of the surfactant. And, the higher the calcium ion-capturing ability is used, the more the granules for supporting have a superior builder ability to suppress the decrease in the activity of the surfactant.

Here, the preferred calcium ion-capturing ability of the acrylic acid polymer in the present invention is 160 mg C
aCO ₃ / g or more, more preferably 180 m 2 from the viewpoint of exhibiting even higher washing 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.

Measurement of stability constant (5): A value obtained under the following measurement conditions is substituted into the following equation to obtain a value. 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,
A calcium ion solution having a concentration of 0.01 mol / L is added to a 0.1 M NH ₄ Cl—NH ₄ OH buffer (pH 10).
(Using CaCl ₂ ) and put 50 g into a 100 ml beaker. 50 mg (in terms of solid content) of an acrylic acid polymer is charged. Adjust the pH to 10. 0.15 g of sodium chloride is added as a calcium ion electrode stabilizer.

The concentration of free calcium ions is measured using a calcium ion electrode. Free calcium ion concentration: [Ca] Immobilized calcium ion concentration: [CaS] Free chelate sites: [S] Number of chelate sites: [SO] Stability constant: [log] × [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 obtained by calculation from the slope and intercept.

The stability constant for calcium ions is
It indicates the degree to which the calcium ion concentration in the washing water is reduced, and also indicates the degree to which calcium ions present in dirt or the like adhering to laundry clothes are extracted. As the acrylic acid polymer having a higher stability constant is used, calcium ions can be more strongly extracted from the dirt attached to the laundry and the dirt is more easily removed. As the acrylic acid polymer having a higher stability constant with respect to calcium ions is used, the supporting granules have more excellent builder ability.

Here, the stability constant of the acrylic acid polymer in the present invention with respect to a preferable calcium ion is as follows:
2.6 or more, more preferably 2.7 or more, further preferably 2.8 or more, especially from the viewpoint of exhibiting higher washing performance by capturing more calcium ions present in the washing bath. It is preferably at least 2.9, most preferably at least 3.0.

Incidentally, the internal structure of the granules for supporting a surfactant of the present invention can be confirmed by using a mercury porosimeter as a pore volume distribution of the granules for supporting a surfactant. Mercury porosimeter (eg, "Poisizer 932" manufactured by Shimadzu Corporation)
0 "), the distribution of the pore volume per pore diameter inside the supporting granule (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 diameter, the more the ability to retain the liquid composition once absorbed by capillary action (supporting force).
Will be higher. Therefore, when the pore volume is larger and the pore diameter is smaller, the carrying capacity of the surfactant becomes higher,
A large amount of the liquid composition can be supported, and at the same time, the liquid composition can be prevented from being stained. Accordingly, the surfactant-supporting granules of the present invention suitable for supporting the liquid composition have a mode diameter of the pore volume distribution (the pore diameter having the largest pore volume in the obtained pore volume distribution). 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.1 μm
The following is more preferable, and 1.0 μm or less is particularly preferable, and among them, 0.9 μm or less is preferable, and 0.8 μm or less is preferable.
It is particularly preferred that: Further, regarding the pore volume of the particles for supporting a surfactant of the present invention, a pore diameter of 0.01
The pore volume of ~ 3.0 µm is preferably 0.3 mL / g or more, and the pore volume of 0.01 ~ 2.5 µm is more preferably 0.3 mL / g or more. More preferably, the pore volume of 0.01 to 2.0 μm is 0.3 mL / g or more, and the pore diameter is 0.01 to 1.5 μm.
It is particularly preferable that the pore volume of μm is 0.3 mL / g or more, and it is particularly preferable that the pore volume of 0.01 to 1.0 μm is 0.3 mL / g or more.

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

Further, quinones generally used as polymerization inhibitors in the acrylic acid monomer raw material used in synthesizing the acrylic acid-based polymer, for example, p-methoxyphenol (hereinafter also referred to as methoquinone), are added to the preparation liquid. When it is contained, the surfactant-supporting granules obtained by spray drying may become pink and deteriorate the hue. 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 quinones content when blending the acrylic acid polymer into 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, still more preferably 2 ppm
Hereinafter, most preferably, quinones are substantially not contained (1
It is preferably in the form of an aqueous solution.

As a method of reducing quinones, there is a method of reducing the content of quinones in an acrylic acid monomer raw material when synthesizing an acrylic acid-based polymer. Further, a treatment such as oxidizing 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 may be performed. . Preferred oxidation methods include p
H is set to 10 or more, and treatment with hydrogen peroxide in an equimolar amount or more of quinones is included. At this time, the method of adding the oxidizing agent to be added or the auxiliary agent (aqueous sodium hydroxide solution) for improving the effect may be either continuous or batchwise.

The method for detecting quinones is exemplified below for methoquinone. The amount of methoquinone in the aqueous acrylic acid polymer solution is determined by high performance liquid chromatography under the following measurement conditions.

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

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

The acrylic acid polymer used in the support 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 diameter by light scattering, a ratio of particles having a particle diameter of more than 800 nm, and further, if necessary, dispersing performance of mud particles, calcium ion trapping ability and stability to calcium ions. The constant may be in the range defined above. Here, as the monomer components other than acrylic acid and / or its salt contained in the acrylic acid polymer, unsaturated monocarboxylic acids represented by methacrylic acid, α-hydroxyacrylic acid, crotonic acid, etc. , Unsaturated polycarboxylic acids represented by maleic acid, methylmaleic acid, fumaric acid, itaconic acid, aconitic acid and salts thereof, and unsaturated sulfonic acids represented by allylsulfonic acid, styrenesulfonic acid, etc. And a water-soluble ethylenically unsaturated monomer component exemplified by salts thereof.
The acrylic acid-based polymer may contain one or more of the water-soluble ethylenically unsaturated monomer components in addition to acrylic acid and a salt thereof.

From the viewpoint of adjusting the burkeite crystals to be finer by acting on the burkeite crystals precipitated in the preparation of the preparation liquid and the spray drying step, acrylic acid-based polymers include acrylic acid and acrylic acid. It is preferable that the amount of the monomer component other than / or the salt thereof is not more than 1 / 2.5, more preferably not more than 1/3, further preferably not more than 1 / 2.5 in molar ratio with respect to the amount of acrylic acid and / or the salt thereof. Is 1 /
5 or less, preferably 1/10 or less, most preferably substantially composed of acrylic acid and / or a salt thereof.

The content of the acrylic acid 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 still more preferably 7 to 26% by weight. Preferably, 8 to 24% by weight is particularly preferred,
Most preferred is 10 to 22% by weight. Within this range, the ability to support the liquid composition is high and the granule strength is satisfactory.

The particles for supporting a surfactant of the present invention may contain a water-soluble polymer other than the acrylic acid polymer together with the acrylic acid polymer. Carboxylic acid-based polymers other than acrylic acid-based polymers include, for example, polymers such as polyglyoxylate, cellulose derivatives such as carboxymethyl cellulose and aminocarboxylic acid-based polymers such as polyaspartate also sequestering ability, It can be used as having a dispersing ability and a re-contamination preventing ability.

In addition, polyvinylpyrrolidone (PV
P), polyethylene glycol (PEG), polypropylene glycol (PPG) and the like.
PEG and PPG having a molecular weight of about 1,000 to 20,000 are preferred as a color transfer preventive agent, and are preferred because the powder detergent improves the viscosity characteristics of the paste produced when the powder detergent contains water.

The particles for supporting a surfactant according to the present invention contain sodium carbonate and sodium sulfate which are water-soluble salts. 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 and sodium carbonate which are precipitated in a preparation step of the preparation liquid and a step of spray-drying the preparation liquid The size and shape of burkeite, which is a double salt of sodium sulfate, is important for enhancing the loading capacity of the loading granules. That is, in order to improve the supporting ability of the supporting granules, it is preferable to generate a large number of fine and needle-like burkeites which are affected by the acrylic acid polymer inside the supporting granules. From this viewpoint, the total content of sodium carbonate and sodium sulfate in the surfactant-supporting granules is from 19/1 to 1 / (weight ratio) with respect to the polymer content.
It is preferably 1/2, more preferably 17/1
To 1/1, more preferably 15/1 to 2/1, among which 13/1 to 3/1, most preferably 11 / 1-1.
1 to 4/1. Further, 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, further preferably 1
/ 6 to 6/1, among which preferably 1/4 to 4/1,
Among them, the ratio is more preferably 1/3 to 3/1, most preferably 1/2 to 2/1.

Other water-soluble salts which 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, halides such as chlorides, bromides, iodides, and fluorides such as alkali metals (for example, sodium or potassium) and alkaline earth metals (for example, calcium or magnesium) are included.

Of these, potassium carbonate, potassium sulfate, sodium sulfite and potassium sulfite are preferred.
Potassium carbonate is preferable as an alkaline agent showing a suitable pH buffer region in the washing liquid, and sulfite reduces hypochlorite ion contained in tap water, and hypochlorite as a detergent component such as enzymes and fragrances. It has the effect of preventing oxidative degradation by ions.

[0085] Sodium tripolyphosphate can also be used as a water-soluble salt. When an alkali metal salt such as sodium chloride is added to a preparation solution containing sodium carbonate and sodium sulfate, the salt itself dissolves and instead precipitates fine crystals of a double salt of sodium carbonate and sodium sulfate. Since it has the effect of causing the particles to be supported, it effectively acts on the formation of the support site of the support granules. Furthermore, these alkali metal halides also have an effect of partially suppressing the formation of a surface film during the drying process, and also have an effect of increasing the loading speed of the liquid composition of the loading granules. Of particular importance from.

The water-soluble salts which 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. Also, from the point of detergency, methyl iminodiacetic acid, iminodisuccinate, ethylenediamine disuccinate, taurine diacetate, hydroxyethyl iminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate Salt, glutamic acid diacetate, asparagine diacetate, serine diacetate and the like are preferred.

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

Further, the particles for supporting a surfactant of the present invention may contain a water-insoluble substance. As the water-insoluble substance, crystalline aluminosilicates, amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds, clay compounds such as perlite and bentonite can be used. Crystalline aluminosilicates and amorphous aluminosilicates are preferred because of their contribution and the reason that they do not promote the generation of undissolved residues. 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”;
Nippon Builders Co., Ltd., product name: "VALFOR10
0 "; PQ CHEMICALS (Thailand)
Ltd, trade name: "VEGOBOND"; CONDEA
Product name: "ZEOBUILDER"; ZEOBU
ILDER Ltd, trade name: "VEGOBOND
A "; OMAN CHEMICAL INDUSTRI
ES Ltd, trade name: "Zeolite"; THAI
SILICATE CHEMICALS Ltd), which is also preferable in terms of sequestering ability and economy.
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, product name "Douci"
l A24 "and" ZSE064 "; Crosfield
Oil absorption capacity 60-150 mL / 100 g) or X type (for example, trade name: "WessalithXD"); Degus
sa company; oil absorption capacity 80 to 100 mL / 100 g). Hybrid zeolites described in WO 9842222 are also mentioned as suitable crystalline aluminosilicates.

Further, amorphous aluminosilicate, amorphous silica or the like having a low sequestering ability but a high oil absorbing ability can also be used as a water-insoluble substance. For example, JP
JP-A-2-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (especially the initial temperature is preferably in the range of 15 to 60 ° C.), and JP-A-62-191419, page 2 Amorphous aluminosilicate described in lower right column, line 20 to page 5, lower left column, line 11 (oil absorption is preferably 170 mL / 100 g), and JP-A No. 9-132794, No. 17
Column 46, line 18 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-119622, column 2, line 18 to column 3, line 47 (oil absorption capacity 285)
mL / 100 g). For example,
"TOKUSHIR NR" (manufactured by Tokuyama Soda Co., Ltd .: Oil absorption capacity 21)
0 to 270 mL / 100 g), "Flolite" (same as above:
Oil absorption capacity 400-600mL / 100g), "TIXOL
EX25 ”(manufactured by Korea and France Chemical Co., Ltd .: 220-270 mL of oil absorption capacity)
/ 100 g) and "Silopure" (manufactured by Fuji Divison Co., Ltd .: oil absorption capacity 240 to 280 mL / 100 g). Particularly, as an oil-absorbing carrier, JP-A-6-179899, column 12, line 12 to 1
Those described in column 3, line 1, column 17, line 34 to column 19, line 17 are preferred.

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

A surfactant may be added to the support granules as another component. However, when a preparation solution containing a surfactant is spray-dried to produce the support granules, a surfactant is required. Since a film tends to be formed on the surface of the supporting granules to be obtained, as a result, the absorption rate of the supporting granules to the liquid surfactant composition tends to decrease. Therefore, from such a viewpoint, it is preferable that the surfactant content in the supporting granules is smaller, and it is rather preferable that no surfactant is present. From the above, the content of the surfactant in the support granules is preferably 0 to 5% by weight, more preferably 0 to 3% by weight, still more preferably 0 to 2% by weight, and 0 to 1% by weight. Among them, it is preferable, and among them, it is most preferable that it is not substantially contained.

As examples of the surfactant, the same surfactant as the liquid surfactant composition to be supported on the supporting granules described below can be used.

The amorphous silicate has the effect of increasing the granule strength of the supporting granules. However, when an aluminosilicate is used as the water-insoluble substance contained in the supporting granules, the amorphous silicate Is formed in the preparation liquid for preparing the supporting granules, and forms an aggregate that becomes hardly soluble in water with time, so that the supporting granules of the present invention are not substantially contained. Is preferred. In addition, since crystalline silicate is also dissolved in the preparation liquid and becomes amorphous, it is preferable not to mix the same in 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, so that the silicate contained in the preparation liquid is ,
It is preferably at most 10% by weight, more preferably at most 5% by weight, further preferably at most 3% by weight, particularly preferably at most 2% by weight, based on the water-soluble salts other than the silicate contained in the support granules. Hereinafter, it is preferably 1% by weight or less, and most preferably substantially not contained.

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

4. Method for Producing Surfactant-Supporting Granules The surfactant-supporting granules of the present invention can be prepared by a process comprising the following steps (a) and (b). Step (a): As a first step, a step of preparing a preparation solution containing an acrylic acid polymer and sodium carbonate and sodium sulfate. Step (b): a step of spray-drying the solution prepared in step (a).

Step (b) is a step of drying the preparation liquid obtained in step (a) to obtain particles for supporting a surfactant.
Regarding the drying method, any drying method, for example, freeze drying, drying under reduced pressure, etc. can be used, but from the viewpoint of precipitating finer burkeite and effectively acting for supporting the liquid composition, the prepared liquid Is preferably flash dried, and a particularly preferred drying method is a spray drying method.
As the spray-drying tower, any of a counter-current tower and a co-current tower can be used, but a counter-current tower is preferable in terms of productivity. Further, a pulse shock wave dryer using a pulse burner as a heat source of the spray drying tower is also exemplified as one of the preferable drying devices. In the pulse shock wave dryer, since the droplets of the prepared liquid are dried in a high-temperature combustion gas accompanied by a shock wave, the drying speed of the droplets is increased. An example of a pulse shock wave dryer is Palcon (manufactured by Osaka Fuji Industry Co., Ltd.). The step (a) will be described in detail below.

4-1. Step (a) is a step of preparing a preparation liquid containing an acrylic acid-based polymer, sodium carbonate and sodium sulfate. From the viewpoint of further improving the carrying ability of the particles for supporting a surfactant by precipitating more burkeite, at least one or more of the fine burkeite precipitation steps (I) to (III) described below and / or The step (a) preferably 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 for precipitating fine burkeite from sodium carbonate and sodium sulfate dissolved in the preparation solution. The burkeite precipitated in the process is:
Fine particles produced from the liquid phase of the preparation liquid and affected by the acrylic acid polymer. The step (IV) is to add the fine burkeite to the preparation liquid to exhibit the same effect as when the fine burkeite is precipitated in the preparation liquid. In the step (V), coarse burkeite, for example, burkeite generated by using sodium carbonate particles as a nucleus in the preparation liquid is pulverized to make fine or fine burkeite finer.

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

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

The crystal precipitating agent is a substance other than sodium carbonate and sodium sulfate contained in the preparation liquid before adding the precipitating agent, and has a function of precipitating burkeite by adding to the preparation liquid. It is.

First, in the case where the crystal precipitating agent is a water-soluble substance, when the preparation liquid before adding the crystal precipitating agent contains sodium carbonate and sodium sulfate, the crystal precipitating agent was added with the precipitating agent. At a temperature, its dissolution strength is greater than that of burkeite, which is a double salt of sodium carbonate and sodium sulfate. The dissolution strength as used herein means ease of dissolution. A substance that can be used as a crystal precipitation agent is determined by the following method. For example, when sodium chloride is added to a saturated solution containing an acrylic acid polymer and sodium carbonate and sodium sulfate, sodium chloride dissolves and fine needle crystals of burkeite, which is a double salt of sodium carbonate and sodium sulfate, are formed. Precipitates without agglomeration. In this case, sodium chloride is the preferred crystallization precipitant for the preparation containing sodium carbonate and sodium sulfate.

The burkeite precipitated in the preparation liquid by the crystal precipitation agent is fine. Regarding the size of the crystal precipitated in the preparation solution, the in-line type particle droplet monitoring system described above (“TSUB-TEC M” manufactured by LASENTEC) was used.
100 ").

Further, the effect of the fine crystal precipitation by the crystal precipitation agent can be confirmed as an increase in the number of particles over time observed after the addition of the precipitation agent by the in-line type particle droplet monitoring system.

A method for confirming the effect of the crystal precipitant on fine crystal precipitation will be described below. First, a saturated solution containing both sodium sulfate and sodium carbonate is prepared by the following method. Ion-exchanged water 1500 adjusted to the preparation temperature of the preparation liquid
g to sodium sulfate (anhydrous anhydrous sodium sulfate, Shikoku Chemicals Co., Ltd.)
Is added and dissolved in a thermostat at the temperature of the preparation liquid for 20 minutes. 400 g of sodium carbonate (dense ash, manufactured by Central Glass Co., Ltd.)
Add and prepare the 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. Here, the preparation temperature of the preparation liquid means any temperature in a temperature range of 30 to 80 ° C.

In a 1 L stainless steel beaker, 1000 g of the saturated solution of sodium sulfate / sodium carbonate prepared by any of the above methods was weighed, and three propeller blades of 2 × 4 cm were attached in a thermostat at a temperature for preparing a slurry or the like. The stirring blade is rotated at a speed of 200 r / min to stir. Add 100 g of test sample within 30 seconds and continue stirring for 60 minutes. When burkeite crystals precipitate after 60 minutes, the test sample is a crystal 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 precipitating agent include salts having high dissolution strength such as halides such as chloride, bromide, iodide and fluoride of sodium, potassium, calcium and magnesium. Solvents that are compatible with water, such as ethanol, methanol, and acetone, and substances having high hydration power such as zeolite (anhydrous) among water-insoluble substances are also examples of the crystal precipitating agent.

From the viewpoint of dissolution strength, bromide and iodide are preferable, but from the viewpoint of storage stability of the detergent particles, etc.,
Chloride is preferred, and alkali metal salts are preferred due to their effect on cleaning performance. Among them, sodium chloride is particularly preferred from an economic viewpoint.

The content of the crystal precipitating agent in the particles for supporting a surfactant is determined from the viewpoints of exhibiting a sufficient crystal precipitating effect and maintaining the cleaning performance when the detergent composition is obtained.
0.2 to 35% by weight is preferred, 0.5 to 30% by weight is more preferred, 1 to 25% by weight is still more preferred,
Especially preferred is 2 to 15% by weight, especially 2 to 15% by weight.

The solubility of the water-soluble crystal precipitating agent in the preparation liquid is determined by dissolving more in the solution part of the preparation liquid to generate a larger number of precipitates. From the viewpoint of making the supporting site for the composition a more preferable structure, a higher one is preferable. The dissolution rate of the crystal precipitating 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, among which, preferably 95% by weight or more, and most preferably. Means complete dissolution.

The dissolution rate of the crystal precipitant in the preparation can be measured by combining known analytical techniques. For example, the prepared solution is filtered under reduced pressure, and the water concentration P
₁ (%) is a far-infrared heater type moisture meter (Shimadzu Corporation)
Manufactured). Further, the concentration S of the crystal precipitant in the filtrate is
Determine ₁ (%) by ion chromatography or the like. Assuming that the water content of the preparation liquid is Q ₁ (%) and the content of the crystal precipitant in the preparation liquid is T ₁ (%), the dissolution rate of the crystal precipitant is calculated by the following equation. However, if the calculated dissolution rate exceeds 100%, the dissolution rate is set to 100%. Dissolution rate (%) = (100 × S ₁ × Q ₁ ) / (P ₁ × T ₁ ) (1)

Regarding the procedure for blending sodium carbonate and sodium sulfate in the preparation liquid, it is preferable to add sodium carbonate after sufficiently dissolving sodium sulfate from the viewpoint of increasing the supporting ability of the supporting granules.

The water content of the prepared solution is more preferably from 35 to 65, from the viewpoints of reducing coarse burkeite particles having an average particle diameter of 40 μm or more, which are formed with sodium carbonate particles as nuclei, and sufficiently exhibiting the effect of the crystal precipitation agent. weight%,
40-60% by weight is most preferred. Further, the temperature of the prepared solution is preferably 30 to 80 ° C., more preferably 35 to 80 ° C., in view of the dissolution amount of the water-soluble salts and pumpability.
７５75 ° C.

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

4-1-2. Step (II) Precipitation by Concentration of Preparation Solution As a result of examining a method of precipitating fine burkeite, a method of precipitating the preparation solution by concentration was found. That is, by performing an operation of precipitating burkeite from sodium carbonate and sodium sulfate in a dissolved state in the presence of an acrylic acid-based polymer, a large number of fine crystals can be generated in the preparation liquid.
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, sodium carbonate and sodium sulfate may be mixed in any order. However, when sodium carbonate and sodium sulfate in the preparation are not completely dissolved, it is preferable to mix sodium sulfate before sodium carbonate.
When compounding the above-mentioned crystal precipitating agent, it is preferable to mix after blending the acrylic acid polymer and sodium carbonate and sodium sulfate, and may be blended after the concentration operation of the preparation liquid. When a water-insoluble substance is blended, it may be blended before or after concentration of the preparation liquid.

The smaller the amount of coarse burkeite present in the preparation liquid before concentration (however, in the case of adding a crystal precipitant, the preparation liquid before mixing the crystal precipitation agent), the smaller the amount of the supporting granules obtained after spray drying becomes. The ability becomes higher. Therefore, the total dissolution rate of sodium carbonate and sodium sulfate in the preparation before concentration is preferably 50 to 100% by weight, and 70 to 10% by weight.
0% by weight is more preferable, and 90 to 100% by weight is particularly preferable. When the dissolution rate is less than 100% by weight, it is also a preferable embodiment to pulverize the prepared liquid using a wet pulverizer described below or the like to make undissolved matter fine. The wet grinding 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 preparation is determined by ion chromatography or the like. The prepared solution is filtered under reduced pressure, and the moisture concentration P ₂ (%) in the filtrate is measured by a far-infrared heater type moisture 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 preparation
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 equation. However, the calculated dissolution rate is 100
%, The dissolution rate is 100%. Dissolution rate (%) = (100 × S ₂ × Q ₂ ) / (P ₂ × T ₂ ) (2)

Next, the prepared solution is concentrated to precipitate water-soluble salts dissolved in the prepared solution. As a device for concentration, any device can be used as long as it is a commonly used concentration device. For example, a natural circulation evaporator in which the liquid rises while boiling in the heating tube inside the evaporator, collects in the central concentrated liquid collection tube, falls, and circulates naturally, or a circulation pump between the evaporator and the heating can The liquid is circulated at high speed using an evaporator to evaporate water, and the forced heating circulation type evaporator or the liquid flows in from the upper part of the vertical heating can and flows down the inner wall of the heating tube as a uniform liquid film. There are thin film falling evaporators in which evaporative concentration is performed in between, and these may be used alone or multiple effects may be used. A flash type evaporator that evaporates water by injecting a liquid heated to a boiling point or higher into an evaporator with reduced pressure is also effective.

Since the preparation solution used in the present invention produces crystals of water-soluble salts with concentration, the scale easily adheres to the concentration device. Therefore, it is more preferable to use a concentrator having a function of removing the attached scale or a concentrator having a structure to which the scale is hardly attached. As the former device, there is a device in which a stirring blade for scraping scale is provided in the above-mentioned thin film falling-down type evaporator, for example, Wiplen (manufactured by Shinko Pantech Co., Ltd.). As the latter device, there is a Rothko evaporator (manufactured by Sumitomo Heavy Industries, Ltd.) in which a plate-type heating element is held inside an evaporator and concentrated by flowing a liquid on the surface of the heating element under reduced pressure.

4-1-3. Step (III) Precipitation by adjusting the temperature of the prepared solution As a result of studying the method of precipitating fine burkeite, a method of changing the temperature of the prepared solution so as to reduce the amount of sodium carbonate and sodium sulfate dissolved in the prepared solution was reduced. I found it. That is, the temperature of the preparation solution is adjusted so that the dissolution 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, whereby the preparation solution is prepared. Many fine burkeites can be generated. The precipitation method by adjusting the temperature of the preparation liquid will be described in more detail.

First, the preparation solution before the temperature change operation may be prepared by a known method. When the above-mentioned crystal precipitation agent is blended, after the acrylic acid polymer, sodium carbonate and sodium sulfate are blended, It is preferable to mix them, and after the operation of changing the temperature of the preparation liquid, a crystal precipitating agent may be mixed. When a water-insoluble substance is blended, it may be blended before the temperature change operation of the preparation liquid or the like, or may be blended after the temperature change operation. Further, a part of the acrylic acid polymer may be blended in the prepared solution after the operation. Thereby, the size of the crystals of the water-soluble salts deposited can be adjusted.

The smaller the amount of coarse burkeite present in the preparation before the temperature change operation, the higher the supporting ability of the obtained particles for supporting a surfactant. Therefore, the total dissolution rate of sodium carbonate and sodium sulfate in the preparation 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.
% By weight is particularly preferred. When the dissolution rate is less than 100% by weight, it is also a preferred embodiment to pulverize the prepared liquid using a wet pulverizer or the like described below to make coarse burkeite fine. The wet pulverization of the preparation may be performed on the preparation 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 prepared solution, a part of the dissolved sodium carbonate and sodium sulfate is precipitated as burkeite. As a method of changing the temperature of the preparation liquid, there is a method of using a device provided with an outer jacket, an internal coil, and the like when preparing the preparation liquid, and heating / cooling using these devices.

Before the temperature changing operation, the temperature of the prepared solution is
It is preferable to set so as to increase the dissolution rate of sodium carbonate and sodium sulfate contained in the preparation liquid.

The temperature of the preparation after the temperature change operation is set so that the dissolution rate of sodium carbonate and sodium sulfate in the preparation becomes low. When these materials are used, the prepared solution before the temperature change operation is
Adjust to about 0 ° C, and adjust the temperature of the
It is preferable to adjust the temperature to 0 to 70 ° C.

It is to be noted that, in addition to changing the temperature of the prepared solution, the prepared solution is subjected to, for example, flash concentration, whereby
It is also a preferred embodiment to promote the precipitation of dissolved water-soluble salts.

4-1-4. Step (IV) Addition of Fine Berkeite Particles to Preparation Solution As a result of examining a method for exhibiting the same effect as when fine burkeite is precipitated in the preparation solution, a method of adding fine particles of burkeite to the preparation solution was found.

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

As a method for producing fine particles of burkeite, a commercially available substance may be finely pulverized, but it is more preferable that the substance is finely crystallized 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 refined by a pulverizer to obtain burkeite fine particles. Examples of the fine pulverizer include a roller mill, a ball mill, and an impact type pulverizer. The roller mills include a USV mill (Ube Industries, Ltd.), an MRS mill (Mitsubishi Heavy Industries, Ltd.), and an SH mill (IHI). Ball mills include dynamic mills (manufactured by Mitsui Miike Kakoki Co., Ltd.), vibration mills (manufactured by Chuo Kakoki Shoji Co., Ltd.), and impact-type pulverizers include atomizers and pulperizers (both of which are Fuji Powder Co., Ltd.).

The smaller the average particle size of the burkeite fine particles, the greater the effect of improving the carrying ability of the particles for supporting a surfactant obtained by spray drying in the step (b). In this respect, the average particle diameter of the fine particles is preferably 40 μm or less, more preferably 35 μm or less, and 30 μm or less.
μm or less, more preferably 25 μm or less, particularly preferably 20 μm or less, and more preferably 1 μm or less.
More preferably, the thickness is 5 μm or less.
It is particularly preferable that the thickness be set to μm or less. The average particle size is measured by the following method.

In a 1 L stainless steel beaker, add ethanol 1
Weigh 2,000 g and place it in a 2 x 4 cm 3
The stirring blade with the propeller blades is rotated at a speed of 200 r / min to stir. Subsequently, the fine particles described above were
g. The particle size distribution at the time of measurement for 10 minutes is measured by the above-described method using the in-line type particle monitoring system (TSUB-TEC M100) manufactured by LASENTEC.
The median code (the particle size when the integrated value of the number of particles is 50%) is defined as the average particle size.

4-1-5. Step (V) Wet Pulverization of Preparation Solution As a result of examining a method for expressing the same effect as when fine burkeite is precipitated in the preparation solution, a method of wet pulverizing the preparation solution was found. By the method of wet-grinding the preparation, coarse burkeite generated by using sodium carbonate particles as a nucleus in the preparation can be refined, and the fine burkeite can be further refined.
The preparation liquid before the wet pulverization is prepared by a known method, but the acrylic acid polymer, sodium carbonate and sodium sulfate may be mixed in any order. When a water-insoluble substance is blended, it may be blended before the preparation liquid is wet-pulverized, or may be blended after the wet pulverization. It is more preferable to mix them before wet pulverization. For example, a crystalline aluminosilicate, which is a water-insoluble substance, can improve the calcium exchange rate by being compounded before wet grinding.

Further, the finer the burkeite contained in the preparation liquid, the greater the effect of improving the carrying ability of the particles for supporting a surfactant obtained by spray drying in the step (b). The wet pulverization of the preparation liquid allows the burkeite to be used for forming a supporting site in the supporting granules obtained after spray drying by pulverizing burkeite present in the preparation liquid. For example, when burkeite is formed in the preparation liquid by blending sodium carbonate following the acrylic acid-based polymer and sodium sulfate, the burkeite is mostly coarse particles formed on the surface of the sodium carbonate added. Exists as Barkite, if present as such coarse particles, can hardly contribute to the formation of the supporting site of the supporting granules,
By making the particles fine by wet pulverization, the particles are effectively used for forming the supporting site in the supporting granules, and the supporting ability of the granules is improved.

As for the apparatus for pulverization, any apparatus can be used as long as it is a commonly known wet pulverizer. Examples of commonly used wet pulverizers include (i) a pulverizer using a pulverizing medium, and (ii) a pulverizer between a gap between a pulverizing blade and a stator.

As (i), while the medium in the vertical cylindrical vessel is stirred by a stirring blade or a stirring disk, the processing liquid is supplied from the lower part of the vessel, and the pulverization is performed by the shearing force generated by the difference in the flow speed of the medium. There is a device for discharging the processing liquid from the upper part of the vessel. There are a sand grinder (manufactured by Igarashi Machine Manufacturing Co., Ltd.) and a universal mill (manufactured by Mitsui Miike Seisakusho) as a continuous type of such an apparatus, and an aquamizer (manufactured by Hosokawa Micron Corporation) as a batch type. . As a horizontal continuous type having a similar structure, there is a Dynomill (manufactured by WAB). or,
Diamond Fine Mill (Mitsubishi Heavy Industries, Ltd.), which consists of a cylindrical rotor and an annular casing that wraps it, and crushes the processing liquid supplied from the lower center of the rotor by the high-speed rotation of the media, Koball Mill (Shinko Pantech Co., Ltd.).

(Ii) A colloid mill (Shinko Pantech Co., Ltd.) composed of a rotor having crushing teeth and a stator and crushing by repeatedly applying a shearing force when the processing liquid passes through this gap. And Trigonal (manufactured by Mitsui Miike Kakoki Co., Ltd.). It has a similar grinding mechanism, but has a glow mill (manufactured by Glow Engineering Co., Ltd.), whose rotor and stator are whetstones, a mass colloider (manufactured by Masuko Sangyo Co., Ltd.), and a corundum mill (manufactured by Shinko Pantech Co., Ltd.) . Further, there is a homomic line mill (manufactured by Tokushu Kika Kogyo Co., Ltd.) in which a first turbine and a stator coarsely pulverize and a second rotor and a stator finely pulverize. In addition, a specially shaped rotor that rotates at high speed with a wet emulsifying and dispersing machine that has functions of emulsification, dispersion, uniform mixing, and atomization,
There is a Cavitron (manufactured by Taiheiyo Kiko Co., Ltd.), which can apply a strong shock of megahertz to the liquid by a stator interlocking with it and obtain a dispersion effect comparable to a high-pressure homogenizer.

[0138] 5. Physical Properties of Particles for Supporting Surfactant The bulk density of the particles for support of the present invention secures the bulk density after supporting the liquid surfactant composition and the viewpoint of securing the supporting capacity of the liquid surfactant composition. From the viewpoint of
000 g / L is preferred, 350 to 800 g / L is more preferred, 400 to 700 g / L is still more preferred,
Particularly preferred is 0 to 600 g / L.

The average particle size of the supporting granules from the viewpoint of powdering properties and solubility when a detergent composition containing the detergent particles comprising the liquid surfactant composition supported on the supporting granules is used. The diameter is preferably 140 to 600 μm,
-500 µm is more preferable, and 180-400 µm is further preferable.

The water content of the supporting granules as measured by an infrared moisture meter is preferably small from the viewpoint of increasing the supporting capacity of the liquid surfactant composition of the granules, and is preferably 14 or less.
% By weight, more preferably 10% by weight or less, still more preferably 6% by weight or less, and most preferably 2% by weight or less.

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

6. Composition and Physical Properties of Detergent Particles The detergent particles of the present invention are obtained by supporting a surfactant composition on the supporting granules.

In the surfactant composition, the anionic surfactant and the nonionic surfactant can be used alone, but it is more preferable to use a mixture of both. In particular, when a nonionic surfactant having a melting point of 30 ° C. or lower is used, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 10,000 to 30,000 has an effect of increasing 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 in combination. In addition, as a melting point raising agent which can be used in the present invention, for example, polyethylene glycol, polypropylene glycol and the like can be mentioned. Further, an amphoteric surfactant or a cationic surfactant can be used in combination according to the purpose. In addition, by incorporating 5 to 25% by weight of an anionic surfactant such as an alkylbenzene sulfonate into the detergent particles, the effect of improving the dispersibility of the detergent particles in low-temperature water is exhibited.

As the surfactant composition, for example, at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant is used. be able to. Examples of the anionic surfactant include an alkyl benzene sulfonate, an alkyl or alkenyl ether sulfate, an α-olefin sulfonate, an α-sulfofatty acid salt or an ester thereof, an alkyl or alkenyl ether carboxylate, and an amino acid type surfactant. , N-acylamino acid type surfactants and the like. Particularly, a linear alkylbenzene sulfonate having 10 to 14 carbon atoms, an alkyl sulfate or an alkyl ether sulfate having 10 to 18 carbon atoms can be mentioned, and as counter ions, alkali metals such as sodium and potassium, monoethanolamine, diethanolamine and the like can be mentioned. Are preferred.

Further, a fatty acid salt can be used in combination to obtain a defoaming effect. Preferred fatty acids have 12 carbon atoms.
~ 18.

Examples of the nonionic surfactant include polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl or alkenyl phenyl ether,
Polyoxyethylene polyoxypropylene alkyl or alkenyl ether, polyoxyethylene polyoxypropylene glycol represented by the trademark Pluronic, polyoxyethylene alkylamine, higher fatty acid alkanolamide, alkylglucoside, alkylglucoseamide, alkylamine oxide and the like. . Among them, those having high hydrophilicity and those having low ability to form liquid crystal or not generating liquid crystal when mixed with water are preferable, and polyoxyalkylene alkyl or alkenyl ether is particularly preferable. Preferably 10 to 18 carbon atoms,
It is preferably 12 to 14, and the average number of moles added is preferably 5 to 30, more preferably 7 to 30, still more preferably 9 to 30, and particularly preferably 11 to 30. Ethylene oxide (hereinafter EO) addition of alcohol. EO adducts of alcohols having 8 to 18 carbon atoms and propylene oxide (hereinafter referred to as PO) adducts. As the order of addition, a sequence obtained by adding PO after adding EO, a sequence obtained by adding EO after adding PO, or a sequence obtained by randomly adding EO and PO can be used. After adding EO, PO is added as a block,
A general formula in which O is added as a block: R—O— (EO) _X — (PO) _Y — (EO) _Z —H wherein R is a hydrocarbon group having 8 to 18 carbon atoms, preferably an alkyl group or alkenyl. EO represents an oxyethylene group, PO represents an oxypropylene group, and X, Y and Z each represent an average number of moles added. X> 0, Z> 0, X + Y + Z = 6 to 14;
+ Z = 5 to 12, and Y = 1 to 4.

Examples of the cationic surfactant include a quaternary ammonium salt such as an alkyltrimethylammonium salt.

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

The amount of the anionic surfactant is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, particularly preferably 30 to 180 parts by weight, per 100 parts by weight of the nonionic surfactant. It is. The blending amount of the nonionic surfactant's melting point increasing agent is as follows.
The amount is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight based on 00 parts by weight. Within this range, the surfactant composition has a viscosity of 10 Pa · s or less, preferably 5 Pa · s at a temperature equal to or higher than the pour point of the composition.
Or less, particularly preferably has a temperature range of 2 Pas or less, and the penetration hardness of the composition is 10 kPa or more in a temperature range lower than the pour point of the composition and higher than the melting point of the nonionic surfactant, preferably Has a temperature range of 30 kPa or more, particularly preferably 50 kPa or more,
The composition and the detergent particles are preferred because they can be easily handled at the time of production and the stains of the nonionic surfactant can be suppressed during storage of the detergent particles.

The physical properties of the surfactant composition can be measured by the following methods. The pour point is JIS K22
69 can be measured. Melting point is FP
"Mettler FP81" (Met
tler Instrumente AG)
It is measured at a heating rate of 0.2 ° C./min. The viscosity was measured using a B-type viscometer (“DVM-B” manufactured by TOKYO KEIKI).
Type "), rotor No. It is determined by measuring under the conditions of 3, 60 r / min. If the measured value under these conditions exceeds 2 Pa · s and measurement becomes impossible, the rotor No. 3, 12r
/ Min. The penetration hardness is measured with a 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 , and the load when the adapter enters the surfactant composition at a penetration speed of 20 mm / min by 20 mm is applied to the bottom of the circular adapter. It is the value divided by the area.

The amount of the surfactant composition to be added is preferably in the range of 10 to 100 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the supporting granules from the viewpoint of detergency and solubility.
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 referred to here is a value that does not include the amount of the surfactant even if the surfactant is added to the preparation liquid.

When mixing the surfactant composition and the granules for support, powder raw materials other than the granules may be added, if desired. Therefore, 0 to 150 parts by weight is preferable. Examples of the powder material include aluminosilicate, crystalline silicate such as SKS-6 (manufactured by Clariant), and the like.

The detergent particles may contain water-soluble polymers, water-soluble salts, water-insoluble substances, and other components exemplified in the support granules as components other than the above-mentioned surfactant composition. When a water-insoluble substance is used, it may contain a crystalline silicate described below.

When a detergent particle group is manufactured using a component such as a surfactant which can be a binder and a powder raw material,
In some cases, the detergent particles are coated with an agglomerated layer of the component and the physical properties and the like of the supporting granules cannot be confirmed only from the appearance. In this case, as one of the methods for confirming the physical properties and the like of the supporting granules, an organic solvent-soluble component is extracted from the detergent particles and the supporting granules are separated and confirmed. The type of the organic solvent used for the extraction is appropriately selected according to the type of the binder substance binding each constituent unit of the detergent particles.

A method for confirming the physical properties and the like of the particles for supporting a surfactant by solvent extraction will be described below. After 15 g of the reduced and weighed detergent particles are refluxed with 300 mL of 95% ethanol heated in a water bath for 1 hour, the ethanol-insoluble matter is gradually removed by suction filtration while sufficiently washing with hot ethanol. The separated ethanol-insoluble matter is 2
After drying under reduced pressure for 4 hours, the insoluble components are carefully collected so as not to destroy the granular structure. This operation is repeated several times to obtain 100 g of ethanol-insoluble matter. The obtained ethanol-insoluble matter was filtered using a standard sieve of JIS Z8801 for 1 hour.
After being shaken for 0 minutes, the weight on each sieve was measured and the granules classified by the respective opening sieves were observed and analyzed, and whether the obtained granules were the supporting granules of the present invention or not. And the presence or absence of ethanol-insoluble components added in the post-process. When ethanol-insoluble components added to the support granules in the post-process are confirmed in the ethanol-insoluble components, the influence on the particle size distribution due to the post-process addition is removed to determine the average particle size of the support granules. . That is, by performing an operation of separating a solvent-insoluble component by an appropriately selected solvent or a combination thereof, after removing the surfactant composition and components added in a subsequent step, the physical properties of the supporting granules are removed. You can check.

Preferred physical properties of the detergent particles 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 size is preferably from 150 to 500 μm, more preferably from 180 to 400 μm.

[0157] 7. Method for Producing Detergent Particles A preferred production method for obtaining detergent particles comprises the following step (I), and may further comprise step (II) if necessary. Step (I): a step of mixing the surfactant composition 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) includes the case where the disintegration proceeds simultaneously.

<Step (I)> As a method of supporting the surfactant composition on the supporting granules, for example, using a batch type or continuous mixer, the supporting granules and the surfactant composition may be used. Is mixed. Here, when the batch method is used, the method of charging the mixer is as follows: (1) First, the support granules are charged into the mixer, and then the surfactant composition is added. (3) After loading a part of the supporting granules into a mixer, the remaining supporting granules and the surfactant composition are added little by little. A method such as charging can be used.

Among the surfactant compositions, those which exist in a solid or paste state even when the temperature is raised within a practical temperature range, for example, 50 to 90 ° C., are prepared by preliminarily preparing a low-viscosity non-liquid Disperse or dissolve in an ionic surfactant or nonionic surfactant aqueous solution or water to prepare a mixed solution or aqueous solution of the surfactant composition, and add the mixture or aqueous solution to the support granules in the form of the mixed solution or aqueous solution Just do it. According to this method, a surfactant composition existing in a solid or paste state can be easily added to the support granules. The mixing ratio of the low-viscosity surfactant composition or water and the solid or paste-like surfactant composition is preferably within a viscosity range in which the resulting mixed solution or aqueous solution can be sprayed.

The mixed liquid may be produced, for example, by adding a solid or paste-like surfactant composition to a low-viscosity surfactant or water and mixing the mixture, or in a low-viscosity surfactant or in water. A mixture of surfactant compositions is neutralized by neutralizing an acid precursor of a surfactant, for example, an acid precursor of an anionic surfactant with an alkali agent (for example, an aqueous solution of sodium hydroxide or potassium hydroxide). It may be prepared.

In this step, before the addition of the surfactant composition, simultaneously with 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 anionic surfactant acid precursor, the surfactant is highly compounded, the loading capacity of the supporting granules is controlled, the loading capacity is controlled, and the non-ionic surfactant of the detergent particles is prevented from being stained. In addition, it is possible to improve physical properties and quality such as fluidity.

The acid precursor of the anionic surfactant which can be used in the present invention includes, for example, alkyl benzene sulfonic acid, alkyl or alkenyl ether sulfuric acid,
Examples thereof include alkyl or alkenyl sulfate, α-olefin sulfonic acid, α-sulfonated fatty acid, alkyl or alkenyl ether carboxylic acid, and fatty acid. It is particularly preferable to add the fatty acid after the addition of the surfactant from the viewpoint of improving the fluidity of the detergent particles.

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, more preferably 1 to 20 parts by weight, per 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 for adding the acid precursor of the anionic surfactant, it is preferable to supply the liquid precursor at room temperature by spraying, and the solid at room temperature may be added as a powder, It may be supplied after spraying. However, when the powder is added, it is preferable to raise the temperature of the detergent particles in the mixer to a temperature at which the powder melts.

The following are specific examples of preferred mixing apparatuses. (1)-
(3) is preferred. (1) Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), vertical granulator (manufactured by Powrex Co., Ltd.), Ladyge mixer (manufactured by Matsuzaka Giken Co., Ltd.) , Proshare Mixer (Taikai Kiko Co., Ltd.)
Manufactured), JP-A-10-296064, JP-A-10-96064
(2) ribbon mixer (manufactured by Nichiwa Machine Industry Co., Ltd.), batch kneader (manufactured by Satake Chemical Machinery Co., Ltd.), ribocorn (manufactured by Okawara Seisakusho), etc. 3) Nauta mixer (manufactured by Hosokawa Micron Corporation), SV mixer (Shinko Pantech Co., Ltd.)
Manufactured). Among the above-mentioned mixers, preferably, a Lodige mixer, a pro-share mixer, and JP-A-10-29
Japanese Patent Application Laid-Open No. 6064 and Japanese Patent Application Laid-Open No. 10-296065 include a mixing apparatus and the like, and the following step (II) can be performed by the same apparatus, which is preferable in terms of simplification of equipment. Among them, the mixing devices described in JP-A-10-296064 and JP-A-10-296065 are preferable since the moisture and temperature of the mixture can be adjusted by aeration and the disintegration of the particles for supporting a surfactant can be suppressed. Further, a mixing device such as a Nauta mixer, an SV mixer, a ribbon mixer or the like capable of mixing the powder and the liquid without giving a strong shearing force is also preferable in that the disintegration of the particles for supporting a surfactant can be suppressed.

Further, the supporting granules and the surfactant composition may be mixed by using the continuous type apparatus of the above mixer.
In addition, examples of continuous mixers other than those described above include a flexomix type (manufactured by Powrex Corporation) and a turbulizer (manufactured by Hosokawa Micron Corporation).

In the case where a nonionic surfactant is used in this step, it has a function of increasing the melting point of the surfactant, a melting point of 45 to 100 ° C. and a molecular weight of 1,000 to 1,000.
30,000 water-soluble nonionic organic compounds (hereinafter referred to as a melting point increasing agent) or an aqueous solution thereof are added 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 after adding the surfactant composition, or to mix the surfactant composition in advance with the surfactant composition. By adding a melting point increasing agent, caking properties of detergent particles,
It is possible to suppress the bleeding property of the surfactant in the detergent particles. In addition, as these melting point increasing agents, the same ones as exemplified in the melting point increasing agent of the composition of the detergent particles described above can be used. The amount of the melting point increasing agent used is preferably 0.5 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and
3 parts by weight are most preferred. This range, suppression of aggregation between particles of detergent particles contained in the detergent particle group, high-speed solubility,
It is preferable from the viewpoint of suppressing spotting and caking. As a method of adding the melting point raising agent, it is possible to mix and add a surfactant and an arbitrary method in advance, or to add the melting point raising agent after the addition of the surfactant, it is possible to remove stains of the detergent particles group and the caking property. It is advantageous for suppression.

It is more preferable that the temperature in the mixer in the present step is increased to a temperature not lower than the pour point of the surfactant composition to perform the mixing. The pour point of the surfactant composition is determined according to JIS.
It is measured by the method specified in K2269. Here, the temperature for raising the temperature may be higher than the pour point of the surfactant composition to be added in order to promote the loading of the surfactant composition. The temperature is preferably up to 50 ° C. above the pour point, more preferably 10 ° C. to 30 ° C. above the pour point. In addition, 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
-20 minutes is preferable, and 2-10 minutes is more preferable.

When a surfactant aqueous solution or a water-soluble nonionic organic compound aqueous solution is added as a surfactant composition, a step of drying excess water during and / or after mixing is provided. Is also good.

Before, simultaneously with, during or after the addition of the surfactant composition, a powdered surfactant and / or a powder builder can be added. By adding the powder builder, the particle size of the detergent particles can be controlled, and the detergency can be improved. In particular, 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 accelerating the neutralization reaction. The powder builder 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 alkaline ability such as crystalline silicates, and other bases such as sodium sulfate which enhance ionic strength.

Here, the crystalline silicate is disclosed in
No. 79013, column 3, line 17 (particularly 500 to 10
It is preferable to crystallize by firing at 00 ° C. ), JP-A-7-89712, column 2, line 45;
No. 227895, page 2, lower right column, line 18 (particularly
The silicates in the table are preferred. The crystalline silicates described under (1) can be used as preferred powder builders. here,
Those SiO ₂ / M ₂ O of an alkali metal silicate (wherein M represents an alkali metal.) Is from 0.5 to 3.2, preferably used is more preferably that of 1.5 to 2.6.

The amount of the powder builder to be used is preferably 0.5 to 12 parts by weight, more preferably 1 to 6 parts by weight, per 100 parts by weight of the supporting granules. When the amount of the powder builder for detergent 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 modifying the surface of the detergent particles.

<Step (II)> In the present invention, in order to modify the particle surface of the detergent particles carrying the surfactant in step (I), the following (1) fine powder (2) One or more steps of adding (II) various surface coating agents such as a liquid material may be performed.

When the surface of the particles of the detergent particles of the present invention is coated, the fluidity and the caking resistance of the particles of the detergent tend to be improved. Therefore, it is preferable to provide a surface modification step.
As the apparatus used in the step (II), for example, among the mixers exemplified in the step (I), those having both a stirring blade and a crushing blade are preferable. The surface coating agent will be described below.

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

The fine powder is preferably an aluminosilicate, and may be either crystalline or amorphous. Other than aluminosilicates, fine powders such as sodium sulfate, calcium silicate, silicon dioxide, bentonite, talc, clay, silicate compounds such as amorphous silica derivatives and crystalline silicate compounds are also preferable. In addition, metal soap having a primary particle of 0.1 to 10 μm, powdered surfactant (for example, alkyl sulfate, etc.)
And water-soluble organic salts can also be used. When a crystalline silicate compound is used, it is preferably used in combination with a fine powder other than the crystalline silicate compound for the purpose of preventing the crystalline silicate compound from being deteriorated due to aggregation or the like due to moisture absorption or carbon dioxide gas.

The amount of the fine powder used is as follows.
0.5 to 40 parts by weight is preferable with respect to 0 parts by weight,
30 parts by weight is more preferable, and 2 to 20 parts by weight is particularly preferable. When the use amount of the fine powder is in this range, the fluidity is improved and a good feeling of use is given to the consumer.

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

(2-1) Water-soluble polymer Examples of the water-soluble polymer include polycarboxylates such as carboxymethyl cellulose, polyethylene glycol, polyacrylic acid or a salt thereof, a copolymer of acrylic acid and maleic acid, or a salt thereof. No. 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 particles. When the amount of the water-soluble polymer used is in this range, it is possible to obtain a detergent particle group showing good solubility, good fluidity, and anti-caking properties.

(2-2) Fatty Acid Examples of the fatty acid 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,
Particularly preferred is 0.5 to 3 parts by weight. In the case of a solid at room temperature, it is preferable to heat the mixture to a temperature at which it exhibits fluidity and then supply it by spraying.

8. Detergent composition The detergent composition in the present invention is a composition containing the above-described detergent particles, and further contains a detergent component (eg, builder granules, fluorescent dye, enzyme, Perfume, defoamer, bleach, bleach activator, etc.).

The content of the detergent particles in the detergent composition is preferably at least 50% by weight, more preferably at least 60% by weight, even more preferably at least 70% by weight from the viewpoint of detergency.
Particularly preferred is 80% by weight or more and 100% by weight or less.

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

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 to 1000 g / L, more preferably 6
00 to 1000 g / L, particularly preferably 650 to 850
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 particles and a separately added detergent component. Since the detergent composition thus obtained contains detergent particles having a large carrying capacity of a surfactant, even a small amount of the detergent composition can exhibit a sufficient washing effect.
The use of such a detergent composition is not particularly limited as long as it is a use using a powder detergent, for example, a powder detergent for clothing,
And automatic dishwashing detergents.

(11) Physical property measurement method The physical property value in this specification refers to a value measured by the following method. (Bulk density): Measured by a method specified by JIS K 3362. (Average particle size): Determined using a sieve specified in JIS Z8801. For example, the aperture is 2000 μm, 1400 μ
m, 1000 μm, 710 μm, 500 μm, 355 μm
m, 250 μm, 180 μm, and 125 μm using a 9-stage sieve and a tray, and a low tap machine (HEIKO SEISAK
USHO, tapping: 156 times / min, rolling: 29
0 times / min), 100 g of sample was shaken for 10 minutes and sieved.
μm, 250 μm, 355 μm, 500 μm, 710 μm
m, 1000 μm, 1400 μm, and 2000 μm, the weight frequency is accumulated on the tray and each sieve in the order, and the opening of the first sieve at which the cumulative weight frequency becomes 50% or more is αμ.
m, and the opening of the sieve one step larger than αμm is βμm
When the integration of the weight frequency from the pan to the αμm sieve is γ%, and the weight frequency on the αμm sieve is θ%,

[0188]

(Equation 3)

Can be obtained according to the following equation.

(Granule strength): 20 g of a sample was placed in a cylindrical container having an inner diameter of 3 cm × a height of 8 cm, and tapping was performed 30 times (Tsutsui Rikagiki Co., Ltd., TVP1 type tapping type tightly packed bulk density meter, tapping conditions; 36 cycles / minute,
A free fall is performed from a height of 60 mm, and the sample height at that time (initial sample height) is measured. Then, the entire upper end surface of the sample held in the container by a pressure tester was 10 mm / m
The pressure is applied at a speed of in, and a load-displacement curve is obtained. The initial sample height is multiplied by the slope in the linear portion where the displacement ratio is 5% or less, and the value obtained by dividing the area by the pressed area is defined as the granule strength.

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

(Pore volume distribution): The pore volume of the granules for supporting a surfactant was measured by the method of "SHIMAD" manufactured by Shimadzu Corporation.
Using a ZU-made pore sizer 9320 ", based on the instruction manual, the procedure is as follows. That is, the particles for supporting a surfactant were put into a cell, and mercury to be injected was introduced into a low pressure part (0 to 14.2 psi).
a) and a high pressure section (14.2 to 30000 psia) are measured. The data is smoothed by taking a moving average of two data before and after each to obtain a mode diameter in the range of 0.01 μm to 3 μm and a pore volume of 0.01 μm to 3 μm.

(Fluidity): The flow time was determined according to JIS K3
From the hopper for bulk density measurement specified by 362,
The time required for 100 mL of powder to flow out.
(Liquid surfactant composition carrying capacity): 100 g of granules were put into a cylindrical mixing tank having an inner diameter of 5 cm and a height of 15 cm equipped with a stirring blade inside, and stirred at 350 rpm at 30 ° C.
With polyoxyethylene alkyl ether [C ₁₂ / C ₁₄ =
6/4 (molar ratio), EO = 7.7, melting point = 25 ° C.]
The solution is dropped at a rate of 0 mL / min, and the change over time in the stirring power is measured. The amount of polyoxyethylene alkyl ether charged when the stirring power was the highest was determined by the weight of the granules (10
0 g) is defined as the carrying capacity (mL / g) of the granule group.

(Stain removal property): Length × width × height = 10 cm × 6 using two types of filter paper specified in JIS P 3801 (for example, “Quality No. 2 filter paper” manufactured by Toyo Roshi Co., Ltd.).
Make a container with a 4 cm × 4 cm open top. A line having a line width of 0.5 to 1.0 mm is drawn diagonally on the sample filling surface on the bottom surface of the container using an oil marker ("Magic Ink M700-T1" manufactured by Uchida Yoko Co., Ltd.). Sample 1 in the container
The total weight of the acrylic resin plate and the lead plate (or iron plate) is 15 g + 250 g. This was placed in a moisture-proof container, left in a thermostat at a temperature of 30 ° C., and after 7 days, the degree of bleeding of the oily marker was visually determined,
Judge the stainability. The criteria are as follows. Rank 5: Oily marker bleed width is 2 cm or more Rank 4: Oily marker bleed width is 1 cm or more Rank 3: Oily marker bleed width is 0.5 cm or more Rank 2: Oily marker bleeding is slightly recognized Rank 1: No bleeding of oily marker is observed.

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

The composition of the artificial contaminated liquid was 0.44 lauric acid.
Wt%, myristic acid 3.09 wt%, pentadecanoic acid 2.31 wt%, palmitic acid 6.18 wt%, heptadecanoic acid 0.44 wt%, stearic acid 1.57 wt%, oleic acid 7.75 wt% , Trioleic acid13.
06% by weight, n-hexadecyl palmitate 2.18% by weight, squalene 6.53% by weight, egg yolk lecithin liquid crystal 1.94% by weight, Kanuma red clay 8.11% by weight, carbon black 0.01% by weight, tap water Is the amount of balance.

The evaluation of the cleaning performance is performed by the following method.
2.2 kg of clothes (8/2 weight ratio of underwear and Y-shirt) to Matsushita Electric Industrial washing machine "Aizumago NA-F70AP"
And the artificial contaminated cloth 10 cm × 10 cm prepared above
The pieces were sewed on three pieces of 35 cm x 30 cm cotton base cloth and placed uniformly, and 22 g of the evaluation sample was placed on clothing in a gathered state, and water was poured so that water did not directly hit the evaluation sample.
Perform cleaning on the standard course. The washing conditions are as follows.
Washing course: standard course, detergent concentration 0.067% by weight, washing water 71.2mg Hard water with CaCO ₃ / L, molar ratio of Ca / Mg 7/3, water temperature 20 ° C, bath ratio 15L / kg.

The cleaning performance was measured by measuring the reflectance at 550 nm of the original cloth before and after the cleaning and the contaminated cloth before and after the cleaning with a self-recording colorimeter (manufactured by Shimadzu Corporation). Is shown as the cleaning performance. Note that the reflectance after cleaning is A, the reflectance before cleaning is B, and the reflectance C of the original cloth. Washing rate (%) = (AB) / (CB) × 100

[0199]

EXAMPLES In the present experimental examples, the following raw materials were used unless otherwise specified. Sodium sulfate: anhydrous neutral sodium sulfate (manufactured by Shikoku Chemicals Co., Ltd.) Sodium sulfite: sodium sulfite (manufactured by Mitsui Chemicals, Inc.) Fluorescent dye: Tinopearl CBS-X (manufactured by Ciba Specialty Chemicals) Sodium carbonate: dense ash (average grain) Diameter: 290 μm, manufactured by 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), manufactured by zeobuilder ) Polyoxyethylene alkyl ether: Emulgen 10
8KM (average number of moles of ethylene oxide added: 8.5,
(Chain 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 a fluorescent dye were added. Added and stirred for 10 minutes. 125 parts by weight of sodium carbonate were added, and 175 parts by weight of the following acrylic acid-based polymer aqueous solution was added, followed by stirring for 10 minutes. 40 parts by weight of sodium chloride was added as a crystal precipitation 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 was 5
3% by weight and the final temperature of this preparation was 50 ° C.

As the acrylic acid polymer aqueous solution, an aqueous solution of sodium polyacrylate produced according to the following method was used.

The aqueous solution of sodium polyacrylate was produced according to the method described in Examples of Japanese Patent Publication No. 24283/1990. The reaction was performed with a neutralization degree of 95% and a concentration of 37.7% by weight.
Of sodium acrylate at a rate of 3.11 kg / h, an aqueous solution of sodium bisulfite having a concentration of 35% by weight at a rate of 0.13 kg / h, an air supply of 3 m ³ / h, and an average jacket temperature of 20 ° C. Performed in 1000 parts by weight of the obtained aqueous solution of sodium acrylate polymer was charged, and the pH was adjusted to 12 by adding a 48% by weight aqueous solution of sodium hydroxide. The pH-adjusted aqueous solution of sodium acrylate polymer is kept at 40 ° C. and 8.57 parts by weight of 35% by weight aqueous hydrogen peroxide (3,000 mg / k with respect to the aqueous solution of sodium acrylate polymer charged as hydrogen peroxide)
g) was added dropwise, and the mixture was stirred at 40 ° C. for 24 hours. Subsequently, in order to remove residual hydrogen peroxide, 5.54 parts by weight of a 35% by weight aqueous solution of sodium hydrogen sulfite was added, and the mixture was further stirred at 40 ° C. for 24 hours to obtain a target aqueous solution of an acrylic acid polymer (solid content: 40% by weight). %). The weight average molecular weight of the obtained acrylic acid polymer 1 was 10,000. This sodium polyacrylate was synthesized at a low temperature of 20 ° C. by adopting a redox polymerization method and was mildly synthesized. In addition, the acrylic acid-based polymer 1
As a result of measuring the characteristic value of
Is 21.3 nm, the ratio of particles having a particle diameter exceeding 800 nm is 24.7%, and the relative half width in HPLC measurement is 1.30 nm. 68, the adsorption rate to burkeite is 9.6%, the degree of branching is 0.0, the dispersibility of mud particles is 0.83, the calcium ion trapping ability is 211 mg CaCO ₃ / g, and the stability constant for calcium ions is 3.2. Met. In addition, as a result of measuring the content of methoquinone in the 40% by weight aqueous solution of the acrylic acid polymer, it was not detected.

Sampling was performed from the prepared solution 10 minutes after the addition of the acrylic acid-based polymer aqueous solution (before adding sodium chloride) and the prepared solution 60 minutes after the addition of sodium chloride (before zeolite addition), and the TSUB-TEC M100 Was used to measure the particle number and particle size distribution. The number of particles in the preparation liquid before the addition of sodium chloride was 503 / s, and the average particle size (number basis) was 65.3 μm. The number of particles in the preparation solution 60 minutes after the addition of sodium chloride was 6021 / s, and the average particle size was 35.7 μm. From these measurement results, the number of water-soluble salts was 55
The average particle size of burkeite increased by 18 particles / s 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 was 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 checked and evaluated according to the following criteria. Particularly good: Pink colored particles are not observed. Good: Slight pink coloration is observed in a very small part of the particles. Pinking: Pinkish particles are clearly observed.

Detergent particles 1 were produced using surfactant-supporting granules 1 by the following method. Palmitic acid (Lunac P) equivalent to 1.6 parts by weight of polyethylene glycol and 4 parts by weight of sodium palmitate per 21 parts by weight of polyoxyethylene alkyl ether mixed at 80 ° C.
-95, manufactured by Kao Corporation), an alkylbenzenesulfonic acid precursor (Neoperex GS, manufactured by Kao Corporation) corresponding to 25 parts by weight of sodium alkylbenzenesulfonate, and a water content of 11 wt. % Of a water-containing surfactant composition was prepared.

Next, a Lady Ge mixer (Matsuzaka Giken Co., Ltd.)
100 parts by weight of the obtained granules for supporting a surfactant 1 (capacity: 130 L, equipped with a jacket), and stirring of the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s) is started. did. In addition, warm water of 80 ° C was applied to the jacket at a rate of 10 L /
Shed in minutes. Thereto, 58 parts by weight of the above surfactant composition was added over 2 minutes, and then stirred for 5 minutes. Furthermore,
Crystalline sodium silicate ((Clariant Tokuyama,
A roller mill (average particle size of 120 μm) (average particle size of 8 μm)) was charged with 22 parts by weight of zeolite and 12 parts by weight of zeolite as a minimum amount for the stain removal property of the detergent particles to be 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) for 1 minute, and the detergent particles 1-
1 was discharged. Here, the stain removal property of the detergent particles was 1
The smaller the minimum amount of zeolite becomes, the more excellent the ability of the particles for supporting a surfactant to support the liquid composition is. The composition and physical properties of the detergent particles 1-1 are shown in Table 2 (in the table, the detergent particles are abbreviated as "particles"). Further, the cleaning performance of the above-described detergent particle group 1-1 was evaluated. The results are shown in Tables 2 and 3.

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

As a result of measuring the characteristic value of the acrylic acid polymer 2, the particle size on the large particle size side where the height of the peak including 10 nm in light scattering measurement attenuated to half its maximum value was 17. 1%, the ratio of particles having a particle size exceeding 800 nm is 0%, and the relative half width in HPLC measurement is 1.5.
5. Adsorption rate to burkeite is 6.5%, branching degree is 3.
9. The dispersing ability of mud particles was 0.82, the capturing ability of calcium ions was 213 mg CaCO ₃ / g, and the stability constant for calcium ions was 3.3. Further, as a result of measuring the metoquinone content in the acrylic acid polymer aqueous solution,
Not detected.

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

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

Detergent particles 2-1 were produced in the same manner as in Experimental Example 1 using surfactant-supporting granules 2. The amount of zeolite charged as the minimum amount at which the stain removal property of the detergent particles became 1 was 12 parts by weight. Table 2 shows the composition and physical properties of the detergent particle group 2-1. In addition, the above-mentioned detergent particle group 2-1
Was evaluated for cleaning performance. The results are shown in Tables 2 and 3.

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

Sampling was performed from the prepared solution 10 minutes after the addition of the 40% by weight aqueous acrylic acid polymer solution (before adding sodium chloride) and from the prepared solution 60 minutes after the addition of sodium chloride (before zeolite), to obtain TSSUB-TEC M100.
Was used to measure the particle number and particle size distribution. Before the addition of sodium chloride, the number of particles in the preparation liquid was 501 / s, and the average particle size (number basis) was 65.1 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 5293 / s, and the average particle size was 34.7 μm. From these measurement results, the number of water-soluble salts was 47
The average particle size of the burkeite increased by 92 particles / s was 26.8 μm.

In the same manner as in Experimental Example 1, surfactant-supporting granules 3 were obtained. Table 1 shows the composition and physical properties of the surfactant supporting granules 3. In addition, the hue of the obtained granules for supporting a surfactant 3 was good.

Detergent particle group 3-1 was produced in the same manner as in Experimental Example 1 using surfactant-supporting granule group 3. The amount of zeolite charged as the minimum amount at which the stain removal property of the detergent particles became 1 was 12 parts by weight. Table 2 shows the composition and physical properties of the detergent particle group 3-1. In addition, the above detergent particle group 3-1
Was evaluated for cleaning performance. The results are shown in Tables 2 and 3.

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

As a result of measuring the characteristic values 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 light scattering measurement attenuated to half its maximum value was 16. The ratio of particles having a particle diameter exceeding 2 nm and 800 nm is 14.8%, the relative half width in HPLC measurement is 1.81, the adsorption rate to burkeite is 7.4%, and the dispersibility of mud particles is 0.82. Calcium ion trapping ability is 207
The stability constant against mgCaCO ₃ / g and calcium ions was 3.7. Further, as a result of measuring the content of methoquinone in the aqueous solution of the acrylic acid-based polymer, it was not detected.

Sampling was performed from the prepared solution 10 minutes after the addition of the acrylic acid-based polymer aqueous solution (before the addition of sodium chloride) and from the prepared solution 60 minutes after the addition of the sodium chloride (before the addition of zeolite), and the TSUB-TEC M100 was used. 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 (number basis) was 79.5 μm. Add sodium chloride 60
The number of particles in the preparation liquid after one minute was 2,780 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 the increased burkeite was 21.0
μm.

[0220] In the same manner as in Experimental Example 1, surfactant-supporting granules 4 were obtained. Table 1 shows the composition and physical properties of the surfactant-supporting granules 4. The hue of the obtained surfactant-supporting granules 4 was particularly good.

Detergent particles 4-1 were produced in the same manner as in Experimental example 1 using surfactant supporting granules 4. The amount of zeolite charged as the minimum amount at which the stain removal property of the detergent particles became 1 was 12 parts by weight. Table 2 shows the composition and physical properties of the detergent particles 4-1. In addition, the above-mentioned detergent particle group 4-1
Was evaluated for cleaning performance. The results are shown in Tables 2 and 3.

Experimental Example 5 A prepared solution was obtained in the same manner as in Experimental Example 1. The aqueous solution of acrylic acid polymer used was an aqueous solution of sodium polyacrylate produced according to the following method. The aqueous solution of sodium polyacrylate was produced according to the method described in Examples of Japanese Patent Publication No. 2-24283. In the reaction, an aqueous solution of sodium acrylate having a degree of neutralization of 95% and a concentration of 37.7% by weight was supplied at 3.11 kg / h, and an aqueous solution of sodium bisulfite having a concentration of 35% by weight was supplied at 0.13 kg / h. The supply was performed at an average temperature of the jacket of 20 ° C. at a supply rate of 3 m ³ / h to obtain an intended aqueous solution of an acrylic acid-based polymer (solid content: 40% by weight). The weight average molecular weight of the obtained acrylic acid polymer 5 was 10,000. This sodium polyacrylate was synthesized at a low temperature of 20 ° C. by adopting a redox polymerization method and was mildly synthesized. In addition, as a result of measuring the characteristic values 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 light scattering measurement is attenuated to half of the maximum value is 16.1 nm and 800 nm. The ratio of particles having a particle size exceeding 9.3%, the relative half width in HPLC measurement is 1.69, the adsorption rate to burkeite is 9.3%, the degree of branching is 0.0, and the dispersing ability of mud particles is 0.83, the calcium ion trapping ability was 212 mgCaCO ₃ / g, and the stability constant for calcium ions was 3.3. Further, as a result of measuring the content of methoquinone in the 40% by weight aqueous solution of the acrylic acid polymer, it was found that 40 ppm of metoquinone was contained.

Sampling was performed from the prepared solution 10 minutes after the addition of the 40% by weight aqueous solution of the acrylic acid polymer (before adding sodium chloride) and the prepared solution 60 minutes after the addition of sodium chloride (before zeolite), and the TSUB-TEC M100
Was used to measure the particle number and particle size distribution. The number of particles in the preparation liquid before the addition of sodium chloride was 640 / s, and the average particle size (number basis) was 81.1 μm. The number of particles in the preparation 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 adding sodium chloride.
The average particle size of the burkeite increased by 19 particles / s was 14.2 μm.

In the same manner as in Experimental Example 1, a granule group 5 for supporting a surfactant 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 particles 5-1 were produced in the same manner as in Experimental Example 1 using surfactant-supporting granules 5. The amount of zeolite charged as the minimum amount at which the stain removal property of the detergent particles became 1 was 12 parts by weight. Table 2 shows the composition and physical properties of the detergent particle group 5-1. In addition, the above-mentioned detergent particle group 5-1
Was evaluated for cleaning performance. The results are shown in Tables 2 and 3.

Experimental Example 6 A preparation was obtained in the same manner as in Experimental Example 1. As the aqueous solution of the acrylic acid-based polymer, a sodium polyacrylate aqueous solution manufactured by BASF: Sokaran PA-30CL (solid content: 46.8% by weight) was used. Adjusted by the amount of In addition, this Sokaran PA
-30CL is commercially available for use in detergent builders and is used in general detergents.

The characteristic value of the acrylic acid polymer 6 was
As a result of measurement, peaks including 10 nm in light scattering measurement
Particle size on the large particle size side where the height of
Of particles having a particle size exceeding 33.7 nm and 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, dispersibility of mud particles 0.79, calcium ion capture
Noh is 206mgCaCO _Three/ G, against calcium ion
The stability constant was 3.8. In addition, the 46.8 layers
% Of Methoquinone in Aqueous Solution of Acrylic Acid Polymer
As a result of the measurement, 15 ppm of metoquinone was contained.
Was.

Sampling was performed from the prepared solution 10 minutes after the addition of the aqueous acrylic acid polymer solution (before adding sodium chloride) and the prepared solution 60 minutes after the addition of sodium chloride (before zeolite), and the TSUB-TEC M100
Was used to measure the particle number and particle size distribution. The number of particles in the preparation liquid before the addition of sodium chloride was 632 / s, and the average particle size (number basis) was 66.5 μm. The number of particles in the preparation solution 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, surfactant-supporting granules 6 were obtained. Table 1 shows the composition and physical properties of the surfactant supporting granules 6. The hue of the obtained surfactant-supporting granule group 6 was pink.

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

In the same manner as in Experimental Examples 1 to 5, detergent particles 6-2 containing 12 parts by weight of zeolite were prepared, and the cleaning performance was evaluated. Table 3 shows the results.

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

A raw material supply tank for a monomer solution and an initiator solution in a glass reactor (hereinafter referred to as a reactor) equipped with a stirrer, a thermometer, a reflux condenser, an inlet for dropping the monomer solution and the initiator solution, and a heating jacket. (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 maleic acid salt partially neutralized with a 48% by weight aqueous sodium hydroxide solution at a degree of neutralization of 40% is charged into a reactor, and 125 kg of an 80% by weight aqueous acrylic acid solution are charged into a monomer supply tank. . Also, 35
20 kg by weight of a hydrogen peroxide solution was charged into the initiator supply tank. The polymerization temperature is 10 by passing warm water through the jacket of the reactor.
Adjust to 0 ± 3 ° C. An 80% by weight aqueous solution of acrylic acid and a 35% by weight aqueous hydrogen peroxide solution were continuously dropped therein through the inlet and stirred. Dropping is performed in 6 hours, and then 2
Stayed for a time. At this time, although a little 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 polymer 7
Was adjusted to pH 7 using a 48% by weight aqueous sodium hydroxide solution and the concentration was adjusted to 40% by weight to obtain a sodium salt aqueous solution. The acrylic acid polymer 7 was synthesized under a hard condition using a large amount of aqueous hydrogen peroxide to generate a large amount of radicals, and a chain transfer agent and the like were not used in the synthesis. In addition, as a result of measuring the characteristic values of the acrylic acid-based polymer 7, the particle size on the large particle size side where the height of the peak including 10 nm in light scattering measurement attenuated to half of the maximum value was 423.3 nm and 800 nm. Of particles having a particle size exceeding 29.1%, and the adsorption rate to burkeite is 2.3.
%, The ability to disperse mud particles was 0.3, the ability to trap calcium ions was 380 mg CaCO ₃ / g, and the stability constant for calcium ions was 4.0. In addition, as a result of measuring the content of metoquinone in the 40% by weight aqueous solution of the acrylic acid polymer, no metoquinone was detected.

Sampling was performed from the prepared solution 10 minutes after the addition of the aqueous acrylic acid polymer solution (before adding sodium chloride) and from the prepared solution 60 minutes after the addition of sodium chloride (before zeolite), and the TSUB-TEC M100
Was used to measure the particle number and particle size distribution. Before the addition of sodium chloride, the number of particles in the preparation liquid was 589 / s, and the average particle size (number basis) was 65.4 μm. The number of particles in the preparation liquid 60 minutes after the addition of sodium chloride was 601 / s, and the average particle size 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. In addition, the hue of the obtained surfactant supporting granules 7 was particularly good.

Detergent particles 7-1 were produced in the same manner as in Experimental Example 1 using surfactant-supporting granules 7. The amount of zeolite charged as the minimum amount at which the stain removal property of the detergent particles became 1 was 43 parts by weight. Table 2 shows the composition, physical properties, and cleaning performance of the detergent particles 7-1. Experimental Examples 1 to
In the same manner as in Example 5, a detergent particle group 7-2 in which the amount of zeolite was 12 parts by weight was produced, and the cleaning performance was evaluated. Table 3 shows the results.

[0237]

[Table 1]

[0238]

[Table 2]

[0239]

[Table 3]

In the experimental examples of the present invention, burkeite precipitated in the preparation step of the preparation and the spray drying step becomes fine by using an acrylic acid polymer having specific properties. Therefore, the surfactant-containing granules 1 to 5,
The pore volume distribution has a smaller mode diameter and a larger pore volume than the surfactant supporting granules 6 or 7, and has a pore volume distribution in which the ability to support the liquid composition is increased. As a result, the detergent particles of the present invention (detergent particles 1-
1-5-1) can significantly reduce the required amount of zeolite added later to maintain quality (stain 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.
-2 higher cleaning performance (Table 3). In the detergent particle group 6-2 or 7-2, the surfactant composition was exuded into agglomerates, and the dispersion solubility when evaluating the cleaning performance was reduced. That is, by using the surfactant-supporting granules 1 to 5 of the present invention, the surfactant-supporting granules 6 or 7 (the peak height including 10 nm in the light scattering measurement is Detergent particles having higher quality and higher cleaning performance than when using a particle size on the large particle size side which attenuates to a half value of the maximum exceeds 32 nm) can be obtained. Further, by using the surfactant-supporting granules 1 to 4, it is possible to obtain a detergent particle excellent in hue.

[0241]

EFFECTS OF THE INVENTION According to the present invention, a surfactant-supporting granule excellent in the carrying capacity (supporting capacity / supporting power) of the surfactant composition, high quality and high washing performance, and also excellent in hue. And a detergent composition comprising the detergent particles.

[Brief description of the drawings]

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

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

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

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

[Explanation of symbols]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 17/06 C11D 17/06 (72) Inventor Fumihiko Nakamura 1334 Minato, Wakayama-shi Kao Corporation Research Institute ( 72) Inventor Masaji Tanaka 1334 Minato, Wakayama City, Kao Corporation Research Institute (72) Inventor Tadashi Yoshimura 1334 Minato, Wakayama City Kao Corporation Research Institute (72) Inventor Jin Takatani 1334 Minato, Wakayama City Kao Stock F-term (reference) 4H003 AB03 AB19 AC07 BA10 CA21 DA01 EA12 EA16 EA19 EA24 EA28 EB30 EB36 ED02 FA09 FA41

Claims (9)

[Claims] The weight average molecular weight is from 3,000 to 100,000, and the particle size on the large particle size side where the height of a peak including 10 nm in light scattering measurement attenuates to a half of the maximum value is 32 nm.
Spray-drying a preparation solution containing an acrylic acid polymer having a particle size of less than or equal to and having a particle size exceeding 800 nm of 70% or less, and sodium carbonate and sodium sulfate, for supporting a surfactant containing burkeite Manufacturing method of granules. 2. The process for producing particles for supporting a surfactant according to claim 1, wherein the acrylic acid-based polymer has a calcium ion-trapping ability of 160 mg CaCO ₃ / g or more and a stability constant for calcium ions of 2.6 or more. . 3. The surfactant-supporting granules contain 5 to 30% by weight of an acrylic acid polymer, and the total content of sodium carbonate and sodium sulfate is 19% by weight based on the content of the polymer. 3. The method of claim 1, wherein the weight ratio of sodium carbonate to sodium sulfate is 1/10 to 10/1. 4. The method for producing surfactant-supporting granules according to claim 1, wherein the acrylic acid-based polymer to be added to the preparation liquid is in the form of an aqueous solution having a quinone content of 6 ppm or less. 5. The method according to claim 5, wherein said mercury porosimeter is 0.0.
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.
The granule strength is 15 MPa or more.
A surfactant-supporting granule obtained by the production method according to any one of (1) to (4). 6. A particle having a weight-average molecular weight of 3,000 to 100,000 and a particle size on the large particle size side where the height of a peak including 10 nm in light scattering measurement attenuates to a half of the maximum value is 32 nm.
Not more than 5% by weight of an acrylic acid polymer in which the ratio of particles having a particle size exceeding 800 nm is 70% or less, and sodium carbonate and sodium sulfate in a weight ratio of 1/10 to 10 / 1. Surfactant-supporting granules containing burkeite, wherein the total content of sodium carbonate and sodium sulfate is 19/1 to 1/2 by weight relative to the polymer content. 7. The particles for supporting a surfactant according to claim 6, wherein the acrylic acid-based polymer has a calcium ion-scavenging ability of 160 mg CaCO ₃ / g or more and a stability constant for calcium ions of 2.6 or more. 8. Detergent particles comprising 10 to 100 parts by weight of a surfactant composition per 100 parts by weight of the particles for supporting a surfactant according to claim 5. 9. The detergent particle group according to claim 8, wherein
A detergent composition containing 0% by weight and having an average particle size of 150 to 500 µm and a bulk density of 500 to 1000 g / L.