JP3249815B2 - Particles for detergent addition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a detergent additive particle group, a composite detergent particle group, and a granular detergent composition.

BACKGROUND ART In recent years, granular detergent compositions (compact detergents) have become the mainstream of detergents for clothing. The granular detergent composition is manufactured by using various techniques such as mixing, granulation, compression, and pulverization, and has great advantages in simplicity in use and reduction in transportation cost. On the other hand, granular detergent compositions tend to be less soluble than low bulk density detergents, and in particular, a drum type washing machine that distributes (flows) granular detergent compositions placed in an aggregated state into a washing tub by pouring water. In addition, in a dispenser (detergent input tray) of a fully automatic washing machine or the like, there is a problem that troubles often remain due to aggregates (pastes) of the granular detergent composition. To date, many studies have been made to improve the dispensability of granular detergent compositions from dispensers. For example, Japanese Translation of International Patent Publication No. 7-509267
Japanese Patent Application Laid-Open Publication No. H10-15064 discloses a detergent composition in which fine powder or coarse powder of sodium carbonate, sodium citrate, or the like is added as a filler to a base powder having less than 10% by weight of particles having a particle size of less than 150 μm and less than 10% by weight of particles having a size of more than 1700 μm. It has been disclosed. This is to increase the bulk density and improve the dispensability from the dispenser by reducing the fines containing the surfactant and post-adding the fines or coarse, rapidly dissolving ungelled particles. Also, JP-A-11-359
No. 98 discloses a granular high-density detergent in which the composition of the weight frequency of a 50% diameter and a particle diameter of less than 125 μm, the weight frequency of a particle diameter of 1410 μm or less, and the weight frequency of the specific particle diameter is limited to a specific range. It has been disclosed. this is,
It is intended to improve both the dispersibility and the particle solubility of the granular detergent composition by controlling the particle size distribution and has been shown to be suitable for use in dispensers. By these techniques, the dispensability from the dispenser is improved, and the frequency or amount of troubles in which the paste-like high-density detergent composition remains in the dispenser is reduced, but the water pressure at the time of water injection decreases, and the water temperature decreases. Depending on the method of water injection, the type of dispenser, and the like, there is still a concern that the residual detergent will remain in the dispenser. Therefore, it is desired to further improve the dispersibility of the granular detergent composition in the dispenser.

DISCLOSURE OF THE INVENTION The present invention relates to a granular detergent composition having excellent dispensing properties when poured into a dispenser of a drum type washing machine, a fully automatic washing machine, etc., a composite detergent particle group contained in the granular detergent composition, and the composite detergent composition. It is an object of the present invention to provide a detergent additive particle group contained in the detergent particle group.

These and other objects of the invention will be apparent from the description below.

The present invention relates to [1] a detergent additive containing 30 to 100% by weight of two or more water-soluble substances and further containing less than 10% by weight of a surfactant and / or 70% by weight or less of a water-insoluble substance. A particle group having an average particle size of 150 to 600 μm, a bulk density of 300 to 1000 g / L, and 5 ° C.
When the particle group is put into water and stirred for 60 seconds under the following stirring conditions and supplied to a standard sieve specified by JIS Z 8801 (opening: 74 μm), the particle group calculated by the formula (1) Detergent-added particles (a) having a dissolution rate of 90% or more
And an average particle size of 150 to 600 μm and a bulk density of 500
複合 1000 g / L, composite detergent particles obtained by dry-mixing detergent particles (b) containing 10 to 50% by weight of a surfactant, stirring conditions: 1 L of hard water (71.2 mg CaCO ₃ /
L and a molar ratio of Ca / Mg of 7/3), 1 g of the particle group was charged, and the mixture was stirred with a stirrer (length: 35 mm, diameter: 8 mm) in a 1 L beaker (inside diameter: 105 mm). ) = {1- (T / S)} × 100 (1) S: Input weight (g) of detergent-added particles T: When the aqueous solution obtained under the above stirring conditions is supplied to the above sieve, the sieve is used. Dry weight (g) of dissolved residue of the remaining detergent-added particles: [2] 50 to 100 of the composite detergent particles described in [1].
(3) contains 30 to 100% by weight of two or more water-soluble substances, and further contains less than 10% by weight of a surfactant and / or 70% by weight or less of a water-insoluble substance. A particle group for detergent addition which may have an average particle diameter of 150 to 600 μm, a bulk density of 300 to 1000 g / L, and 5 ° C.
When the particle group is put in water and stirred for 60 seconds under the following stirring conditions and supplied to a standard sieve specified by JIS Z 8801 (opening: 74 μm), the particle group calculated by the above formula (1) Relates to the detergent-added particles (a) having a dissolution rate of 90% or more.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a detergent-adding particle group having a specific composition, a specific powder property and a specific high dissolution rate which does not contain a surfactant or has a low surfactant content ( a) + complex detergent particles (a) obtained by preparing a) and mixing with detergent particles (b) containing more surfactant
(B) that the dispersibility in the dispenser is remarkably improved, and the residual trouble in the dispenser of the granular detergent composition can be remarkably improved by allowing the complex detergent particles to be present in the granular detergent composition in a specific amount or more. It is.

 Hereinafter, definitions of terms in the present invention will be described.

1. Definition of Terms Detergent-adding particles are particles that may contain less than 10% by weight of a surfactant and a builder, and the detergent-adding particles are an aggregate thereof. The detergent particles are particles containing 10 to 50% by weight of a surfactant, and the detergent particle group is an aggregate thereof. The composite detergent particles are an aggregate obtained by dry-mixing the detergent-adding particles and the detergent particles. The granular detergent composition means a finished product of a granular detergent comprising a composite detergent particle group obtained by dry-mixing a detergent additive particle group and a detergent particle group, and a detergent component (for example, Builder granules, fluorescent dyes,
Enzymes, fragrances, defoamers, bleaching agents, bleaching activators, etc.) and those containing particles other than the above-mentioned detergent-adding particles and detergent particles are also included.

2. Particles for adding detergent (a) By blending as a component of the granular detergent composition,
The detergent-adding particles of the present invention, which exhibit excellent dispenser dispersibility in a granular detergent composition, do not contain a surfactant or have an extremely low surfactant content of less than 10% by weight, and are described below. It has features.

2-1. The present invention relates to a method of dissolving a particulate detergent composition by discontinuing a continuous, high-concentration surfactant paste layer formed by the particulate detergent composition when water is injected in a dispenser. As a method of enhancing the distribution of the product, a specific composition, a detergent-adding particles having specific powder properties are mixed with the granular detergent composition, and further, the detergent-adding particles have a high-speed solubility described below. It is characterized by the following.

That is, due to the high-speed solubility of the detergent-added particles mixed in the granular detergent composition, a high-concentration paste layer of a surfactant formed upon water injection is rapidly discontinued and the detergent The granular detergent composition can be quickly and efficiently dispensed from the dispenser by the action of the addition particles rapidly dissolving in the water injection. In addition, when the particles having a low dissolution rate are mixed with the detergent particles, the paste formed when the mixture is poured with a dispenser becomes harder, and a phenomenon of lowering the dispersibility from the dispenser is observed. It is extremely important to have fast dissolution.

The high-speed solubility of the detergent-adding particles can be confirmed as showing a remarkably high dissolution rate when dispersed into individual constituent particles in water. The fast dissolving power of the particles for detergent addition of the present invention is 60% by the method described below.
When the mixture is stirred for 2 seconds and supplied to a standard sieve specified by JIS Z 8801 (mesh size: 74 μm), the dissolution rate calculated by the formula (1) is 90% or more. In addition, from the viewpoint of further improving the dispensability from the dispenser, the dissolution rate is 92%.
% Or more is preferable, 94% or more is more preferable, and 96%
Or more, more preferably 97% or more, and 98% or more.
% Is more preferable, and 99% or more is most preferable.

 The method for confirming the fast solubility is described in detail below.

1L hard water (Ca / Mg molar ratio 7/3) corresponding to 71.2 mg CaCO ₃ / L cooled to 5 ° C. was poured into a 1L beaker (a cylindrical type having an inner diameter of 105 mm and a height of 150 mm, for example, a 1L glass beaker manufactured by Iwaki Glass Co., Ltd.) 5)
In a state where the water temperature is kept constant by a water bath, a stirrer (length: 35 mm, diameter: 8 mm, for example, model: ADV
Rotation speed (800) at which the depth of the spiral becomes about 1/3 of the water depth with Teflon SA (round thin type) manufactured by ANTEC.
(rpm). The detergent-added particles, which have been reduced and weighed so as to be 1.0000 ± 0.0010 g, are introduced and dispersed in water with stirring, and stirring is continued. After 60 seconds from the introduction, the particle group dispersion in the beaker is subjected to JIS of known weight.
A standard sieve with a mesh size of 74 μm (diameter 1
00 mm), and the water-containing particles remaining on the sieve are collected together with the sieve into an open container of known weight. The operation time from the start of filtration to the collection of the sieve is 10 ± 2 seconds. The collected residue of the particle group is dried for 1 hour using an electric dryer heated to 105 ° C., and then cooled in a desiccator (25 ° C.) containing silica gel for 30 minutes. After cooling, the total weight of the dried residue of the particle group, the sieve, and the collection container is measured, and the dissolution rate (%) of the detergent addition particle group is calculated by the following equation (1).

Dissolution rate (%) = {1- (T / S)} × 100 (1) S: Input weight of detergent-added particles (g) T: The aqueous solution obtained under the above stirring conditions was subjected to the above sieve. Occasionally, the dry weight (g) of the residue of the detergent-addition particles remaining on the sieve The method for making the detergent-addition particles rapidly soluble is described below.

2-1-1. High-speed solubility by controlling particle size distribution One of the means to express high-speed solubility when the particles for detergent addition is dispersed in water is the relationship between the diameter of the particles constituting the particles for detergent addition and the dissolution rate. It is an effective means to adjust the particle size distribution of the detergent additive particle group in consideration of the above. That is, the dissolution rate per unit time is measured for a group of detergent-added particles classified into a plurality of stages according to the size of the particle diameter, and when the dependency of the particle diameter on the dissolution rate is high, the detergent addition classified by a sieve is used. High-speed solubility can be expressed by a method of reconstituting a particle size distribution having a high dissolution rate using the particle group for use.

2-1-2. High-speed Solubility Due to Intraparticle Voids Another means for achieving high-speed solubility can be achieved by significantly increasing the dissolution rate of the particles (detergent-adding particles) constituting the detergent-adding particles. High-speed solubility can be exhibited by constituting the detergent-adding particles with particles having fine spaces inside the particles. The particles for detergent addition having a fine space inside are not only gradually dissolved from the surface, but also water penetrates into the fine space inside the particles after the surface is dissolved, and dissolution from the inside and disintegration of the particles due to the penetrated water. The dissolution rate per unit time is increased. The fine space inside the particles can be measured as a pore volume of 0.01 to 4 μm by a mercury intrusion method, and the pore volume is preferably 0.2 mL / g or more. In addition, from the viewpoint of expressing more excellent high-speed solubility by infiltrating more water into the inside of the particles, the pore volume is more preferably 0.25 mL / g or more, more preferably 0. .3m
L / g or more, most preferably 0.35 mL / g or more. In addition, from the viewpoint of securing an appropriate particle density and particle strength, the pore volume is preferably 1.2 mL / g or less,
1.0 mL / g or less is more preferable, and 0.8 mL / g or less is still more preferable. When obtaining the pore volume of the detergent-added particles, a mercury porosimeter, for example, SHIMADZ
A U-made pore sizer 9320 can be used. The pore volume is a value of a pore volume of 0.01 to 4 μm measured with a mercury porosimeter on the sample detergent sample that has been reduced.

2-1-3. Another method for developing high-speed solubility by releasing bubbles is to use a detergent-adding particle group in the process of dissolving in water to reduce the particle size to 1/10 of the particle size.
High-speed solubility can be exhibited by comprising detergent-adding particles (bubble-releasing detergent-adding particles) having a structure capable of releasing bubbles having the above diameter. The detergent-adding particles dissolve not only from the surface but also water inside the particles due to the release of air bubbles from the inside of the particles, and dissolution from the inside due to the penetrated water and dissolution per unit time due to the disintegration of the particles. The rate is raised.

Such a dissolution behavior is such that when the particles for adding bubble releasing detergent are dissolved in water, the particle diameter is at least 1/10, preferably at least 1/5, more preferably at least 1/4, more preferably at least 1/4 of the particle diameter of the particles. 1/3 or more, and among them, preferably 1/2
The phenomenon of releasing bubbles having the above diameter (hereinafter, referred to as bubbles of a predetermined size) can be confirmed with a digital microscope, an optical microscope, or the like. When the particles for adding the bubble releasing detergent are dissolved in water in a static state, 120
Preferably, bubbles of a predetermined size are generated within seconds, more preferably within 60 seconds, more preferably within 45 seconds, more preferably within 30 seconds, more preferably within 20 seconds, and most preferably within 10 seconds. .

The bubble-adding detergent-adding particles only need to have pores (single or plural) capable of releasing bubbles of a predetermined size, and are not particularly limited to the shape and structure of the particles. For example, detergent-adding particles that release a single bubble may be used, or detergent-adding particles that release a plurality of bubbles obtained by aggregating the detergent-adding particles may be used. In addition, the bubble releasing detergent-adding particles are preferably contained in the detergent-adding particles at 50% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, and more preferably 80% by weight or more. Most preferred is at least 90% by weight.

In addition, when the detergent-adding particles containing the bubble-releasing detergent-adding particles are mixed with the granular detergent composition, in addition to the effect of the high-speed dissolution, the granular detergent composition is injected when dispensed with a dispenser. The dispersibility is also improved by the release of air bubbles from the air and the accompanying effect of water intrusion.

 The bubble diameter is measured as follows.

A double-sided tape is attached to the center of the bottom of the glass Petri dish (50 mm in inner diameter). The particles for detergent addition are deposited on the double-sided tape. First, the equivalent circle diameter (αμm) of each particle from an image obtained using a digital microscope
Is measured. As the digital microscope, for example, "VH-6300" manufactured by KEYENCE can be used.

Subsequently, 5 m of ion-exchanged water at 20 ° C. was placed in a glass Petri dish.
L is injected and the dissolution behavior of the individual particles to be measured is observed. When bubbles are released from the inside of the particles, the circle equivalent diameter of the bubbles (βμ
m) is measured. When a plurality of bubbles are released from the inside of the particle, the maximum value of the equivalent circle diameter measured for each bubble is set to β μm. Then, the ratio of the bubble diameter to the particle diameter (β / α) is determined for each particle.

In the preferred particles for adding a bubble releasing detergent, 1/10 to 4/5 of the particle diameter, preferably 1/5 to 4
/ 5, more preferably 1/4 to 4/5, more preferably 1/3 to 4/5, particularly preferably 1/2 to 4/5.
It is preferred that pores having a diameter of

 The pore diameter can be measured as follows.

The selected detergent-adding particles are cut with a scalpel or the like on a surface including the maximum particle diameter so as not to break the selected particles. The cut surface is observed with a scanning electron microscope (SEM), and the equivalent circle diameter (particle diameter) (γ μm) of the cut surface of the cut particle and the equivalent circle diameter of the pore when the presence of pores inside the particle are confirmed (γ) The pore diameter) (δ μm) is measured. When a plurality of pores are confirmed,
The equivalent circle diameter of the largest pore is δ μm. Then, the ratio of the pore diameter to the particle diameter (δ / γ) is determined.

Further, as a preferable shape of the particles for adding a bubble releasing detergent, a shape having a hollow portion inside the particle and opening the surface of the particle to communicate with the hollow portion inside (the surface of the particle is depressed) can be mentioned. The detergent-added particles having the depressions (recessed particles) rapidly release pores from the inside of the particles,
This has the advantage that water enters the inside of the particle quickly, and dissolution from the inside and disintegration of the particle by the entered water are accelerated.

The preferred size of the depression hole in the depression particles included in the detergent-added particle group of the present invention will be described. As shown in FIG. 1, the equivalent circle diameter of the particle is obtained by photographing the particle using a microscope around the opening of the depression and using the projected area (S1) of the particle measured from the photographed particle image. ,
It is determined by equation (2).

Particle equivalent circle diameter = 2 × (S1 / π) ^1/2 (2) Further, the circle equivalent diameter of a hole (recessed hole) is a hole measured by the same method as the above-described projected area of the particle as an opening. Is obtained by Expression (3) using the projection area (S2) of

Equivalent diameter of hole = 2 × (S2 / π) ^1/2 (3) As the microscope in the above measurement, for example, KEY
Digital microscope VH-6300 manufactured by ENCE
And an SEM such as a Hitachi S-4000 type field emission scanning electron microscope. For calculating the projection area, for example, WinRoof manufactured by Mitani can be used.

Regarding the preferred diameter of the hole present in the depressed particles included in the detergent-added particles of the present invention, [(equivalent circle diameter of the hole) / (equivalent circle diameter of the particle)] × 100 is 2% or more of the hole. is there. In addition, from the viewpoint of allowing water to easily penetrate into the depressed holes and the viewpoint that the particle shape is closer to a spherical shape is desirable in appearance, the ratio is more preferably 2 to 70%, still more preferably 4 to 60%, 6 to 50% is more preferable, 8 to 40% is further preferable, and 10 to 30% is most preferable.

As shown in FIG. 2, the depth of the hole present in the particles contained in the detergent-added particles of the present invention is determined by the tangent X to the opening surface of the depression and the tangent Y to the bottom of the hole parallel to the tangent X. The ratio of (the distance d) / (the equivalent circle diameter of the particles)] × 100 is the ratio of the distance d to the equivalent circle diameter of the particles. The depth of the hole can be determined, for example, by cutting the particle with a scalpel or the like on a plane perpendicular to the opening of the depression as shown by the broken line in FIG. 1, and photographing the cross section with an SEM or the like. Can be measured. The ratio of the depth of the holes present in the depressed particles included in the detergent-added particles of the present invention is preferably 10% or more.
In addition, from the viewpoint of further increasing the amount of water entering the inside of the particles and the viewpoint of ensuring the strength of the particles, the ratio is 10 to
90% is more preferable, 15 to 80% is still more preferable,
20-70% is particularly preferred.

The depressed particles are preferably contained in the detergent-added particles at 50% by weight or more, more preferably 60% by weight or more, more preferably 70% by weight or more, more preferably 80% by weight or more, and preferably 90% by weight or more. Most preferred.

2-1-4. High-speed solubility due to uneven distribution of the composition The high-speed solubility from the particle surface can be expressed separately from or together with the above-mentioned bubble release mechanism which significantly increases the dissolution rate of the detergent-adding particles. As a characteristic, the particles constituting the particle group obtained by the drying process used as the detergent-adding particle group or as a main component of the detergent-adding particle group have uneven distribution in which the composition near the inside and near the surface differs in the structure. Is to have. For example, in the case where the particles obtained by the drying step are composed of a water-soluble substance and a water-insoluble substance, the water-soluble substance has an uneven distribution in which the water-soluble substance is present more near the surface than inside thereof, so that the water-soluble substance is near the surface in water. The water-soluble substance dissolves faster, and exhibits a dissolution behavior in which the disintegration of the particles from the particle surface is promoted, whereby high-speed solubility can be exhibited. Here, the water-soluble substance has a solubility in water at 25 ° C. of 0.5 g / 100 g or more. Among them, water-soluble salts are those having a molecular weight of less than 1,000, and water-soluble polymers are organic polymers having a molecular weight of 1,000 or more. A water-insoluble substance has a solubility in water at 25 ° C. of 0.5 g /
It is less than 100 g. In addition, even when the particles obtained by the drying step are composed of only a water-soluble substance, high-speed solubility can be exhibited due to the uneven distribution of the composition between the inside and the vicinity of the surface. For example, in the case of a water-soluble polymer and a water-soluble salt, since the water-soluble polymer has a more uneven distribution near the surface than inside thereof, the water-soluble polymer near the surface dissolves faster in water. By exhibiting a dissolution behavior in which the strength of the particles is reduced and disintegration is promoted, high-speed solubility can be exhibited. In addition, as the most preferable mode for expressing high-speed solubility, the unevenly distributed structure of the composition, the fine space inside the particle, and further having a hollow portion, and the surface of the particle is open and communicates with the internal hollow portion. This is a detergent-added particle group having a shape.

 The uneven distribution is confirmed as follows.

As a method for confirming uneven distribution, for example, a method using a combination of Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) (abbreviated as “FT-IR / PAS”) can be used. The method is APPLIED SPECT
ROSCOPY vol. 47 1311-1316
As described in (1993), the distribution state of a substance in the depth direction from the surface of the sample can be confirmed.

A measurement method for specifying the structure of the detergent-added particles of the present invention will be exemplified below.

A cell is filled with two different types of detergent-adding particles in different states, and FT-IR / PAS measurement is performed. By comparing the results, the structure of the detergent-adding particles can be specified. In other words, one of the particles for detergent addition was subjected to FT-IR / PAS measurement while maintaining the desired structure of the particles for detergent addition, and the comparative sample was a particle group for detergent addition which was sufficiently pulverized in an agate mortar or the like to make it uniform. FT-IR / PAS measurement is performed. FT-
The measurement of IR / PAS is performed, for example, in Bio-Rad Labo.
This is performed using a "FTS-60A / 896 type infrared spectrophotometer" manufactured by Ratories and a "300 type photoacoustic detector" manufactured by MTEC as a PAS cell. The measurement conditions are a resolution of 8 cm ⁻¹ , a scan speed of 0.63 cm / s, and an integration of 128 times. These measurement conditions include information from the particle surface of the detergent-added particle group to about 10 μm. In the PAS spectrum of the detergent-added particles, for example,
The characteristic peaks of sodium carbonate, sodium sulfate, zeolite and sodium polyacrylate were each 1434.
cm ^-1 _(CO ^{3 2-} heavy stretching vibration), 1149cm
^-1 (degenerate stretching vibration of SO ₄ ^2- ), 1009 cm ^-1
Anti-symmetric stretching vibration of Si-O-Si), and 1576 cm
The area intensity of the peak is read as ⁻¹ (reverse symmetric stretching vibration of CO ₂ ⁻ ). The characteristic peak of one kind of substance determined in each of the case where the measurement is performed while maintaining the structure of the detergent-adding particles and the case where the measurement is performed in a uniform state by pulverization, for example, sodium carbonate or sodium sulfate relative to the characteristic peak of zeolite By comparing the relative area intensities of the characteristic peaks of the water-soluble salts and the characteristic peaks of the water-soluble polymer with the characteristic peaks of the zeolite, the structural characteristics of the particles for detergent addition can be specified. To specifically explain the above example, it is to prove that there is more water-soluble polymer and / or water-soluble salts near the surface than inside and more water-insoluble materials inside than near the surface. Is possible. Even in cases other than the above examples, when there are two or more types of substances that can be measured by FT-IR / PAS, it is possible to prove the uneven distribution by comparing the relative area intensities of their characteristic peaks.

As for the particles for detergent addition, the relative area intensity with respect to the characteristic peak of a reference substance (select a substance located inside from the vicinity of the surface) when measured while maintaining the uneven distribution structure of the components is uniform after grinding. When the ratio is determined with respect to the relative area intensity with respect to the characteristic peak of the above-mentioned reference substance when measured as a state, at least one kind of substance other than the above-mentioned reference substance has a higher fast solubility of 1.1 or more From the viewpoint of expression, it is preferably 1.2 or more, more preferably 1.3 or more, still more preferably 1.4 or more, and particularly preferably 1.5 or more. It can be said that it has an uneven distribution structure when it has these relative area intensities.

As other measurement methods, energy dispersive X-ray spectroscopy (EDS) and electron probe microscopic analysis (EPMA) can be used. Thus, the two-dimensional distribution of elements can be analyzed by scanning the sample surface with an electron beam.

For example, as an energy dispersive X-ray analyzer, "EMAX 377" manufactured by Horiba, which is attached to an SEM such as "S-4000 field emission scanning electron microscope" manufactured by Hitachi, Ltd.
0 "can be used. For example, when water-soluble salts, water-insoluble substances, and water-soluble polymers are contained in the detergent-addition particles, the detergent-addition particles are embedded in a resin, and the C of the cut surface of the detergent-addition particles cut out with a microtome is cut. , N
The distribution states of the elements measured for a, Al, Si, S, and the like are such that C, Na, and S are mostly outside the particle cross section and A is in the center.
It is possible to confirm a structure in which the element distribution is high in l and Si, the water-soluble salts are contained much near the surface, and the water-insoluble substance is mostly contained in the center.

2-2. Composition of Detergent-Adding Particle Group (a) The detergent-adding particle group of the present invention contains two to more than 30% by weight of a water-soluble substance, and further contains less than 10% by weight of a surfactant and / or a water-insoluble substance. It may contain up to 70% by weight. The water-soluble substance in the present invention is a substance that dissolves in an amount of 0.1 g or more in 100 g of pure water at 20 ° C., and the water-insoluble substance is pure water 100 g at 20 ° C.
It shows that the amount dissolved per g is less than 0.1 g. However,
In the present invention, the crystalline silicate is handled as a water-insoluble substance, and the surfactant is handled without being included in the water-soluble substance and the water-insoluble substance.

The composition of the detergent-added particles of the present invention is characterized by containing no surfactant or having a very low surfactant content, and the surfactant content is less than 10% by weight. By mixing the detergent-adding particles into the granular detergent composition having a higher surfactant content, the effect of discontinuing the surfactant paste layer formed by the granular detergent composition at the time of water injection in a dispenser is exhibited. , Dispenser dispensability can be enhanced. In addition, from the viewpoint of exhibiting more excellent effects, the preferable content of the surfactant is 0 to 8% by weight, more preferably 6% by weight.
Less than 4% by weight, more preferably less than 2% by weight, more preferably less than 1% by weight, and most preferably substantially free of surfactant. .

The water-soluble substance in the present invention causes the detergent-adding particles to exhibit high-speed solubility and also has the effect of discontinuing the surfactant paste layer formed by the granular detergent composition when injected with a dispenser. Therefore, it is necessary to set the blending amount to 30 to 100% by weight. Further, from the viewpoint of enhancing the above-mentioned effects by reducing the above-mentioned surfactant content and the content of a water-insoluble substance described later, it is preferably 40% by weight or more, more preferably 50% by weight or more, and more preferably 60% by weight or more. Wt% or more, more preferably 7%
It is composed of at least 0% by weight, more preferably at least 80% by weight, more preferably at least 90% by weight, and most preferably substantially only a water-soluble substance.

The water-insoluble substance in the present invention contained water due to the phenomenon that the paste of the granular detergent composition formed when the dispenser was poured with water was hardened by the water-insoluble substance, that is, the rheological properties exhibited when the water-insoluble substance was mixed with water. The content of the water-insoluble substance needs to be 70% by weight or less in order to improve the dispensability from the dispenser by reducing the phenomenon that the flowability of the granular detergent composition is reduced. Further, from the viewpoint of suppressing the hardening of the granular detergent composition by the above-mentioned water-insoluble substance and thereby increasing the dispensability from the dispenser, the content of the water-insoluble substance is preferably 60% by weight or less, more preferably 50% by weight. Or less, more preferably 40% by weight or less, more preferably 30% by weight or less, more preferably 20% by weight
Below, more preferably not more than 10% by weight, most preferably substantially free of water-insoluble substances.

2-2-1. Water-soluble substance Examples of the water-soluble substance in the present invention include a carbonate group, a hydrogen carbonate group, a sulfate group, a sulfite group, a hydrogen sulfate group, a hydrochloric acid group, a bromate group, an iodate group, a silicate group and a phosphate group. Examples thereof include water-soluble inorganic salts such as alkali metal salts, ammonium salts, and amine salts, and low molecular weight water-soluble organic acid salts such as citrate and fumarate (provided that the surfactant is Not included). Of these, a carbonate group, a sulfate group and a sulfite group are preferred. When the water-soluble inorganic salt reacts with water to generate heat of hydration and heat of dissolution, the disintegrability of the detergent-addition particles in water and the bubbles when the detergent-addition particles are bubble releasing particles expand bubbles.
It is preferable because it promotes the self-disintegration of the particles.

It is preferable that the water-soluble substance contains a plurality of types rather than a single type. When the water-soluble substance is one kind of water-soluble substance (for example, sodium carbonate, sodium sulfate, etc.) which forms a hydrated crystal at a low temperature, if the temperature of water to be injected is high, mixing of the detergent-adding particles is performed. Although the dispersibility of the particulate detergent composition is sufficiently improved by the discontinuous effect of the high-concentration surfactant paste layer due to the above, when water with a lower temperature is injected, the water-soluble substance is hydrated. The phenomenon that the water-containing granular detergent composition hardens due to precipitation as crystals occurs, and the effect of improving dispenser distributability due to mixing of the detergent-adding particles tends to decrease.
A water-soluble substance that forms a hydrated crystal in low-temperature water as a preferred content form of the water-soluble substance, from the viewpoint of exhibiting an excellent distribution-improving effect of the detergent-added particles even when low-temperature water is injected. In the case of containing a water-soluble substance or the like in which the crystal is precipitated due to a decrease in solubility with a decrease in water temperature,
It is preferable that the coexistence of two or more water-soluble substances suppresses or delays the growth of hydrated crystals or the like due to a single water-soluble substance. More specifically, it is preferable that one or more water-soluble substances are contained in a molar ratio of 9/1 or less with respect to one water-soluble substance contained in the detergent additive particle group, and more preferably. Is 8/2 or less, more preferably 7 /
3 or less, particularly preferably 6/4 or less, most preferably about 5/5.

In addition, sodium carbonate is also preferable as an alkaline agent showing a suitable pH buffer region in the washing liquid. Other alkaline agents include amorphous silicates. Also,
Salts having a high degree of dissociation, such as sodium sulfate, potassium sulfate, and sodium sulfite, increase the ionic strength of the washing liquid, and also suitably act on sebum stain cleaning properties. Further, the sulfite group reduces hypochlorite ion contained in tap water, and has an effect of preventing oxidative deterioration of detergent components such as enzymes and fragrances. Further, sodium tripolyphosphate having excellent sequestering ability and alkali ability is also preferably used. As the low molecular weight water-soluble organic salt, a base having a large pKCa ²⁺ and / or a large cation exchange capacity is preferable in view of a sequestering ability of a metal ion. In addition to citrate, methyliminodiacetate, iminodisuccinate, ethylenediaminedisuccinate, taurine diacetate, hydroxyethyliminodiacetate, β-alanine diacetate, hydroxyiminodisuccinate, methylglycine diacetate, Glutamine diacetate, asparagine diacetate, serine diacetate and the like can be mentioned.

Other examples include water-soluble polymers. The water-soluble polymer has the effect of increasing the particle strength of the detergent-adding particles when the detergent-adding particles of the present invention are obtained by a production method including a drying process, and when the drying process is a spray-drying process, the water-soluble polymer has an effect. Because the particles have a bubble release structure, an uneven distribution structure of the composition, a fine space inside the particles, and a hollow part, and the function of imparting a shape that is open to the surface of the particles and communicates with the internal hollow part. preferable. From the viewpoint of imparting appropriate strength to the detergent-addition particles and a particle structure that expresses high-speed solubility in spray drying, the detergent-addition particles preferably contain 1 to 40% by weight,
More preferably 2 to 30% by weight, more preferably 3 to 2% by weight.
0% by weight, more preferably 4 to 15% by weight, especially 5 to 1%
It is preferably contained at 0% by weight. Examples of the water-soluble polymer include a carboxylic acid-based polymer, carboxymethyl cellulose, soluble starch, and saccharides. Among them, a carboxylic acid-based polymer is preferable from the viewpoint of improving the cleaning performance of the granular detergent composition. In particular, salts of acrylic acid-maleic acid copolymers and polyacrylates (Na, K, NH
₄ ) are particularly excellent.

The molecular weight of the water-soluble polymer is from 1,000 to 100,000, more preferably from 2,000 to 80,000, and particularly preferably from 5,000 to 50,000.

In addition to the carboxylic acid-based polymers, polymers such as polyglyoxylate, cellulose derivatives such as carboxymethylcellulose, and aminocarboxylic acid-based polymers such as polyaspartate also have sequestering ability, dispersing ability, and anti-recontamination ability. .

Other examples include polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), and polypropylene glycol (PPG). PVA is preferred as a color transfer preventive, and PEG and PPG having a molecular weight of about 100 to 20,000 are preferred because they have an effect of further reducing the viscosity of a paste produced when the aggregate of the granular detergent composition of the present invention contains water. .

2-2-2. Surfactant As the surfactant in the present invention, at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant can be used. Examples of the anionic surfactant include an alkylbenzene 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, an amino acid surfactant, N-acyl amino acid type surfactants are exemplified. Especially 10 carbon atoms
To 14 linear alkylbenzene sulfonates, 1 carbon atom
Examples thereof include an alkyl or alkyl ether sulfate of 0 to 18, and a counter ion thereof is preferably sodium, potassium, monoethanolamine, diethanolamine, or the like.

Furthermore, a fatty acid salt having 12 to 18 carbon atoms can be used in combination to obtain an antifoaming effect.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene glycol represented by the trademark "Pluronic", and polyoxyethylene alkyl. Examples include amines, higher fatty acid alkanolamides, alkylglucosides, alkylglucoseamides, and alkylamine oxides. Among them, those having high hydrophilicity and / or those having low ability to form liquid crystal or not generating liquid crystal when mixed with water are preferable, and polyoxyalkylene alkyl ethers are particularly preferable. Moreover, carbon number 10-18, Preferably it is 12-.
14, the average number of moles of addition 5 to 30, preferably 7 to 30,
More preferably 9 to 30, particularly preferably 11 to 30 ethylene oxide (hereinafter EO) adduct of alcohol,
EO adducts of alcohols having 8 to 18 carbon atoms and propylene oxide (hereinafter PO) adducts are also preferred. The order in which PO is added after adding EO, PO
, Followed by EO, or EO and P
O can be added randomly, but
As a compound having a particularly preferred addition order, a general formula in which EO is added, PO is added in a block, and EO is further added in a block: RO- (EO) _X- (PO) _Y- (EO) _Z- H wherein R represents an alkyl group or an alkenyl group;
O represents an oxyethylene group, PO represents an oxypropylene group, and X, Y, and Z each represent an average addition mole number. And the most preferred relationship among the average number of moles added is X> 0, Z> 0, X + Y + Z.
= 6 to 14, X + 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.

2-2-3. Water-insoluble substance The water-insoluble inorganic substance, which is a water-insoluble substance, is preferably a fine particle having an average primary particle size of less than 0.1 to 20 μm from the viewpoint of quality, for example, crystalline or amorphous. Aluminosilicates, silicon dioxide, hydrated silicate compounds, perlite, clay compounds such as bentonite and the like can be used, and crystalline or amorphous aluminosilicates, silicon dioxide, hydrated silicate compounds are preferred. Yes, of which crystalline aluminosilicates are preferred as sequestering agents.

The (average) particle size of the primary particles of the crystalline aluminosilicate may be 0.1 to less than 20 μm, but in consideration of the cation exchange rate and the persistence in laundry clothes, the particle size of the primary particles is A smaller one is preferred. The particle size can be confirmed with a scanning electron microscope. Also, an aggregate of primary particles can be used. For example, zeolite A can be used in terms of sequestering ability and cost. When it is necessary to carry a liquid component, for example, a liquid surfactant on the detergent-added particles, it is effective to use a water-insoluble substance having an oil absorbing ability. The value of the oil absorption capacity of A-type zeolite according to the JIS K 5101 method is 40 to 50 mL / 100 g (for example, trade name: Toyo Builder; manufactured by Tosoh Corporation). In addition, P type (for example, Doucil A24 or ZSE)
O64 and the like; manufactured by Crosfield; oil absorption capacity 60 to 150
mL / 100 g) or X type (for example, trade name: Wessal)
itXD; manufactured by Degussa; oil absorption capacity 80-100
mL / 100 g). WO 98/42622
The hybrid zeolite described in No. 1 is also mentioned as a suitable crystalline aluminosilicate.

In addition, amorphous silica, amorphous aluminosilicate, etc., which have a low sequestering ability but a high oil absorbing ability, can also be used as the water-insoluble substance. For example, JP-A-62-19
No. 1417, 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.), JP-A-62-191419, page 2, lower right. Column, line 20-page 5, lower left column, line 11 (especially oil absorption is 170
mL / 100 g is preferred. ), And column 17 (4) of JP-A-9-132794.
Line 6 to column 18, line 38, JP-A-7-10526, column 3, line 3 to column 5, line 9, JP-A-6-227811
No. 2, line 15 to column 5, line 2;
No. 9622, column 2, line 18 to column 3, line 47 (oil absorption capacity 285 mL /
100g) and the like. For example, "TOKUSHIR NR" (manufactured by Tokuyama Soda Co., Ltd .: oil absorption capacity 210-2)
70mL / 100g), "FLORITE" (same: oil absorption capacity 400-600mL / 100g), "TIXOLEX2"
5 "(manufactured by Korea and France Chemical Co., Ltd .: oil absorption capacity 220-270 mL / 10
0g) and "Silopure" (manufactured by Fuji Divison Co., Ltd .: oil absorption capacity 240 to 280 mL / 100 g). Particularly, as the oil-absorbing carrier, those described in JP-A-6-179899, column 12, line 12 to column 13, line 1, and column 17, line 34 to column 19, line 17 are preferred.

Further, the water-insoluble substance in the present invention preferably contains a crystalline silicate. European Patent 0630855
No. 18, page 18 (preferably the crystalline silicate obtained in Example 23), and JP-A-5-279013, No. 3
Column line 17 to column 6 line 24 (particularly 500 to 1000
The method of baking at ℃ and crystallizing is preferable. ), JP-A-7-89712, column 2, line 45 to column 9, line 34
Row, lower right column, page 2, page 1 of JP-A-60-227895
The crystalline silicate described in line 8 to page 4, upper right column, line 3 (especially the silicates in Table 2 is preferable) is exemplified as a base having both alkali ability and sequestering ability. here,
The alkali metal silicate SiO ₂ / M ₂ O (where M represents an alkali metal) is preferably 0.5 to 3.2, more preferably 1.5 to 2.6.
Preferred compounding methods are 1 to less than 20 μm, preferably 1 to
This is a method in which after finely pulverizing to a size of less than 10 μm, it is used as a surface modifier.

2-3. Next, the powder properties of the detergent-adding particles of the present invention will be described.

2-3-1. Average Particle Size The average particle size of the detergent additive particle group of the present invention is JIS Z
After shaking for 5 minutes using an 8801 standard sieve, it is measured from the weight fraction depending on the sieve size. The average particle size is set to 150 μm or more in order to suppress dusting when handling a granular detergent composition obtained by mixing the particle groups, and 600 μm in order to ensure high-speed solubility of the detergent additive particle groups.
m or less, from the viewpoint of satisfying the above requirements and suppressing the classification of the particles for detergent addition in the granular detergent composition, preferably 170 to 500 μm, more preferably 180 to 450 μm, more preferably 190-400
μm, most preferably 200 to 350 μm. In addition, by suppressing the classification of the detergent-adding particles in the granular detergent composition, the effect of improving the dispenser distribution property of the particles is constantly exhibited, and the interface formed when the granular detergent composition is injected with water. From the viewpoint of efficiently discontinuing the activator paste layer by the particle group, the average particle diameter is preferably close to the average particle diameter of the detergent particle group (b) described later, and the preferable detergent-adding particle group. And the difference between the detergent particles (b) are preferably within 350 μm, more preferably within 300 μm, more preferably within 250 μm, more preferably within 200 μm, and more preferably within 1 μm.
It is preferably within 50 μm, more preferably within 100 μm, and most preferably within 50 μm.

2-3-2. Bulk Density The bulk density of the particles for detergent addition of the present invention is JIS K
3362. The bulk density imparts more excellent high-speed solubility, improves the dispersibility of the granular detergent composition obtained by mixing the detergent-adding particles in a dispenser, and preferably sets the bulk density of the granular detergent composition. In order to suppress the classification of the particles for adding detergent in the granular detergent composition, 300 to 1000 g / L, preferably 320 to 900 g / L, and more preferably 340 to 900 g / L.
850 g / L, more preferably 360 to 800 g / L,
More preferably 380-750 g / L, more preferably 400-700 g / L, most preferably 420-650.
g / L.

2-4. Method for Producing Detergent-Adding Particle Group The detergent-adding particle group of the present invention is produced by a step including the following steps (X) and (Y).

Step (X): a step of preparing a solution or suspension containing a water-soluble substance and, if necessary, further containing a surfactant and / or a water-insoluble substance (hereinafter referred to as a slurry or the like).

In the present invention, the term “solution” refers to a water-soluble substance or an aqueous solution of a water-soluble substance and a surfactant, and the term “suspension” refers to a substance containing an undissolved substance and / or a water-insoluble substance of a water-soluble substance. , Paste form.

Step (Y): a step of drying the slurry or the like obtained in step (X).

The detergent additive particle group of the present invention is produced by including the above-described steps, and a step of adjusting the particle size distribution described below can be added as necessary. As the particle size distribution adjusting step, for example, a crushing / crushing step for obtaining a desired particle size, a classifying step using a sieve, a crushing / crushing step of coarse particles generated at that time, a wind force or a several-stage sieve are used. A readjustment step of the particle size distribution can be added. The addition of the particle size distribution adjusting step is such that the particles obtained in the above-mentioned step (Y) emit bubbles, are unevenly distributed in the composition, have a fine space inside the particles, and further have a hollow portion, and the surface of the particles is open. In the case where the particles do not have high-speed solubility due to a particle structure such as a shape communicating with an internal hollow portion, it is particularly preferable from the viewpoint of imparting high-speed solubility to the particle group.

In addition, if necessary, a step of post-adding an amount of a surfactant and a precursor thereof limited to the composition range of the detergent-adding particles of the present invention, and adding the water-soluble substance in the form of a paste, a slurry or a solution. A step of adding and a step of post-adding a water-insoluble substance of less than 1 to 20 μm and a water-soluble substance of less than 1 to 20 μm to adhere to the particle surface may be added. However,
The total amount of the substance added in the post-addition step is determined by the particle group obtained in the drying step (Y) in order to sufficiently exhibit the effect of improving the distributability in the dispenser of the particles obtained in the drying step (Y). 1/4 by weight
Or less, more preferably 1/9 or less, more preferably 1/19 or less, more preferably 1/19 or less.
It is most preferred that no additional addition be made, of 49 or less, more preferably 1/99 or less.

Preferred embodiments of the steps (X) and (Y) will be described.

2-4-1. Step (X) The slurry and the like may be any non-curable liquid that can be sent by a pump, and the method and order of adding the components may be appropriately changed depending on the situation. The content of each component such as a water-soluble substance in the slurry or the like is as described above.

2-4-2. Step (Y) Regarding the drying method, any drying method, for example, freeze drying, drying under reduced pressure, or the like can be used, but the particle structure after drying may be a structure having pores of 0.2 mL / g or more inside the particle, In order to obtain a structure having pores capable of releasing bubbles having a diameter of 1/10 or more of the particle diameter of the particles, a structure having depressed holes, and / or a structure having uneven distribution of components, a slurry or the like is prepared Drying is preferred, and a particularly preferred drying method is a spray drying method.

3. Detergent Particle Group (b) As the detergent particle group, a detergent particle group used in an ordinary granular detergent composition can be used, and any method can be used as long as the detergent particle group has the following composition and powder properties. May be done.

The detergent particles (b) containing 10% by weight or more of the surfactant supplement the cleaning performance of the detergent-added particles (a) with the insufficient surfactant. Detergent particle group (b)
Are dry-mixed with the detergent-adding particle group (a) to form a composite detergent particle group having excellent dispersibility in a dispenser. When the surfactant contained in the detergent particles (b) is a surfactant having a liquid crystal forming ability, the detergent-adding particles (a) are dry-mixed to form a composite detergent particle. The distribution property improving effect in the dispenser is more remarkably exhibited. The above-mentioned surfactant having a liquid crystal forming ability is defined as having a water content of 0 to 99% and a temperature of 5%.
It is a surfactant in which lamella-type and hexagonal-type liquid crystals are observed in the range of -70 ° C.

3-1. Composition of Detergent Particle Group (b) The content of the surfactant in the detergent particle group (b) is adjusted so as to impart detergency to the composite detergent particles and to make the detergent particles have desired powder properties. b) 10 to 50% by weight in
However, it is preferably 15 to 49% by weight, more preferably 20 to 48% by weight, more preferably 25 to 47% by weight, particularly preferably 30 to 46% by weight.

The detergent particles contain an anionic surfactant and / or a nonionic surfactant, and may contain a cationic surfactant and an amphoteric surfactant as needed.

In addition, as for these surfactants, the same ones as exemplified in the above-mentioned detergent-added particle group are exemplified.

Further, the detergent particles may contain a water-soluble substance as a component other than the above-mentioned surfactant. The preferred content of the water-soluble substance is 20 to 90% by weight, and the water-soluble substance used for the detergent particles is the same as the water-soluble substance used for the detergent-added particles described above. Is done.

Further, if desired, a water-insoluble substance can be contained.
The preferable content of the water-insoluble substance is 0 to 70% by weight, and as the water-insoluble substance used in the detergent particle group, the same as those exemplified in the above-described detergent addition particle group are exemplified.

3-2. Powder properties of detergent particle group (b) 3-2-1. Average particle size The average particle size of the detergent particles measured using a standard sieve according to JIS Z8801 is 150 to suppress dusting when handling a granular detergent composition containing the detergent particles.
μm or more, and 600 μm to ensure solubility in the washing tub after the detergent particles have been dispensed from the dispenser.
μm or less, more preferably 170 to 500 μm,
More preferably 180 to 450 μm, more preferably 1 to 450 μm
90-400 μm, most preferably 200-350 μm
It is.

3-2-2. Bulk Density The bulk density of the detergent particles as measured according to JIS K 3362 is 500 to 1000 g / L, taking into account the improvement of the transport efficiency of the granular detergent composition containing the detergent particles and the simplicity of the user. Then, preferably 550 to 100
0 g / L, more preferably 600 to 1000 g / L, further preferably 650 to 1000 g / L, and among them, preferably 700 to 1000 g / L.

3-3. Method for Producing Detergent Particle Group (b) As a method for producing the detergent particle group, a method of obtaining spray-dried particles from a surfactant or a builder and increasing the bulk density thereof can be used. As this method, for example, a method of increasing the bulk density by stirring and granulating a group of spray-dried particles by a vertical or horizontal mixer is exemplified. Examples thereof include a method of stirring and granulating spray-dried particles described in JP-A-61-69897, a method of pulverizing and granulating dried particles described in JP-A-62-169900, JP-A-3-33199 discloses a method of kneading and mixing detergent raw materials described in JP-A-62-236897 and pulverizing a solid detergent obtained and a method not using a spray-drying tower from the viewpoint of energy saving. In the high-speed mixer described in Japanese Patent Application Laid-Open No. H10-284, a method in which an acid precursor of an anionic surfactant is dry-neutralized with a granular solid alkali agent and then granulated by adding a liquid binder can be used.

Further, described in JP-A-10-176200, a mixture of an acid precursor of a nonionic surfactant and an anionic surfactant capable of lamellar alignment can be neutralized with a mixture of an alkali agent and a stirring granulator at or above a temperature at which neutralization can be performed. A method of granulating while rolling can be used.

Further, the method may include a step of separating particles (coarse particles) having an unnecessarily large particle size contained in the detergent particle group obtained by the above-mentioned operation using a sieve or the like. It can also be used as a detergent particle group after being sized. Examples of the coarse particle crusher include an impact crusher such as a hammer crusher, an impact crusher such as an atomizer and a pin mill, and a shear crusher such as a flash mill. These may be a single-stage operation or a multi-stage operation of the same or different types of pulverizers. In this case, it is preferable to add fine powder as an in-machine adhesion inhibitor or a pulverized surface modifying agent. The fine powder is preferably an inorganic powder such as aluminosilicate, silicon dioxide, bentonite, talc, clay amorphous silica derivative, and particularly preferably a crystalline or amorphous aluminosilicate. In addition, fine powder of a water-soluble substance such as sodium carbonate, sodium sulfate, and sodium tripolyphosphate is also used.

Further, a surface modification step may be provided for the purpose of fixing and smoothing the surface modifier in order to improve the fluidity of the crushed particles. For example, the composition is fed batchwise or continuously into a rotary cylinder machine or a stirrer to perform rolling or stirring.

4. Composite detergent particles The composite detergent particles of the present invention are obtained by dry-mixing the above-mentioned detergent-adding particles (a) and the detergent particles (b). The mixture has excellent dispersibility from the dispenser by mixing, and has excellent washing performance by dry-mixing the detergent particles (b). That is, a continuous, high-concentration surfactant paste layer formed by the detergent particles (b) when injected with a dispenser is used to form a detergent-adding particles having a specific composition, specific powder properties, and high-speed solubility. (A) allows rapid discontinuity. Further, due to the action of the detergent addition particles (a) dissolving at high speed in the water injection together with the discontinuity, the composite detergent particles can be quickly and efficiently distributed in the dispenser. From the viewpoint of expressing better dispensability from the dispenser and better cleaning performance from the composite detergent particles,
Regarding a preferable mixing ratio of the detergent additive particle group (a) and the detergent particle group (b), the weight ratio of (a) / (b) is 1/9.
9-70 / 30 is preferable, and 2 / 98- is more preferable.
60/40, more preferably 3/97 to 55/45, more preferably 5/95 to 50/50, more preferably 1
0 / 90-45 / 55, more preferably 15 / 85-4
0/60 and 20/80 to 35/65 are most preferred.

Regarding the degree of dry mixing of the detergent-adding particles (a) and the detergent particles (b), even though the mixing is low, the effect of improving the dispensing property in the dispenser is exhibited, The detergent-added particle group (a) allows the surfactant paste layer to be constantly expressed and formed when water is injected, to be more efficiently discontinued. Therefore, from this viewpoint, it is preferable that the degree of dry mixing is higher. For example, in a composite detergent particle group and / or a granular detergent composition containing the composite detergent particle group, 2
If the difference in the surfactant content of the sample of about 20 g collected at the location indicates the degree of dry mixing, the difference in the surfactant content is preferably within 7%, and preferably within 5%. Is more preferably within 3%, most preferably within 1%.

In addition, as a method of dry mixing, a batch type or continuous type blending method such as a V-type mixer can be used.

5. Granular detergent composition The granular detergent composition of the present invention contains the above composite detergent particles in an amount of 50 to 100% by weight, and has excellent dispensability from a dispenser. In addition, from the viewpoint of further reflecting the excellent dispenser dispensability of the composite detergent particles in the detergent composition, the content of the composite detergent particles is preferably 60% by weight or more, more preferably 70% by weight or more. Preferably 80% by weight or more, more preferably 85% by weight or more, more preferably 90% by weight
More preferably, it is at least 95% by weight.

Further, the preferable content of the detergent-added particles (a) in the granular detergent composition is from 1 to 70% by weight from the viewpoint of achieving both the dispersibility from the dispenser and the cleaning performance.
Is preferable, more preferably 2 to 60% by weight, more preferably 3 to 55% by weight, more preferably 5 to 50% by weight, more preferably 10 to 45% by weight, more preferably 15 to 40% by weight, and 20 to 20% by weight. 35% by weight is most preferred.

In addition, the granular detergent composition of the present invention, in which the dispersibility from a dispenser is improved by containing the detergent-adding particles (a), includes bleaching agents such as percarbonate and effervescent percarbonate, and granules. Crystalline silicate, JP-A-6-31670
No. 0, bleach activators such as tetraacetylethylenediamine, enzymes such as protease, cellulase, amylase and lipase; fluorescent dyes of biphenyl type and stilbene type; antifoaming agents such as silicone / silica type; antioxidants A component group such as a bluing agent or a flavor and / or a particle group containing the component can be appropriately blended regardless of the dissolution rate of the particle group.

Example [Preparation of Detergent-Adding Particle Group (a)] The detergent-adding particle group 1 of the present invention was prepared by the method described below.

415 kg of water was added to a 1 m ³ mixing tank having stirring blades, the water temperature was adjusted to 50 ° C., and sodium sulfate 135 k
g, 115 kg of sodium carbonate and 100 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. One more
After stirring for 5 minutes while controlling the temperature at 50 ° C., 185 kg of zeolite was added, and the mixture was further stirred for 30 minutes while controlling the temperature at 50 ° C. to obtain a homogeneous slurry.

This slurry is supplied to a spray drying tower by a pump, and a spray pressure of 25 kg / c is supplied from a pressure spray nozzle installed near the top of the tower.
It was sprayed at a m ^2. The high-temperature gas supplied to the spray drying tower is supplied at a temperature of 220 ° C. from the lower part of the tower, and is supplied from the top of the tower at a temperature of 220 ° C.
Discharged at 03 ° C. Subsequently, the particles for crude detergent addition obtained from below the tower were dried in a fluidized bed with hot air at 100 ° C. until the water content became 5% by weight. The obtained coarse particles of the particle group were removed with a 1410 μm sieve to obtain detergent addition particle group 1. Table 1 shows the composition and physical properties of the obtained Particle Group 1.

In addition, the pore volume of 0.01 to 4 μm measured with the mercury porosimeter for the detergent addition particle group 1 is 0.40 m
L / g. Also, as a result of observing the dissolution behavior with a digital microscope, it was found that 92% of the particles had a particle diameter of 1 /
It was confirmed that bubbles having a diameter of 10 or more were released.
(The average value of the diameter of bubbles / particle diameter released from the 92% of the particles was 5.8 / 10.) Further, as a result of analyzing the sinking hole for the detergent addition particle group 1, it was found that
2% or more of the equivalent circle diameter of the particle and 1
82% of the depressed particles contained one or more holes having a depth of 0% or more. Further, the average of [equivalent circle diameter of hole / equivalent circle diameter of particles] × 100 of the depressed hole obtained for 82% of the depressed particles was 22%. The average of the depth of the depression is 50% of the equivalent circle diameter of the particle.
Met. Further, FT-IR / P
Analysis by AS and EDS confirmed that the ratio of zeolite was high inside the particles and that the ratio of water-soluble polymer and water-soluble inorganic salts was high near the particle surface, and the particles had a highly uneven distribution structure. Was done.

The detergent additive particle group 2 of the present invention was prepared by the method described below.

Water 390kg added to a mixing tank of 1 m ³ having a stirring blade, to adjust the water temperature to 50 ° C., it was added a 50 wt% alkyl benzene sulfonate aqueous solution of sodium 50 kg.
After stirring for 15 minutes, 125 kg of sodium sulfate, 110 kg of sodium carbonate and 100 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. After stirring for 15 minutes while controlling the temperature at 50 ° C., 175 kg of zeolite was added, and stirring was further performed for 30 minutes while controlling the temperature at 50 ° C. to obtain a homogeneous slurry.

This slurry is supplied to a spray drying tower by a pump, and a spray pressure of 25 kg / c is supplied from a pressure spray nozzle installed near the top of the tower.
It was sprayed at a m ^2. The high-temperature gas supplied to the spray drying tower is supplied at a temperature of 218 ° C. from the lower part of the tower, and is supplied from the top of the tower at a temperature of 218 ° C.
Discharged at 01 ° C. Subsequently, the particles for crude detergent addition obtained from below the tower were dried in a fluidized bed with hot air at 100 ° C. until the water content became 5% by weight. 14 g of the coarse particles
The particles were removed with a 10 μm sieve to obtain detergent-added particles 2. Table 1 shows the composition and physical properties of the obtained Particle Group 2.

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.44 mL / g. Further, as a result of observing the dissolution behavior with a digital microscope, 88
% Of the particles released bubbles having a diameter of 1/10 or more of the particle diameter. (The average value of the diameter of bubbles / particle diameter released from the 88% of the particles was 6.0 / 10.) Further, as a result of analyzing the depressed holes for the detergent addition particle group 2, it was found that the particles 2% of the circle equivalent diameter of
The hole having the above circle equivalent diameter and the depth of 10% or more is 1
It contained 11% of depressed particles present in more than one place. Also,
The average of [equivalent circle diameter of hole / equivalent circle diameter of particle] × 100 of the depressed hole determined for the 11% of depressed particles is 14
%Met. The average depth of the depressions was 61% of the equivalent circle diameter of the particles. Further, when the particle group 2 for detergent addition was analyzed by FT-IR / PAS and EDS, it was confirmed that the particle structure had uneven distribution like the particle group 1 for detergent addition.

The detergent additive particle group 3 of the present invention was prepared by the method described below.

416 kg of water is added to a 1 m ³ mixing tank having stirring blades, the water temperature is adjusted to 50 ° C., and sodium sulfate 248 k
g, 92 kg of sodium carbonate and 100 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. 30 more
The mixture was stirred for 50 minutes at a temperature of 50 ° C. to obtain a homogeneous slurry.

This slurry is supplied to a spray drying tower by a pump, and a spray pressure of 25 kg / c is supplied from a pressure spray nozzle installed near the top of the tower.
It was sprayed at a m ^2. The high-temperature gas supplied to the spray drying tower is supplied at a temperature of 228 ° C. from the lower part of the tower, and is supplied from the top of the tower at a temperature of 228 ° C.
Discharged at 00 ° C. Subsequently, the particles for crude detergent addition obtained from below the tower were dried in a fluidized bed with hot air at 100 ° C. until the water content became 5% by weight. The obtained coarse particles of the particle group were removed with a 1410 μm sieve to obtain detergent addition particle group 3. Table 1 shows the composition and physical properties of the obtained Particle Group 3.

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.50 mL / g. In addition, as a result of observing the dissolution behavior with a digital microscope, 90
% Of the particles released bubbles having a diameter of 1/10 or more of the particle diameter. (The average value of the bubble diameter / particle diameter released from the 90% of the particles was 6.3 / 10.) In addition, as a result of analyzing the depressed holes for the detergent addition particle group 3, the particles 2% of the circle equivalent diameter of
The hole having the above circle equivalent diameter and the depth of 10% or more is 1
It contained 27% of depressed particles present at more than one location. Also,
An average of [equivalent circle diameter of hole / equivalent circle diameter of particle] × 100 of the depression hole obtained for the 27% of the depression particles is 18
%Met. The average depth of the depressions was 68% of the equivalent circle diameter of the particles. Further, when the particle group 3 for detergent addition was analyzed by FT-IR / PAS and EDS, the ratio of the polymer inside the particle was low, and the ratio of the polymer was high near the particle surface. Was confirmed.

The detergent additive particle group 4 of the present invention was prepared by the method described below.

4% by weight of the polyoxyethylene alkyl ether shown in Table 1 was heated to 60 ° C. Next, 196% by weight of particles for detergent addition was put into a Loedige mixer (manufactured by Matsuzaka Giken Co., Ltd., capacity: 20 L, with jacket), and stirring of the main shaft (150 rpm) and the chopper (4000 rpm) was started. The jacket was heated to 60 ° C. Then, the above polyoxyethylene alkyl ether was added to 30
Then, the mixture was stirred for 4 seconds and then stirred for 4 minutes to obtain detergent addition particles 4. Table 1 shows the composition and physical properties of the obtained Particle Group 4.

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.38 mL / g. Also, as a result of observing the dissolution behavior with a digital microscope, 89
% Of the particles released bubbles having a diameter of 1/10 or more of the particle diameter. (The average value of the bubble diameter / particle diameter released from the 89% of the particles was 5.8 / 10.) Further, as a result of analyzing the depressions of the detergent-adding particle group 4, it was found that the particles 2% of the circle equivalent diameter of
The hole having the above circle equivalent diameter and the depth of 10% or more is 1
It contained 80% of depressed particles existing at more than one place. Also,
The average of [equivalent circle diameter of the hole / equivalent circle diameter of the particle] × 100 of the depression hole obtained for the 80% of the depression particles is 21%.
%Met. The average depth of the depressions was 49% of the equivalent circle diameter of the particles. Further, when the particle group 4 for detergent addition was analyzed by FT-IR / PAS and EDS, it was confirmed that the particle structure had uneven distribution like the particle group 1 for detergent addition.

The detergent additive particle group 5 of the present invention was prepared by the method described below.

A patch kneader equipped with a jacket was heated to 50 ° C., 24.9 kg of water was added, and sodium sulfate 8.1 k was added.
g, 6.9 kg of sodium carbonate and 6 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. After stirring for another 15 minutes while controlling the temperature at 50 ° C., 11.1 kg of zeolite was added. After stirring for 30 minutes while controlling the temperature at 50 ° C., the jacket temperature was reduced to 80 ° C.
C. and the pressure in the mixing tank of the batch kneader was reduced to dryness while mixing until the water content became 5% by weight. The coarse particles of the obtained particles were removed with a 500 μm sieve to obtain particles 5 for detergent addition. Table 1 shows the composition and physical properties of Particle Group 5.
Shown in

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.21 mL / g. When the dissolution behavior was observed with a digital microscope, 9%
It was confirmed that bubbles having a diameter of 1/10 or more of the particle diameter were released from the particles. (The average value of the diameter of bubbles / particle diameter released from the above 9% of the particles was 1.7 / 10.) Further, as a result of the analysis of the depressed holes for the detergent addition particle group 5, the particles 2% of the circle equivalent diameter of
The hole having the above circle equivalent diameter and the depth of 10% or more is 1
No depressed particles were present at more than one location. Also,
When the detergent addition particle group 5 was analyzed by FT-IR / PAS and EDS, no clear uneven distribution was observed.

Comparative Particle Group 1 as a comparative example of the present invention was prepared by the method described below.

Stirring blade Water 347.5kg mixing vessel of 1 m ³ having added thereto to adjust the water temperature to 50 ° C., it was added 50 wt% aqueous solution of sodium 150kg alkylbenzenesulfonate. After stirring for 15 minutes, sodium sulfate 115k
g, 100 kg of sodium carbonate and 87.5 kg of a 40% by weight aqueous solution of sodium polyacrylate. After stirring for 15 minutes while adjusting the temperature to 50 ° C,
150 kg of zeolite was added, and the mixture was further stirred for 30 minutes while controlling the temperature at 50 ° C. to obtain a homogeneous slurry.

This slurry is supplied to a spray drying tower by a pump, and a spray pressure of 25 kg / c is supplied from a pressure spray nozzle installed near the top of the tower.
It was sprayed at a m ^2. The high-temperature gas supplied to the spray drying tower is supplied at a temperature of 222 ° C. from the lower part of the tower, and is supplied from the top of the tower at a temperature of 222 ° C.
Discharged at 05 ° C. Subsequently, the particles obtained from the bottom of the column are cooled to 100 ° C. in a fluidized bed until the water content becomes 5% by weight.
And dried with hot air. 1410 μm of coarse particles of the obtained particle group
m, and Comparative Particle Group 1 was obtained. Comparative particle group 1
Is shown in Table 1.

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.43 mL / g. In addition, as a result of observing the dissolution behavior with a digital microscope, 85
% Of the particles released bubbles having a diameter of 1/10 or more of the particle diameter. (The average value of the diameter of bubbles / particle diameter released from the above 85% of the particles was 6.2 / 10.) Further, as a result of analyzing the depressions of the comparative particle group 1, the circle of the particles was found. It contained 8% of depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the equivalent diameter. In addition, the average of [equivalent circle diameter of hole / equivalent circle diameter of the particles] × 100 of the depression hole obtained for the 8% depression particles was 10%. The average depth of the depressions was 65% of the equivalent circle diameter of the particles. In addition, Comparative Particle Group 1 was FT-
Analysis by IR / PAS and EDS shows that the zeolite has a high ratio inside the particles, and the ratio of the water-soluble polymer or water-soluble inorganic salt is high near the particle surface. Was confirmed.

Comparative particle group 2 as a comparative example of the present invention was prepared by the method described below.

A batch kneader equipped with a jacket was heated to 50 ° C., 20.85 kg of water was added, and 9 kg of a 50% by weight aqueous solution of sodium alkylbenzenesulfonate was added.
After stirring for 15 minutes, 6.9 kg of sodium sulfate, 6 kg of sodium carbonate, and 5.25 kg of a 40% by weight aqueous solution of sodium polyacrylate were added. 5 additional 15 minutes
After stirring while adjusting the temperature to 0 ° C, 9 kg of zeolite was added, and the mixture was further stirred for 30 minutes while adjusting the temperature to 50 ° C. Then, the temperature of the jacket was raised to 80 ° C and the mixture in the mixing tank of the batch kneader was added. Was dried under reduced pressure until the water content became 5% by weight. The coarse particles of the obtained particle group were removed with a 1000 μm sieve to obtain Comparative Particle Group 2. Table 1 shows the composition and physical properties of Comparative Particle Group 2.

In addition, 0.01-4 micrometers measured with a mercury porosimeter
Had a pore volume of 0.19 mL / g. When the dissolution behavior was observed with a digital microscope, 8%
It was confirmed that bubbles having a diameter of 1/10 or more of the particle diameter were released from the particles. (The average value of the ratio of the bubble diameter / particle diameter released from the 8% particles was 1.6 / 10.) Further, as a result of analyzing the collapsed hole for the comparative particle group 2, the particle circle was obtained. No depressed particles having one or more holes having a circle equivalent diameter of 2% or more and a depth of 10% or more with respect to the equivalent diameter were found. Moreover, when the comparative particle group 2 was analyzed by FT-IR / PAS and EDS, no clear uneven distribution was observed.

As a comparative particle group 3 as a comparative example of the present invention, a sodium carbonate particle group (Dense Ash: manufactured by Central Glass Co., Ltd.) and a comparative particle group 4 as a sodium percarbonate granulated particle group (KCPZ: Nippon Peroxide ( Co., Ltd.) and Comparative Particle Group 5 as Enzyme Granulated Particle Group (Savinase 18T
Type W: manufactured by Novo Nordisk). Table 1 shows the composition and physical properties of the comparative particle groups 3 to 5.

[Preparation of Detergent Particle Group (b)] Detergent particle group 1 was prepared by the method described below.

Of the raw materials of the detergent particle group 1 shown in Table 2, 50% by weight of the polyoxyethylene alkyl ether content, the total amount of the crystalline silicate and 50% by weight of the zeolite content
A slurry having a moisture content of 48% containing components other than the above was spray-dried to obtain a spray-dried dough having a bulk density of 310 g / L. next,
This spray-dried dough was put into a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd., equipped with a stirring tumbling granulator, equipped with a jacket), and 20% by weight of the zeolite blending amount and the total amount of the crystalline silicate were added. The remaining 50 of the blended amount heated to
A granulation operation was carried out by spray addition of polyoxyethylene alkyl ether in an amount of 0.5% by weight, and a surface treatment was performed by adding 20% by weight of the zeolite blending amount 60 seconds before the end of the granulation to obtain a granulated product. Further, the granulated product is
And 10% by weight of the remaining zeolite is added to coarse particles of 1410 μm or more, and the mixture is subjected to 1410 μm with a Fitzmill (pulverizer, manufactured by Hosokawa Micron Corporation).
m, and then mixed with the granulated material that passed through the sieve to obtain detergent particle group 1.

Detergent Particle Group 2 was prepared by the method described below.

Of the raw materials of the detergent particle group 2 shown in Table 2, 50% by weight of the polyoxyethylene alkyl ether compounding amount, the total amount of the crystalline silicate compounding amount, and 50% by weight of the zeolite compounding amount
A slurry having a moisture content of 48% containing components other than the above was spray-dried to obtain a spray-dried dough having a bulk density of 302 g / L. next,
This spray-dried dough was put into a high-speed mixer (manufactured by Fukae Kogyo Co., Ltd., equipped with a stirring tumbling granulator, equipped with a jacket), and 20% by weight of the zeolite blending amount and the total amount of the crystalline silicate were added. The remaining 50 of the blended amount heated to
A granulation operation was carried out by spray addition of polyoxyethylene alkyl ether in an amount of 0.5% by weight, and a surface treatment was performed by adding 20% by weight of the zeolite blending amount 60 seconds before the end of the granulation to obtain a granulated product. Furthermore, the same treatment as in the detergent particle group 1 was performed on the granulated product to obtain the detergent particle group 2.

Detergent Particle Group 3 was prepared by the method described below.

Spray-dry a 50% moisture slurry containing the total amount of sodium polyacrylate, PEG, sodium sulfate, sodium sulfite, soap, fluorescent dye, 50% by weight of zeolite and 50% by weight of sodium carbonate. And a spray-dried dough having a bulk density of 460 g / L. The remaining 50% by weight of the total amount of the resulting spray-dried dough, amorphous aluminosilicate and crystalline silicate and sodium carbonate was added to a Loedige mixer, and stirring was started. Warm water of 40 ° C. was flowed through the jacket. The total amount of the polyoxyethylene alkyl ether heated to 70 ° C. was added by spraying to perform granulation. Further, 60% before the end of granulation, 30% by weight of the zeolite compounding amount was added to perform a surface treatment to obtain a granulated product. 1410
Pulverizer (Pulverizer manufactured by Hosokawa Micron Corporation) by adding 20% by weight of zeolite to coarse particles having a particle diameter of 1410 μm or more.
And then mixed with the material passed through a sieve to obtain detergent particle group 3.

Subsequently, V-type mixing was carried out with the detergent-adding particle groups 1 to 5 and the comparative particle groups 1 to 5 of the present invention and the detergent particle groups 1 to 3 in a weight ratio of 5/95, 10/90, and 30/70. The composite detergent particles of the present invention and the composite detergent particles as a comparative example were obtained by dry-mixing with a mixer for 5 minutes.

Further, 0.4 parts by weight of 1 part by weight of an enzyme granulated product (cellulase (manufactured by Kao Corporation, "KAC500"), 99 parts by weight of the detergent particles 1 to 3 and 99 parts by weight of the composite detergent particles), (Novo Nordisk, "Savinase 12.0T-W") 0.3 part by weight, and lipase (Novo Nordisk, "Lipolase 100T" containing 0.3 part by weight) were added and V was added for 5 minutes. The granular detergent composition of the present invention and a granular detergent composition as a comparative example were obtained by dry mixing with a mold mixer.

The dispersibility of the granular detergent composition obtained above in a dispenser of a drum type washing machine was evaluated by the following method.

[Evaluation of dispensability in dispenser]

Drum type washing machine "ES-E60" manufactured by Sharp Corporation
20 g of the granular detergent composition was placed in a dry detergent charging case, and the drum was emptied, and tap water at 20 ° C. was injected. After the completion of the water injection, the granular detergent composition remaining in the detergent charging case was recovered, dried at 105 ° C. for 4 hours, weighed, and the residual ratio was calculated by the following equation (4).

Residual rate (%) = 100 × (dry weight of residue (g)) / 20 (g) (4) Evaluation results of granular detergent composition mixed with particles for detergent addition of the present invention and comparative examples thereof Table 3 shows the (residual rate).
It describes in.

From the results in Table 3, it can be seen that all of the granular detergent compositions in which the detergent-added particles of the present invention are mixed have remarkably excellent distribution properties as compared with Comparative Examples.

Further, the composite detergent particles obtained by dry-mixing the detergent-added particles 1 and the detergent particles 1 in a weight ratio of 5/95, 10/90, 30/70 with a V-type mixer for 5 minutes are transported. As a result of the classification test, no classification of the detergent-added particles was observed.

INDUSTRIAL APPLICABILITY The detergent-adding particles of the present invention have an effect of enhancing the distribution of a granular detergent composition obtained by mixing the detergent particles with running water, and the granular detergent composition is used in a drum-type washing machine or the like. If you use the dispenser that came with the washing machine,
The trouble that the granular detergent composition is well distributed in the washing tub and remains as an aggregate in the dispenser is improved.

In the present invention described above, there are clearly a large number of devices in the range of identity. Such variations are not considered to be a departure from the spirit and scope of the invention, and all such modifications that are obvious to those skilled in the art are included within the scope of the following claims.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of detergent-adding particles as viewed from the surface centered on a depression hole. S1 indicates the projected area of the particle measured around the opening of the depression. S2 indicates the projected area of the hole measured as the opening.

FIG. 2 is a schematic side view of a cross section obtained by cutting the depressed particles perpendicular to a plane centered on the depressed hole as indicated by a broken line in FIG. X indicates a tangent to the opening surface of the depression hole. Y indicates a tangent to the bottom of the hole parallel to the tangent X. d indicates the distance between the tangent X and the tangent Y.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Hiroyuki Yamashita 1334 Minato, Wakayama-shi, Wakayama Kao Co., Ltd. (56) References JP-A-63-69894 (JP, A) (58) Fields investigated (Int .Cl. ⁷ , DB name) C11D 17/06 C11D 3/04 C11D 3/37 C11D 11/02

Claims (15)

(57) [Claims] 1. A detergent-adding particle group containing 30 to 100% by weight of two or more water-soluble substances and further containing less than 10% by weight of a surfactant and / or 70% by weight or less of a water-insoluble substance. Having an average particle size of 150 to 600 μm.
m, the bulk density is 300 to 1000 g / L, and the particle group is put into water at 5 ° C. and stirred for 60 seconds under the following stirring conditions, and the mixture is stirred with a standard sieve specified by JIS Z 8801 (opening 74 μm). ), The dissolving rate of the particle group calculated by the formula (1) is 90% or more, the detergent-adding particle group (a), the average particle diameter is 150 to 600 μm, and the bulk density is 500
A composite detergent particle group obtained by dry-mixing detergent particle group (b) having a surfactant content of 10 to 50 g / L and a surfactant content of 10 to 50% by weight. Stirring conditions: 1 L of hard water (71.2 mg CaCO ₃ / L,
1 g of the particle group was added to a molar ratio of Ca / Mg of 7/3),
In a 1L beaker (inside diameter 105mm), stirrer (length 35)
mm, diameter 8 mm), rotation speed 800 rpm, dissolution rate (%) = {1− (T / S)} × 100 (1) S: input weight (g) of detergent-added particles T: the above stirring conditions When the aqueous solution obtained in the above is subjected to the sieve, the dry weight (g) of the residue of the detergent-added particles remaining on the sieve 2. The detergent-added particle group (a) has a pore volume of 0.01 to 4 μm as measured by a mercury intrusion method.
The composite detergent particle group according to claim 1, which has a content of 2 mL / g or more and 1.2 mL / g or less. 3. The detergent-added particle group (a) contains particles capable of releasing bubbles having a particle diameter of 1/10 or more from the inside of the particles during the process of dissolving in water.
Or the composite detergent particles according to 2. 4. The detergent-added particle group (a) contains particles having a hollow portion inside the particle and having a shape in which the surface of the particle is open and communicates with the internal hollow portion. The composite detergent particles according to any one of claims 1 to 3. 5. The composite detergent according to any one of claims 1 to 4, wherein the detergent-adding particle group (a) contains unevenly distributed particles having different compositions in the structure between the inside and the vicinity of the surface. Particle group. 6. The detergent-added particles (a) are obtained by a step of spray-drying an aqueous solution or suspension containing a water-soluble substance and further containing a surfactant and / or a water-insoluble substance. The composite detergent particles according to any one of claims 1 to 5, which are to be used. 7. The composite detergent particles according to claim 1, wherein the detergent-added particles (a) contain a water-soluble polymer as a water-soluble substance. 8. A granular detergent composition comprising the composite detergent particles according to claim 1 in an amount of 50 to 100% by weight. 9. Particles for detergent addition which contain 30 to 100% by weight of two or more water-soluble substances and may further contain less than 10% by weight of a surfactant and / or 70% by weight or less of a water-insoluble substance. Having an average particle size of 150 to 600 μm.
m, the bulk density is 300 to 1000 g / L, and the particles are put in water at 5 ° C. and stirred for 60 seconds under the following stirring conditions, and the mixture is stirred using a standard sieve specified by JIS Z 8801 (opening 74 μm). ), A detergent-added particle group (a) in which the dissolution rate of the particle group calculated by the formula (1) is 90% or more. Stirring conditions: 1 L of hard water (71.2 mg CaCO ₃ / L,
1 g of the particle group was added to a Ca / Mg molar ratio of 7/3),
In a 1L beaker (inside diameter 105mm), stirrer (length 35)
mm, diameter 8 mm), rotation speed 800 rpm, dissolution rate (%) = {1− (T / S)} × 100 (1) S: input weight (g) of detergent-added particles T: the above stirring conditions When the aqueous solution obtained in the above is subjected to the sieve, the dry weight (g) of the residue of the detergent-added particles remaining on the sieve 10. The detergent-added particle group (a) has a pore volume of 0.01 to 4 μm, measured by a mercury intrusion method, of 0.2 mL / g or more and 1.2 mL / g or less. 9. Particles for detergent addition according to 9. 11. The detergent-adding particle group (a) contains particles capable of releasing bubbles having a particle diameter of 1/10 or more from the inside of the particles during the process of dissolving in water.
The particles for detergent addition according to the above. 12. The detergent-added particle group (a) contains particles having a hollow portion inside the particle and having a shape in which the surface of the particle is open and communicates with the internal hollow portion. 9 ~
12. The particle group for detergent addition according to any one of 11). 13. The detergent-adding particle group according to claim 9, wherein the detergent-adding particle group (a) contains unevenly distributed particles whose composition in the structure differs between the inside and the vicinity of the surface. . 14. The detergent-added particle group (a) is obtained by a step of spray-drying an aqueous solution or suspension containing a water-soluble substance and further containing a surfactant and / or a water-insoluble substance. The detergent additive particles according to any one of claims 9 to 13. 15. The detergent-added particle group (a) contains a water-soluble polymer as a water-soluble substance.
The particles for detergent addition according to any one of the above.