JP2009249511A - Detergent particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide detergent particles excellent in solubility, anticaking performance and bleedout blocking of a surface active agent, etc., and to provide a detergent composition containing the detergent particles, and a method for manufacturing the detergent particles. <P>SOLUTION: [1] The detergent particles are obtained by surface modifying base detergent particles (A) of a median particle diameter of 150-500 μm with a surface modifier (B). The surface modifier (B) has following general formula (I): [Mg<SB>a</SB>Al<SB>b</SB>(Si<SB>2</SB>O<SB>5</SB>)<SB>4</SB>(OH)<SB>4</SB>]<SP>X-</SP>-X/n[Me]<SP>n+</SP>(I) (wherein 0<a≤6, 0≤b≤4, 0.2≤x≤1.2, Me is Na, K, Li, Ca, Mg, NH<SB>4</SB>, etc., n is the valence of Me, and the molar ratio of [(Na+K+Li)/(Ca+Mg+NH<SB>4</SB>)] in [Me]<SP>n+</SP>is ≥1.0), has a median particle diameter of 1-40 μm, and includes a layered clay mineral (a) the Na content of which is 1.0-10.0 mass%. [2] The detergent composition containing the detergent particles and [3] the method for manufacturing the detergent particles are also disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to detergent particles, and in particular, to detergent particles, a detergent composition containing the same, and a method for producing detergent particles.

It is known to add a softening agent to the detergent to prevent the textile product after washing from losing its softness due to dropping off of the fiber treatment agent or adhesion of salts, etc. . For example, Patent Document 1 discloses a detergent composition containing a smectite-type clay softening agent. Patent Document 2 discloses a granular detergent composition in which a swellable clay composed of sodium montmorillonite or the like is added to a granular substance containing a detergent active substance and a water-soluble crystalline inorganic salt, and is processed with a high-speed mixer / granulator. A method for manufacturing a product is disclosed.
In Patent Documents 1 and 2, the swellable clay is not used for surface modification, but is contained in the detergent composition particles.

On the other hand, nonionic surfactants have been added as part of the enhancement of detergent cleaning power. Nonionic surfactants are particularly effective against oil stains. However, when nonionic surfactants are added to detergents containing clay minerals as softening agents, the solubility of clay minerals themselves decreases and remains in clothing. There is a problem of causing it.
Moreover, powder detergent has the subject of caking which detergent particle | grains couple | bond together when it preserve | saves for a long period of time, and it will be in the solidified state. One cause of caking is liquid cross-linking between detergent particles due to spotting of a nonionic surfactant that is liquid at room temperature. This caking not only deteriorates the appearance, but also causes a problem that the usability of the detergent is remarkably impaired such that accurate weighing cannot be performed. Various studies have been made to solve such problems.

For example, Patent Document 3 discloses a method for producing a detergent particle group in which a surfactant is supported on a base granule group, and then a fine powder and an anionic surfactant acid precursor are mixed to coat the surface, Patent Document 4 Is a detergent particle having a surface layer formed on the surface of the detergent particle and then surface-coated with a surface modifier. In Patent Document 5, the surface of the base detergent particle is neutralized with an acid precursor of an anionic surfactant. Detergent particles obtained by performing the same operation as in Patent Document 4 are disclosed.
However, the detergent particles of Patent Documents 3 to 5 are not fully satisfactory in terms of suppressing the occurrence of stains such as surfactants, and the effect of improving the caking resistance is insufficient. There is also a problem that the solubility of the fine powder in the detergent is remarkably lowered and the softening effect is not exhibited.

JP-A 49-85102 JP-A-3-210398 JP 2001-3095 A JP 2004-143394 A JP 2006-291139 A

  It is an object of the present invention to provide a detergent particle excellent in solubility, caking resistance, and stain-suppressing suppression of a surfactant, a detergent composition containing the detergent particle, and a method for producing the detergent particle. To do.

That is, the present invention provides the following [1] to [3].
[1] For 100 parts by mass of the base detergent particles (A) having a median particle diameter of 150 to 500 μm, the median particle diameter is 1 to 40 μm and the sodium content is 1. Detergent particles obtained by surface-modifying 10 to 50 parts by mass of a surface modifier (B) containing 10% by mass or more of a layered clay mineral (a) of 0 to 10.0% by mass.
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · X / n [Me] n + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 ≦ b ≦ 4, 0.2 ≦ x ≦ 1.2, x = 12- (2a + 3b), respectively, Me is Na, At least one selected from K, Li, Ca, Mg, and NH ₄ , and n represents the valence of Me. [Me] ^{n +} molar ratio of alkali metal ions to alkaline earth metal ions [(Na + K + Li ) / (Ca + Mg + NH ₄ )] is 1.0 or more.)
[2] A detergent composition containing the detergent particles of [1].
[3] A method for producing detergent particles having the following steps (1) to (4).
Step (1): Step of preparing a slurry of detergent particles Step (2): Step of spray drying the slurry obtained in Step (1) to prepare spray-dried particles (d) Step (3): Step (2) Step of preparing base detergent particles (A) by supporting the surfactant composition (e) on the spray-dried particles (d) obtained in step) Step (4): Base detergent obtained in step (3) A step of surface-modifying the particles (A) with a surface modifier (B) containing a layered clay mineral (a)

  According to the present invention, there are provided detergent particles excellent in storage stability such as solubility, caking resistance, and suppression of stains such as surfactants, a detergent composition containing the detergent particles, and a method for producing the detergent particles. Can be provided. In addition, according to the present invention, by using a layered clay mineral as a main component of the surface modifier, it is possible to impart sufficient flexibility to the clothes after washing, and the persistence to clothes (insoluble components of the detergent) It is possible to provide detergent particles having a low property of remaining in clothing.

The detergent particles of the present invention are represented by the following general formula (I) with respect to 100 parts by mass of the base detergent particles (A) having a median particle diameter of 150 to 500 μm, have a median particle diameter of 1 to 40 μm, and contain sodium. The surface modification agent (B) containing 10% by mass or more of the layered clay mineral (a) having an amount of 1.0 to 10.0% by mass is brought into contact with 10 to 50 parts by mass to be surface-modified. Features.
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · X / n [Me] n + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 ≦ b ≦ 4, 0.2 ≦ x ≦ 1.2, x = 12- (2a + 3b), respectively, Me is Na, At least one selected from K, Li, Ca, Mg, and NH ₄ , and n represents the valence of Me. [Me] ^{n +} molar ratio of alkali metal ions to alkaline earth metal ions [(Na + K + Li ) / (Ca + Mg + NH ₄ )] is 1.0 or more.)

<Base detergent particles (A)>
The base detergent particles (A) used in the present invention are particles containing at least one component selected from surfactants, cleaning builders, alkaline agents, and other detergent components used in ordinary powder detergents. And means a particle having a median particle diameter of 150 to 500 μm before the surface modification by the surface modifying agent (B) mainly composed of the layered clay mineral (a). The median particle diameter is preferably 175 to 450 μm, more preferably 200 to 400 μm. The median diameter of the base detergent particles (A) here is calculated from the mass fraction according to the size of the sieve mesh after vibrating for 5 minutes using a standard sieve (mesh 2000 to 125 μm) of JIS Z8801. is there.

(Surfactant)
As the surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be used as necessary.
Anionic surfactants include higher alcohol sulfates, higher alcohol ethoxylate sulfates, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts or alkyls thereof. Examples thereof include ester salts and fatty acid salts. In particular, a linear alkylbenzene sulfonate having 10 to 18 carbon atoms, more preferably 12 to 14 carbon atoms, and a sulfate ester salt of a higher alcohol having 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms are preferable.
Nonionic surfactants include ethylene oxide (hereinafter referred to as “EO”) adducts of higher alcohols, or EO / propylene oxide (hereinafter referred to as “PO”) adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like. In particular, EO 1-10 mol adducts of alcohols having 10 to 16 carbon atoms are compatible with removal of sebum soil, hard water resistance, biodegradability, and linear alkylbenzene sulfonates and sulfates of higher alcohols. From the viewpoint of
Examples of amphoteric surfactants include alkyldimethylaminoacetic acid betaines and fatty acid aminopropyl betaines, and examples of cationic surfactants include mono (or di) long chain alkyl type quaternary ammonium salts.

(Washing builder)
The cleaning builder means a powder cleaning power enhancer other than the surfactant. The cleaning builder includes an inorganic builder and an organic builder, and is not particularly limited, but an inorganic builder is preferable.
Specific examples of inorganic builders include bases showing sequestering ability such as citrate, bases showing alkaline ability such as sodium carbonate (dense ash, light ash), potassium carbonate, crystalline silicate, etc. Examples include bases having both sequestering ability and alkali ability, and other bases that increase ionic strength such as sodium sulfate. More specifically, for example, JP-A-5-279013, column 3, line 17 to column 6, line 24 (especially those obtained by calcination and crystallization at 500-1000 ° C.), JP-A-7-89712. Japanese Patent Laid-Open No. 2, line 45 to column 9, line 34, JP-A-60-227895, page 2, lower right column, line 18 to page 4, upper right column, line 3 (particularly the silicates in Table 2) Crystalline silicates described in). Here, the molar ratio (SiO ₂ / M ₂ O) of alkali metal silicate (wherein M represents an alkali metal) is 0.5 to 3.2, preferably 1.5 to 2.6. Is preferred.

(Alkaline agent and other cleaning ingredients)
Examples of the alkali agent include water-soluble inorganic salts such as carbonates, hydrogen carbonates, and silicates, and poorly water-soluble inorganic substances such as crystalline silicates.
Other cleaning ingredients include water-soluble inorganic salts such as sulfate, sulfite, hydrogen sulfate, hydrochloride, phosphate, water-soluble organic acid salts such as citrate and fumarate, crystalline or Examples thereof include poorly water-soluble inorganic substances such as amorphous aluminosilicate, and water-soluble polymers. Examples of the water-soluble salts include those used as the alkali agent and other detergent components.
Examples of the water-soluble polymer include carboxylic acid polymers, carboxymethyl cellulose, soluble starch, saccharides and the like. Among these, carboxylic acid polymers having a weight average molecular weight of several thousand to 100,000 are preferable from the viewpoint of sequestering ability, dispersibility of solid dirt, particle dirt, and the like, and re-fouling prevention ability. Particularly, a salt of acrylic acid-maleic acid copolymer is preferred. Polyacrylate is preferred.

(Composition composition of base detergent particles (A))
The amount of the surfactant, the cleaning builder, the alkaline agent, and other cleaning components in the base detergent particles (A) is not particularly limited, but is as follows from the viewpoint of cleaning performance.
The amount of the surfactant is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and the upper limit thereof is preferably 50% by mass or less, more preferably 45% by mass or less. More preferably, it is 40 mass% or less.
The amount of the cleaning builder is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and the upper limit thereof is preferably 60% by mass or less, more preferably 50% by mass or less, More preferably, it is 40 mass% or less.
The amount of the alkaline agent is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and the upper limit thereof is preferably 70% by mass or less, more preferably 60% by mass or less, More preferably, it is 50 mass% or less.
The amount of the other cleaning component is preferably 20% by mass or more, more preferably 30% by mass or more, and the upper limit thereof is preferably 60% by mass or less, more preferably 50% by mass or less.

(Production method of base detergent particles (A))
The base detergent particles (A) can be obtained by granulating the above-mentioned components in a slurry state and spray-dried by a stirring granulation method, a tumbling granulation method, a kneading / extrusion method or the like. After extrusion granulation, pulverization is preferable for improving fluidity and appearance.
The solid anionic surfactant neutralized product can be obtained by a dry neutralization method in which an anionic surfactant acid precursor and solid alkali particles are neutralized, and this is also used as base detergent particles. be able to. The neutralization method of the dry neutralization method is not particularly limited, and neutralization may be performed by kneading / kneading, followed by crushing and granulation, or performing a neutralization reaction while applying a shearing force in a stirring granulator. May be.
The base detergent particles (A) can also be obtained by dry blending separate particles obtained by spray drying or dry neutralization. Furthermore, other particles such as alkali particles may be dry blended. For example, heavy sodium carbonate (dense ash) particles can be mixed with particles containing a surfactant produced by a spray drying method or the like to obtain a target composition. That is, the manufacturing method is not limited for each particle used for dry blending or the like. However, as will be described later, it is preferable to carry a surfactant composition (e) on spray-dried particles (d) obtained by spray-drying.

(Spray-dried particles (d))
In the present invention, as described above, it is not essential to use spray-dried particles. However, a liquid surfactant composition (e) is added to the spray-dried particles (d) obtained by spray-drying a slurry that does not substantially contain a surfactant (hereinafter also simply referred to as “spray-dried particles (d)”). ) Is preferred in that base detergent particles having excellent solubility and fluidity can be obtained.
In addition, low bulk density particles obtained by spray-drying a slurry containing a surfactant are increased in bulk density by stirring granulation method or tumbling granulation method, or crushed after mixing / extrusion granulation Can also be used.
The average particle size of the spray-dried particles (d) is preferably 150 to 500 μm, more preferably 180 to 350 μm, from the viewpoint of solubility. The bulk density is preferably 400 g / L or more, more preferably 450 g / L or more from the viewpoint of compactification, and preferably 800 g / L or less, more preferably 600 g / L or less from the viewpoint of solubility.
The average particle diameter and bulk density of the spray-dried particles (d) are measured by the method described in the examples.

The spray-dried particles (d) preferably have a higher ability to carry a liquid component (supporting ability) from the viewpoint of suppressing aggregation of the base detergent particles. The carrying capacity is preferably 20 mL / 100 g or more, and more preferably 40 mL / 100 g or more.
Here, with regard to the ability to support spray-dried particles (d), a sample of 100 g was placed in a cylindrical mixing tank having an inner diameter of 5 cm and a height of 15 cm equipped with a stirring blade, and the stirring blade was stirred at 350 rpm. Polyoxyethylene alkyl ether (“Emulgen 106” manufactured by Kao Corporation) at a temperature of 10 ° C. was charged into the tank at a rate of 10 mL / min, and the amount of polyoxyethylene alkyl ether charged when the power required for stirring was highest Carrying capacity.
In addition, from the viewpoint of suppressing the spray-dried particles (d) from collapsing during the mixing operation described later, the spray-dried particles (d) are preferably harder, and specifically, expressed in terms of particle strength, 100 kg / cm ² or more is preferable, and 200 kg / cm ² or more is more preferable.
For the measurement of particle strength, 20 g of a sample was put into a cylindrical container having an inner diameter of 3 cm and a height of 8 cm, and tapping was performed 30 times (Tsutsui Rikenki Co., Ltd., TVP1 type tapping type densely packed bulk density measuring instrument, conditions; period 36 The sample height immediately after the end of the tapping operation is set to the initial sample height, and then the entire upper end surface of the sample held in the container by the pressure tester is 10 mm / min. Pressurize at a rate of min, measure the load-displacement curve, and divide the value obtained by multiplying the slope at the straight line portion where the displacement rate in the curve is 5% or less by the initial sample height by the pressurization area. The value is the particle strength.
As a method of improving the particle strength of the spray-dried particles (d), for example, to increase the blending ratio of an agent having a function of improving the particle strength, such as a water-soluble polymer in the slurry, or to increase the true density of the particles There are various methods such as reducing the water content of the slurry and reducing the water content in the spray-dried particles (d) by raising the drying temperature, and can be appropriately selected.

The spray-dried particles (d) are, for example, 20 to 90% by mass, preferably 30 to 75% by mass, more preferably 40 to 70% by mass, and 2 to 2% of the water-soluble polymer, based on the solid content in the slurry. 30% by weight, preferably 3-20% by weight, more preferably 5-20% by weight,
And a slurry comprising 5 to 78% by mass, preferably 10 to 67% by mass, more preferably 20 to 55% by mass of a water-soluble salt, can be obtained by spray drying. By adjusting the slurry spray drying method, drying conditions, and the like within this range, it is possible to control the average particle diameter, bulk density, supporting ability, and particle strength.
Examples of water-insoluble inorganic materials include aluminosilicates, silicon dioxide, hydrated silicate compounds, pearlite, bentonite and other clay compounds, and water-soluble polymers include carboxylic acid polymers, carboxymethylcellulose, soluble starch, saccharides, etc. Is mentioned.
Examples of water-soluble salts include various alkali metal salts, such as carbonates, hydrogen carbonates, sulfates, sulfites, hydrogen sulfates, hydrochlorides, or phosphates, ammonium salts, and amine salts. And low molecular weight water-soluble organic salts such as citric acid and fumarate.
In addition to these, the spray-dried particles (d) may contain auxiliary components such as surfactants and dyes suitable for the final detergent composition, and the blending amount of the auxiliary components is preferably 10% by mass or less.

The spray-dried particles (d) preferably have the following structure (A) and / or structure (B) from the viewpoint of the solubility of the detergent particles, and may have both structures (A) and (B). More preferred.
Structure (A): When the particles are dissolved in water, the particle diameter is preferably 1/10 or more, more preferably 1/5 or more, still more preferably 1/4 or more, and particularly preferably 1/3 or more. A structure having pores capable of releasing bubbles.
Structure (B): A structure containing a water-insoluble inorganic substance, a water-soluble polymer, and a water-soluble salt, and having a ubiquitous nature in which more water-soluble polymers and / or water-soluble salts are present in the vicinity of the surface than inside.
Since the spray-dried particles (d) have the structure (A), in the process of dissolving the detergent particles in water, first, a small amount of water enters the particles and bubbles of a predetermined size are released from the inside of the particles. Next, when a large amount of water intrudes into the particle, the particle itself collapses (self-disintegration), so that the detergent particles dissolve not only from the vicinity of the surface but also dissolve and disintegrate from the inside of the particles, so that the detergent particles dissolve at high speed. Have sex. This bubble emission phenomenon can be confirmed with a digital microscope or an optical microscope, and the bubble diameter (equivalent circle diameter) can be measured.
The pore diameter of the spray-dried particles (d) is preferably 1/10 to 4/5, more preferably 1/5 to 4/5 of the particle diameter. The calculation of the pore diameter is performed by cutting the surface including the maximum particle diameter with a scalpel or the like so as not to break the spray-dried particles (d), observing the cut surface with a scanning electron microscope, and corresponding to the circle of the cut surface of the cut particles When the diameter (γ μm) and the presence of pores inside the particles are confirmed, the equivalent circle diameter (δ μm) of the pores is measured, and the ratio of the pore diameter to the particle diameter (δ / γ) is obtained. it can. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore is δ μm.

Further, since the spray-dried particles (d) have the structure (B), the water-soluble components in the vicinity of the surface dissolve faster in water, and the dissolution behavior that promotes the disintegration of the detergent particles from the particle surface is exhibited. Thus, high-speed solubility can be expressed.
The uneven distribution of the water-soluble polymer and / or water-soluble salt can be confirmed by the following method.
First, a spray-dried particle (d) to be measured and a pulverized product in which the spray-dried particle (d) is sufficiently pulverized with an agate mortar or the like to prepare a uniform state are prepared. Then, under conditions where information from the surface of the spray-dried particles (d) and the pulverized product to about 10 μm is obtained, both are subjected to Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS), respectively. It is measured by a method used in combination (hereinafter referred to as “FT-IR / PAS”). When the amount of the former water-soluble polymer and / or water-soluble salt is larger than the amount of the latter, the spray-dried particles (d) to be measured have a structure in which they are present in the vicinity of the surface more than the inside. The measurement conditions for obtaining information from the surface of the spray-dried particles (d) and the spray-dried particles (d) to about 10 μm are, for example, a resolution of 8 cm ⁻¹ , a scanning speed of 0.63 cm / s, and a total of 128 times. Conditions are mentioned. Examples of the apparatus to be used include “FTS-60A / 896 type infrared spectrophotometer” manufactured by Bio-Rad Laboratories, and examples of the PAS cell include “300 type photoacoustic detector” manufactured by MTEC. “FT-IR / PAS” is described in APPLIED SPECTROSCOPY vol.47 1311-1316 (1993).

(Other components: Alkaline buffer)
In the present invention, spray-dried particles (d) and powders and / or granules (hereinafter referred to as “alkali buffering agents”) having an alkali buffering ability are mixed in advance and used for supporting the surfactant composition (e). be able to. Examples of the alkali buffer include alkali metal silicates and carbonates, and among them, crystalline sodium silicate and sodium carbonate are preferable.
The crystalline alkali metal silicate is preferably one that has ion exchange ability and dissolves in water to exhibit alkalinity. The ion exchange capacity can be evaluated by measuring, for example, Ca ion exchange capacity, and the value is not particularly limited, but is preferably 10 to 250 mg / g, and more preferably 50 to 250 mg / g. Furthermore, the thing of the range of 120-250 mg / g is preferable at the point which can be mix | blended with a compact detergent, when using as a Ca ion exchanger for detergents, since an effect is exhibited in a small quantity.
As the alkali metal silicate having such ion exchange ability, a composition represented by the following formula (II) is preferable.
xM ₂ O.ySiO ₂ .zMeO.wH ₂ O (II)
(In the formula, M represents Na and / or K, Me represents Ca and / or Mg, y / x = 0.5 to 4.0, z / x = 0 to 1.0, Mg in MeO) / Ca (molar ratio) = 0 to 10.)

Examples of the alkali metal silicate represented by the above formula (II) include sodium metasilicate, potassium metasilicate, powder No. 1 sodium silicate, powder No. 2 sodium silicate and the like. Moreover, the crystalline alkali metal silicate described in JP-B-1-41116 is exemplified as an alkali metal silicate having a particularly high ion exchange capacity.
As a more preferable alkali metal silicate that expresses higher ion exchange capacity, in the above formula (II), y / x = 1.0 to 2.1, z / x = 0.001 to 1.0. Things. Examples of the alkali metal silicate having such a composition include synthetic inorganic builders described in Japanese Patent No. 2525318.
Moreover, the storage stability can be further improved by using the alkali metal silicate containing potassium. As composition of such alkali metal silicate containing potassium, in said formula (II), y / x = 1.4-2.1, z / x = 0.001-1.0, M < ₂ >. K / Na (molar ratio) in O = 0.09 to 1.11. Examples of such alkali metal silicates include crystalline alkali metal silicates described in Japanese Patent No. 2525342.
Most preferable among the crystalline alkali metal silicates is a crystalline layered disilicate in which x = 1, y = 1.9 to 2.2, z = 0, and Me = Na in the above formula (II). It is sodium acid (Na ₂ Si ₂ O ₅ · wH ₂ O). Crystalline layered sodium disilicate is composed of polymorphic phases with varying proportions of α, β, δ and ε. In commercial products, an amorphous fraction may also be present. Therefore, the value of y in commercial products can be an odd number.
The blending amount of the alkaline buffer preliminarily mixed with the spray-dried particles (d) is preferably 10 to 50 parts by weight, and more preferably 20 to 40 parts by weight with respect to 100 parts by weight of the spray-dried particles (d). If it is in this range, sufficient cleaning performance and oil absorption ability can be expected.

(Surfactant composition (e))
The surfactant composition (e) to be supported on the spray-dried particles (d) is one selected from the above-mentioned anionic surfactants, nonionic surfactants, amphoteric surfactants, and cationic surfactants. The above is mentioned. The surfactant composition (e) is preferably in a liquid state when mixed with the spray-dried particles (d). More preferably, it is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, still more preferably 30 to 180 parts by weight with respect to 100 parts by weight of the nonionic surfactant (I) and the nonionic surfactant. The anionic surfactant (B) having a sulfuric acid group or a sulfonic acid group and 100 parts by mass of the nonionic surfactant are preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, Preferably, it is a composition comprising 5 to 30 parts by mass of the nonionic surfactant fixing agent (c).
When these surfactant compositions (e) are used, the solubility and flow characteristics of the detergent particles are improved, the spray dried particles (d) are prevented from collapsing during mixing, and the surfactant composition during storage (room temperature). Since it is possible to suppress the stain of the product (e), it is particularly preferable. When an anionic surfactant having a sulfuric acid group or a sulfonic acid group is blended, it is further advantageous to improve the flow characteristics of the detergent particles and to suppress bleeding of the surfactant composition (e) during storage (at room temperature).
Here, the nonionic surfactant immobilizing agent (c) is a state in which the fluidity of the nonionic surfactant that is liquid at room temperature is suppressed and the surfactant composition (e) loses fluidity. It means a base that can remarkably increase the hardness. Examples of the immobilizing agent include fatty acid salts, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and pluronic type nonionic surfactants.
The blending amount of the surfactant composition (e) is preferably 5 to 80 parts by mass, more preferably 5 to 60 parts by mass with respect to 100 parts by mass of the spray-dried particles (d), from the viewpoint of exerting detergency. More preferably, it is 10-60 mass parts, Most preferably, it is 20-60 mass parts.

<Surface modifier (B)>
The surface modifier (B) contains 10% by mass or more of the layered clay mineral (a), and can further contain zeolite (b) as necessary.
(Layered clay mineral (a))
The layered clay mineral (a) forms the surface layer of the base detergent particles (A), and is used for suppressing caking resistance, suppressing the occurrence of stains such as a surfactant.
The layered clay mineral (a) is represented by the following general formula (I) from the viewpoint of caking resistance and finished feeling, has a median particle diameter of 1 to 40 μm, and a sodium content of 1.0 to 10.0 mass. %, Preferably 1.0 to 8.0% by mass of the layered clay mineral (a) of 10% by mass or more. This layered clay mineral (a) belongs to a smectite-type layered clay mineral, particularly montmorillonite, has swelling and caking properties, and is excellent in the ability to absorb liquid components between layers. It is possible to suppress smearing. Here, “swellability” refers to the property that the layer structure of clay expands in a liquid medium.
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · X / n [Me] n + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 ≦ b ≦ 4, 0.2 ≦ x ≦ 1.2, x = 12- (2a + 3b), respectively, Me is Na, At least one selected from K, Li, Ca, Mg, and NH ₄ , and n represents the valence of Me. [Me] ^{n +} molar ratio of alkali metal ions to alkaline earth metal ions [(Na + K + Li ) / (Ca + Mg + NH ₄ )] is 1.0 or more.)
[Me] ^{n +} is introduced as a result of isomorphic ion substitution, and the degree of isomorphic ion substitution determines the magnitude of the layer charge, which is an important factor in the swelling of layered clay minerals. In the compound represented by the general formula (I), for example, two Al ³⁺ ions in the central octahedral layer may be substituted with three Mg ²⁺ ions, or partially one Mg ² ion. ^{The +} ion may be replaced with one Al ³⁺ ion, and an excessive negative charge may remain in the structure. Excessive negative charge can also occur when the tetrahedral Si ⁴⁺ ions are replaced with Al ³⁺ ions.

From the viewpoint of storage stability and solubility, among the cations, the molar ratio of ions of alkali metals (total of Na, K and Li) to ions of alkaline earth metals (total of Ca and Mg) [( Na + K + Li) / (Ca + Mg)] is 1.0 or more, preferably 1.5 or more, and more preferably 2.0 or more.
As a metal (Me) of ions ([Me] ^{n +} ) between layers, an alkali metal is preferable, and Na is more preferable. That is, it is preferable that Me includes at least Na, and at least one selected from K, Li, Ca, Mg, and NH ₄ as the others.
From the viewpoint of caking resistance, suppression of stains such as surfactants, solubility and the like, the preferred sodium content is 1.0 to 10.0% by mass, more preferably 1.25 to 8.0% by mass, More preferably, it is 1.5-6.0 mass%.
In order to obtain a clay mineral having a high ratio of alkali metal ions, it is only necessary to select the production area if it is a natural product, and it is also possible to adjust it by adding an alkali metal salt. If it is a synthetic product, it can be arbitrarily adjusted by a known method.
As a method for producing a clay mineral having a high ratio of alkali metal ions, (i) a raw clay ore containing 20% or more of moisture is added to an alkali metal salt such as powdered sodium carbonate and mixed thoroughly, and then dried. The manufacturing method including the process to do is mentioned.
The ratio of alkali metal ions to alkaline earth metal ions in the layered clay mineral (a) was determined by pulverizing the clay mineral in a mortar and passing 0.1 g of the sample that passed through a sieve having an opening of 125 μm to a microwave wet ashing device (automatic ) Sulfuric acid-hydrogen peroxide decomposition, then volume up to 50 mL in a volumetric flask and measure with an inductively coupled plasma (ICP) emission spectrometer to quantify and calculate the amount of Na, K, Li, Ca, Mg can do.

Commercial products of the clay mineral represented by the general formula (I) include “Bentonite” manufactured by Raviossa, “Odosolv K-400” manufactured by Kurosaki Shirato Kogyo Co., Ltd., “Round Rosil DGA Powder” manufactured by Sud Kemi. Is mentioned. Among the commercially available products, there are granulated granule types obtained by adding a binder component, but the binder component may be added as long as the effects of the present invention are not impaired. These can be used alone or in combination of two or more.
When using said layered clay mineral (a), it is preferable to crush beforehand until it becomes a suitable particle size as a surface modifier (B). Examples of pulverizers that can be used for crushing include impact crushers such as hammer crushers, impact crushers such as atomizers and pin mills, and shear crushers such as flash mills. The crushing operation using these may be a single-stage operation or a multi-stage operation using the same or different pulverizers.

The median particle diameter of the layered clay mineral (a) is 1 to 40 μm, preferably 3 to 35 μm, more preferably 5 to 30 μm, still more preferably 5 to 25 μm, and particularly preferably 5 to 20 μm.
Here, the average particle diameter of the layered clay mineral (a) is, for example, LB-550 manufactured by Horiba, Ltd. using a dynamic light scattering method, or LA- manufactured by Horiba, Ltd. using a Mie scattering method. Although it can be measured using 920, the Mie scattering method is suitable for measuring the layered clay mineral (a) having a particle diameter suitable for the present invention.
The content of the layered clay mineral (a) in the surface modifier (B) is 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass from the viewpoint of obtaining a sufficient caking resistance effect. % Or more, more preferably 35 parts by mass or more.
Moreover, the addition amount of the layered clay mineral (a) with respect to 100 parts by mass of the base detergent particles (A) is preferably 5 parts by mass or more, more preferably 8 parts by mass or more, from the viewpoint of sufficiently obtaining the effect of the present caking resistance. More preferably, it is 10 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 37 parts by mass or less, and still more preferably 35 parts by mass or less. The layered clay mineral (a) contains a small amount of impurities such as quartz, cristobalite, calcite, feldspar, etc., especially in the case of natural, but the amount of layered clay mineral (a) is also the one containing these impurities. means.

(Zeolite (b))
In the surface modifier (B) used in the present invention, zeolite is not an essential component, but can contain zeolite having high ion exchange ability and high alkali ability from the viewpoint of cleaning performance. The zeolite (b) used as one component of the surface modifier (B) preferably has an average primary particle diameter of 10 μm or less, more preferably 0.1 to 10 μm. When the average particle size is within this range, the coverage of the detergent particles on the particle surface is improved, which is preferable from the viewpoint of improving the fluidity and caking resistance of the detergent particles. The average particle diameter of the fine powder is measured by a method using Mie scattering, for example, LA-920 (manufactured by Horiba, Ltd.). The mass ratio of [zeolite (b) / layered clay mineral (a)] in the surface modifier (B) is preferably 1.66 or less, more preferably 1.48 or less, still more preferably 1.0 or less, 0.5 or less is particularly preferable, and 0 is most preferable.

<Other ingredients>
The surface modifier (B) used in the present invention contains the layered clay mineral (a) as an essential component, but other fine powders having an average primary particle size of 10 μm or less can be used in combination. As the fine powder, an aluminosilicate is desirable, and both crystalline and amorphous can be used. In addition, fine powders of silicate compounds such as sodium sulfate, calcium silicate, silicon dioxide, amorphous silica derivatives, and crystalline silicate compounds are also preferable. In addition, metal soap having primary particles of 0.1 to 10 μm, powdered surfactant (for example, alkyl sulfate) and water-soluble organic salt can also be used. When a crystalline silicate compound is used, it is preferably used by mixing with other fine powders in order to prevent deterioration due to aggregation of particles due to absorption of water or carbon dioxide gas.

  The amount of the surface modifier (B) used is a base from the viewpoint of improving the storage stability such as caking resistance and suppressing the occurrence of stains such as surfactants, and further providing fluidity and a good feeling to the consumer. The surface modifier (B) is 10 to 50 parts by mass, preferably 10 to 45 parts by mass, more preferably 13 to 40 parts by mass, and still more preferably 15 to 100 parts by mass with respect to 100 parts by mass of the detergent particles (A). 35 parts by mass.

In the present invention, when the base detergent particles (A) contain a liquid surfactant, water or the like, the layered clay mineral (a) that has absorbed the liquid components adheres to the base detergent particles (A). Since it has sufficient tackiness, a binder component is not necessarily required, but it is preferable to add a binder component in order to further improve the adhesion of the layered clay mineral (a).
Examples of the binder component include the surfactant composition (e), polyethylene glycol, (meth) acrylic acid polymer, cellulose derivative, and an aqueous solution thereof. Polyethylene glycol preferably has an average molecular weight of 4000 to 20000 from the viewpoint of solidification at a temperature at which a detergent is usually used (room temperature to about 40 ° C.) and solubility after surface treatment. Examples of the cellulose derivative include carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose and the like.
As addition amount of a binder component, 0-8 mass parts is preferable with respect to 100 mass parts of base detergent particles, 0.5-6 mass parts is more preferable, and 1-4 mass parts is still more preferable.

<Manufacture of detergent particles>
Although the manufacturing method of the detergent particle | grains of this invention is not specifically limited, According to the method which has the following process (1)-(4), it can manufacture efficiently.
Step (1): Step of preparing a slurry of detergent particles substantially free of surfactant Step (2): Spray-drying the slurry obtained in Step (1) to prepare spray-dried particles (d) Step Step (3): Step of preparing base detergent particles (A) by supporting the surfactant composition (e) on the spray-dried particles (d) obtained in Step (2) Step (4): Step Step of surface-modifying the base detergent particles (A) obtained in (3) with a surface modifier (B) containing a layered clay mineral (a) Hereinafter, steps (1) to (4) will be described. However, this is only an example, and the base detergent particles (A) used in the present invention can be produced, for example, by a dry neutralization method or the like, or separately obtained by a spray drying method, a dry neutralization method, or the like. It can also be obtained by dry mixing the particles. Furthermore, other particles such as alkali particles may be dry mixed. For example, heavy sodium carbonate (dense ash) particles can be mixed with particles containing a surfactant produced by a spray drying method or the like to obtain a target composition.

(Step (1): Slurry preparation)
The slurry prepared in step (1) is a slurry of detergent particles containing at least one component selected from ordinary cleaning builders, alkaline agents, and other detergent components, and can be pumped and non-cured. The slurry may be any suitable slurry.
Since this slurry does not substantially contain a surfactant, it is possible to obtain spray-dried particles (d) having high particle strength and high bulk density, and to obtain base detergent particles (A) having excellent solubility. Therefore, it is preferable.
Here, “substantially does not contain a surfactant” does not exclude the case where a surfactant is contained, but it depends on the component composition, but it can maintain a substantially spherical shape with a relatively uniform particle size. Indicates a range that may be included. Specifically, it is 10 mass% or less in a slurry, More preferably, it is 5 mass% or less.
The slurry temperature is preferably 30 to 80 ° C, more preferably 35 to 65 ° C. If the slurry temperature is within this range, for example, the solubility of water-soluble salts such as granular sodium carbonate decreases, and there is no inconvenience such as an increase in the amount of undissolved residue.
Moreover, generally the water | moisture content of a slurry becomes like this. Preferably it is 30-70 mass%, More preferably, it is 35-60 mass%, More preferably, it is 40-55 mass%. If the water | moisture content of a slurry exists in this range, the amount of melt | dissolution of water-soluble salts will become enough, and it can suppress the pumping liquid deterioration by the increase in slurry viscosity. Further, since the amount of water evaporated in the step (2) is suppressed, productivity does not decrease.

  There is no restriction | limiting in particular in the addition method and order of each component for slurry formation. For example, first, all or almost all of the water is added to the mixing tank, preferably after the water temperature has nearly reached the set temperature, the other ingredients are added sequentially or simultaneously. The normal order of addition is to first add liquid components such as surfactants and water-soluble polymers, then add water-soluble powder raw materials such as soda ash, and finally add water-insoluble substances such as zeolite. To do. At that time, for the purpose of improving the mixing efficiency, the water-insoluble component may be added in two or more portions. In addition, the powder raw material may be added to the aqueous medium after mixing in advance, or water may be added to adjust the viscosity and slurry moisture after all components are added. In order to finally obtain a homogeneous slurry, after all components are added to the slurry, it is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

(Step (2): Preparation of spray-dried particles (d))
In step (2), the slurry obtained in step (1) is spray-dried to prepare spray-dried particles (d). By spray drying, the shape of the obtained particles becomes substantially spherical.
The spray drying tower is more preferably a countercurrent tower from the viewpoint of improving the thermal efficiency and the particle strength of the spray dried particles (d). The slurry atomization apparatus may be any form of a pressure spray nozzle, a two-fluid spray nozzle, and a rotating disk type, but a pressure spray nozzle is particularly preferable in order to obtain a desired average particle diameter.
The temperature of the gas supplied to the drying tower is preferably as high as possible from the viewpoint of oil absorption capacity, but preferably 200 to 360 ° C, more preferably 220 to 340 ° C in view of productivity, operability, and safety. Especially preferably, it is 240-320 degreeC. The temperature of the gas discharged from the drying tower is preferably 80 to 130 ° C, more preferably 80 to 125 ° C, and particularly preferably 80 to 120 ° C, from the viewpoint of the thermal efficiency of the drying tower. Further, the spray-dried particles (d) after spray-drying may be further dried by an air flow dryer, a fluidized bed dryer, a rotary dryer or the like.

(Step (3): Preparation of base detergent particles (A))
The surfactant composition (e) used in the step (3) is at least one surfactant selected from anionic surfactants, nonionic surfactants, zwitterionic surfactants, and cationic surfactants. It is a composition of an agent.
For surfactants that are solid or pasty in a practical temperature range (room temperature to about 40 ° C.), these are preliminarily solution of low viscosity, for example, nonionic surfactant, nonionic surfactant aqueous solution or water. The surfactant can be dispersed or dissolved to prepare a mixed solution or aqueous solution of the surfactant, and the mixed solution or aqueous solution can be added to the spray-dried particles (d). The mixing ratio of the low-viscosity surfactant or water and the solid or pasty surfactant may be in the viscosity range in which the resulting mixed solution or aqueous solution can be sprayed. For example, polyoxyethylene dodecyl ether and dodecyl benzene sulfone. If it is sodium acid, the sprayable surfactant composition (e) can be obtained by adjusting the ratio of the two in the range of 1: 1.4 to 1.4: 1.

In step (3), the surfactant composition (e) obtained above is added and supported on the spray-dried particles (d) obtained in (2).
The amount of the surfactant composition (e) to be carried on the spray-dried particles (d) is preferably 5 to 80 parts by mass with respect to 100 parts by mass of the spray-dried particles (d) from the viewpoint of exerting detergency. -60 mass parts is more preferable, 10-60 mass parts is still more preferable, and 20-60 mass parts is especially preferable. Here, the loading amount of the anionic surfactant is preferably 0 to 60 parts by mass, more preferably 0 to 50 parts by mass, and particularly preferably 3 to 40 parts by mass. 1-50 mass parts is preferable, as for the load of a nonionic surfactant, 1-45 mass parts is more preferable, and 3-40 mass parts is still more preferable. The nonionic surfactant can be used alone, but preferably mixed with an anionic surfactant. Further, amphoteric surfactants and cationic surfactants can be used in combination for the purpose. The amount of the surfactant composition (e) supported here means that the surfactant is not included when the surfactant is added during the slurry preparation in the step (1).
Examples of the method for supporting the surfactant on the spray-dried particles (d) include a method using a known mixer of batch type or continuous type. When the batch method is used, the mixing method is as follows: (i) Add the spray-dried particles (d) to the mixer and then add the surfactant while operating the mixer. (Ii) Mixing The spray-dried particles (d) and the surfactant are charged little by little in the machine. (Iii) A part of the spray-dried particles (d) is charged into the mixer, and then the remaining spray-dried particles (d) and the surfactant are charged. Can be taken in small amounts.
Among these methods, the above (i) is particularly preferable. The surfactant is preferably added in a liquid state, and it is preferable to spray and supply a surfactant in the liquid state.

Commercially available mixing devices that can be used in step (3) include Henschel mixer (Mitsui Miike Chemical Co., Ltd.), high speed mixer (Fukae Kogyo Co., Ltd.), vertical granulator (Paulec Co., Ltd.), Redige Examples include a mixer (manufactured by Matsuzaka Giken Co., Ltd.), a pro-share mixer (manufactured by Taiheiyo Kiko Co., Ltd.), a nauter mixer (manufactured by Hosokawa Micron Corporation), and the like.
As a preferable mixing device, a strong shearing force is hardly applied to the spray-dried particles (d) from the viewpoint of producing base detergent particles (A) containing a large amount of mononuclear detergent particles having excellent solubility (spray-dried particles ( d) is a device that is difficult to disintegrate, and a device with good mixing efficiency is preferable from the viewpoint of the dispersion efficiency of the surfactant. Of these, a horizontal mixing tank having a stirring shaft at the center of a cylinder, and a mixer (horizontal mixer) of a type that mixes powder by attaching a stirring blade to this shaft, a Ladige mixer and a pro shear mixer Etc.
Other continuous mixing devices include, for example, a flexo-mix type (manufactured by POWREC Co., Ltd.), a turbulizer (manufactured by Hosokawa Micron Co., Ltd.), and the like.
The temperature in the mixing device is preferably higher than the melting point of the surfactant, more preferably up to 50 ° C. higher than the melting point, and even more preferably 10 ° C. to 30 ° C. higher than the melting point. Moreover, when adding the acid precursor of an anionic surfactant at this process, it is more preferable if it heats up to the temperature which the said acid precursor can react, and it mixes.
In addition, the batch mixing time for obtaining suitable base detergent particles and the average residence time in continuous mixing are preferably 1 to 20 minutes, and more preferably 2 to 10 minutes.

When a nonionic surfactant is used, a water-soluble nonionic organic compound having a melting point of 45 to 100 ° C. and a molecular weight of 1000 to 30000 (hereinafter referred to as “melting point raising agent”) or an aqueous solution thereof is used. Before addition, during addition, during addition, or after addition, or pre-mixed and added to the surfactant to suppress caking resistance and the ability of the surfactant in the detergent particles to bleed out . Examples of the melting point raising agent include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, pluronic type nonionic surfactant and the like.
The amount of the melting point raising agent used is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, with respect to 100 parts by mass of the spray-dried particles (d).
In step (3), when an aqueous solution of a surfactant or the like is added in the slurry preparation step (1), the step (3) includes a step of drying excess moisture while mixing and / or mixing with a mixer. May be.
In addition, the cleaning builder can be added before, simultaneously with, during or after the addition of the surfactant. By adding a cleaning builder, the particle size of the base detergent particles can be controlled, and the cleaning power can be improved.
The amount of the cleaning builder used in this step is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the spray-dried particles (d), from the viewpoint of maintaining mononuclearity of the detergent particles, high-speed solubility, and particle diameter control. 5-70 mass parts is more preferable, and 10-60 mass parts is still more preferable.

(Process (4): Surface modification)
In step (4), in order to modify the surface of the base detergent particles (A) obtained in step (3), a surface modification agent (B) containing a layered clay mineral (a) is added. The quality step can be repeated once or twice.
As described above, the median particle diameter of the layered clay mineral (a) is 1 to 40 μm. However, if the average particle diameter and the added amount are within the above ranges, it is sufficient to avoid a decrease in solubility. Can be expected to improve caking resistance.
The addition method of the surface modifier (B) is not particularly limited, but a known batch type or continuous type mixer used in the step (3) is not easily applied with a strong shearing force (the base detergent particles are not easily broken down). ) And high mixing efficiency (high dispersibility), it is preferable because the surface modifier (B) can be appropriately dispersed on the surface of the base detergent particles.
Moreover, it is preferable to add a binder component in the step (4) because adhesion of the surface modifier (B) is increased. Suitable binder components and addition amounts are the same as described above.
Examples of the method for adding the binder component include a method using a known mixer of batch type or continuous type. When performing batchwise, (i) adding the surface modifier (B) and the binder component separately or simultaneously while operating the mixer, (ii) adding a small amount of the surface modifier (B) and the binder component A method of alternately adding them can be employed. Moreover, when using 2 or more types of binder components, you may add simultaneously and may add separately before and after adding a surface modifier (B).
The binder component that is solid at room temperature is preferably supplied by spraying after melting. Moreover, it is preferable to spray and supply the binder component which is liquid at normal temperature after raising the temperature from the inside of the mixer.
Examples of the apparatus preferably used in step (4) include the mixing apparatus described in step (3).
The batch mixing time for obtaining detergent particles having excellent solubility and storage stability and the average residence time in continuous mixing are preferably 1 to 20 minutes, and more preferably 2 to 20 minutes.
It is also possible to add the cleaning builder before, during, and during the addition of the surface modifier (B). By adding a cleaning builder, the particle diameter of the detergent particle group can be controlled, and the cleaning power can be improved.

<Detergent composition>
The detergent composition of the present invention is a composition containing the cleaning particles of the present invention obtained above, and is obtained, for example, by mixing the detergent particles of the present invention and a separately added detergent component. The detergent composition of the present invention can be used without particular limitation as long as it is an application using a powder detergent. For example, it can be particularly suitably used as a powder detergent for clothing, a detergent for automatic dishwashers, and the like.
Separately added detergent components include, for example, known detergent base materials such as builder granules, bleach (percarbonate, perborate, bleach activator, etc.), bleach activator, anti-staining agent (Carboxymethyl cellulose etc.), softening agents, reducing agents (sulfites etc.), fluorescent brighteners, antifoaming agents (silicone etc.), enzymes such as cellulase and protease, dyes, fragrances and the like.
The content of the detergent particles in the detergent composition is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more from the viewpoint of cleaning ability. Further, the content of the separately added detergent component in the detergent composition is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 20% by mass or less.

In the following production examples, examples and comparative examples, “parts” and “%” are “parts by mass” and “mass%” unless otherwise specified. The physical properties of the spray-dried particles (d), the surfactant composition (e) and the detergent particles were measured and evaluated by the following methods.
(1) Moisture: Measured by a method defined in JIS K0068.
(2) Average particle size of layered clay mineral (a) component:
Using LA-920 manufactured by HORIBA, Ltd., using ethanol (reagent special grade) adjusted to 20 ° C as the dispersion medium, adding a layered clay mineral so as to be within the appropriate concentration range while confirming the display, The circulation strength was set to 4 and then measured after dispersion for 1 minute with ultrasonic waves, and the obtained median diameter was defined as the average particle diameter of the layered clay mineral (a).
(3) Average particle size:
The mixture was vibrated for 5 minutes using a standard sieve of JIS Z8801 (mesh opening 2000 to 125 μm), and then the median diameter was calculated from the mass fraction depending on the size of the sieve mesh.

(4) Bulk density: Measured by the method defined in JIS K3362.
(5) Screening rate A box without a top of 10.2 cm in length, 6.2 cm in width, and 4 cm in height was made with filter paper (No. 2 manufactured by ADVANTEC), and the four corners were fastened with a stapler. In order to evaluate the caking state after putting a sample of 50 g and leaving it at a temperature of 30 ° C. and a humidity of 70% RH for 21 days and 28 days, the following sieve passing rate was determined.
Sieve passing rate: The sample after the test is gently transferred onto a sieve (aperture 4760 μm defined in JIS Z 8801), the weight of the passed powder is measured, and the sieve passing rate (%) with respect to the sample after the test is obtained.
The caking resistance of the detergent particles is preferably 90% or more, more preferably 92% or more after storage for 21 days, and preferably 80% or more, more preferably 85%, after 28 days storage. That's it.

(6) Stain removal property The stain appearance state at the bottom (surface not in contact with the powder) of the filter paper container subjected to the sieve passage rate test was visually evaluated. Evaluation was made based on the wetted area at the bottom, and the following 1 to 5 ranks were used.
Rank A: The surface of about 1/4 or less is wet.
Rank B: The surface of about 1/2 is wet.
Rank C: The surface of about 3/4 is wet.
Rank D: The entire surface is almost wet.
If the above evaluation is preferably C rank or higher, and more preferably B rank, the detergent particles have a stain-repelling property because it is not necessary to devise measures for preventing adhesion to equipment and preventing stains on containers in the transport system.

(7) Flexibility (Preparation of evaluation towel)
A commercially available cotton towel (100% cotton) was used in a mini-washing machine ("N-BK2" manufactured by National), and the pretreatment agent at that time was a nonionic surfactant (primary alcohol having 12 carbon atoms and ethylene). An average of 6 moles of oxide added), crystalline silicate (pre-feed granule product), and sodium carbonate mixed at 1: 1: 3 (weight ratio) were used at 0.5 g / L. After washing at a water temperature of 20 ° C. for 7 minutes, centrifugal dehydration, rinsing for 3 minutes, dehydration, rinsing for 3 minutes, and dehydration were repeated 5 times in total to remove the treatment agent.
(Flexible evaluation method)
To 5 L of water at 20 ° C., 5.0 g of the soft detergent composition shown in Table 1 and 0.3 kg of cotton towel (4 pieces of 70 cm × 30 cm) were added and washed for 7 minutes. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes, dehydrated and air-dried.
Five testers made a sensory evaluation of the softness of the hand using a towel and a pre-treated towel as a pair. When there is no difference and when it becomes hard, 0 points, when it becomes slightly softer, 1 point, when it becomes slightly softer, 2 points, when it becomes clear softly 3 points, the total points of 5 people are shown as follows It was. At this time, a grade of ○ or higher was regarded as an acceptable level.
Evaluation criteria ◎: Total of 10 points or more ○: Total of 6 points or more and less than 10 points △: Total of 3 points or more and less than 6 points ×: Total of less than 3 points

(8) Clothes persistence 5 g of water at 5 ° C., 5.0 g of soft detergent composition shown in Table 1, black cotton broad 40 thin fabric (manufactured by Tanigami Shoten Co., Ltd.) 0.3 kg (30 cm × 38 cm processed into 19 sheets) ) And washed for 7 minutes. After dehydration, it was rinsed with 5 L of water for 3 minutes, dehydrated, rinsed for 3 minutes, dehydrated and air-dried.
From the number and size of the front and back residues per black cotton broad cloth washed with the soft detergent composition, the clothing residue was evaluated according to the following evaluation criteria.
Evaluation criteria A: Almost no residue is observed. O: There is no residue of coarse particles having a particle size of 0.5 mm or more, and 2 to 10 residues having a particle size of 0.5 mm or less are observed. There is no residue of coarse particles of 5 mm or more, and 10 or more residues having a particle size of 0.5 mm or less are observed. X: There are coarse particle residues of 0.5 mm or more in particle size, and particles of 0.5 mm or less XX: There are two or more coarse particle residues with a particle size of 0.5 mm or more, and many residues with a particle size of 0.5 mm or less are also observed.

Production Example 1 (Preparation of spray-dried particles (d))
After 410 parts of water was added to the mixing tank and the water temperature reached 45 ° C., 110 parts of sodium sulfate (manufactured by Shikoku Kasei Co., Ltd., anhydrous neutral sodium sulfate), 8 parts of sodium sulfite (manufactured by Mitsui Chemicals, soda sulfite), 2 parts of fluorescent dye (Cino Pearl CBS-X, manufactured by Ciba Specialty Chemicals) was added and stirred for 10 minutes. 120 parts of sodium carbonate (Central Glass Co., Ltd., dense ash, average particle size: 290 μm) is added, and 150 parts of 40% sodium polyacrylate aqueous solution (Kao Corporation, mass average molecular weight 10,000) is added for 10 minutes. Stir, add 40 parts of sodium chloride (Nankai Salt Industries Co., Ltd., Nakuru N) and 160 parts of zeolite (ZEOBUILDER, Zeobuilder, 4A type, average particle size: 3.5 μm) and stir for 15 minutes. And a homogeneous slurry was obtained (slurry moisture 50%, temperature 50 ° C.).
The slurry was supplied to a spray drying tower (counterflow type) with a pump, and sprayed at a spray pressure of 2.5 MPa from a pressure spray nozzle installed near the top of the tower. The hot gas supplied to the spray-drying tower was supplied from the bottom of the tower at a temperature of 285 ° C. and discharged from the top of the tower at 98 ° C. The resulting spray-dried particles (d) had a water content of 0.0%, a bulk density of 510 g / L, and an average particle size of 290 μm.

Production Example 2 (Preparation of surfactant composition (e))
840 parts of polyoxyethylene alkyl ether (manufactured by Kao Corporation, nonionic surfactant, Emulgen 108KM, average added mole number of ethylene oxide: 8.5, carbon number of alkyl chain: 12 to 14) and polyethylene glycol (Mitsui Chemicals, Inc.) 69 parts of PEG 13000, mass average molecular weight: 10000, solid content 60%) are heated to 80 ° C., and 960 parts of dodecylbenzenesulfonic acid (manufactured by Kao Corporation, Neoperex GS) and 258 parts of a 48% aqueous sodium hydroxide solution 258 Parts were added and stirred to prepare a surfactant composition (e).

Example 1 (Preparation of detergent particles)
50 parts of spray-dried particles (d) obtained in Production Example 1 in a Redige mixer (Matsuzaka Giken Co., Ltd., capacity 130 L, with jacket; 80 ° C. hot water flow rate 10 L / min), 7.5 parts of sodium carbonate , 2 parts of crystalline sodium silicate (manufactured by Tokuyama Siltech Co., Ltd., pulverized pre-feed 6N and used with an average particle size of 10 μm) are added, and the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1. 6 m / s) was started, and 21.3 parts of the surfactant composition (e) obtained in Production Example 2 (effective portion 19.1 parts, moisture 2.2 parts, 80 ° C.) were added thereto. After charging for 2 minutes, stirring was performed for 5 minutes, and the surfactant composition (e) was supported on the spray-dried particles (d) to obtain 78.6 parts of base detergent particles.
While maintaining the operating conditions of the Redige mixer with the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), layered clay mineral (Kurasaki Shirato Co., Ltd., smectite-type layered clay mineral, “Odosolve K” -400 ", the median particle diameter: 10 [mu] m, the main _{component: [Mg a Al b (Si} 2 O 5) 4 (OH) 4] X- · Me X +, a = 1, b = 3, x = 1, containing sodium Amount: 1.6%, molar ratio [(Na + K + Li) / (Ca + Mg)] = 2.1) After adding 10 parts, main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation Number: 3600 rpm, peripheral speed: 28 m / s) was stirred for 30 seconds. The operating conditions of the Redige mixer were returned to the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s), and after further adding 10 parts of the layered clay mineral, the main shaft (rotation speed: 120 rpm, peripheral speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were stirred for 30 seconds and then discharged to obtain 100 parts of detergent particles. The water content of the detergent particles obtained was 1.4%, and the water evaporation rate of the surfactant composition (e) was 35%. Table 1 shows the composition and physical properties of the resulting detergent particles.

Examples 2 to 4 and Comparative Example 1 (Preparation of detergent particles)
In Example 1, detergent particles were obtained in the same manner as in Example 1 except that a part of the layered clay mineral used as the surface modifier (B) was replaced with zeolite. The surface modifier (B) was added in two stages, but the zeolite / layered clay mineral ratio was the same in both the first and second stages. Table 1 shows the ratio of the zeolite to the layered clay mineral and the composition and physical properties of the resulting detergent particles.
Comparative Example 2 (Preparation of detergent particles)
Except that the layered clay mineral used was changed to Zland Chemi's Mexican landrosyl powder (average particle size 18 μm, (Na ion + K ion + Li ion) / (Ca ion + Mg ion) = 0.4). In the same manner as in Example 1, detergent particles were obtained. Table 1 shows the composition and physical properties of the resulting detergent particles.

From Table 1, it can be seen that the detergent particles of Examples 1 to 4 have both flexibility and solubility and are excellent in storage stability. On the other hand, since Comparative Example 1 has a low content of the layered clay mineral (a) in the surface modifier (B), it is inferior in flexibility and has a caking resistance and stain resistance after storage. It is significantly inferior to the examples. Although Comparative Example 2 is excellent in flexibility and storage stability, since the ratio of (Na + K + Li) in the layered clay mineral (a) is small, the solubility is remarkably inferior to the examples. From the above results, the content of the layered clay mineral (a) in the surface modifier (B) and the molar ratio [(Na + K + Li) / (Ca + Mg + NH ₄ )] in the layered clay mineral (a) are within the scope of the present invention. It is clear that extremely excellent flexibility, solubility and storage stability can be realized at the same time. Moreover, the detergent particles of Examples 1 to 4 have a bulk density and an average particle size suitable for a compact detergent.

Claims (6)

It is represented by the following general formula (I) with respect to 100 parts by mass of the base detergent particles (A) having a median particle diameter of 150 to 500 μm, the median particle diameter is 1 to 40 μm, and the sodium content is 1.0 to 10 Detergent particles obtained by surface modification by bringing 10 to 50 parts by mass of a surface modifier (B) containing 10% by mass or more of a layered clay mineral (a) of 0.0% by mass.
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · X / n [Me] n + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 ≦ b ≦ 4, 0.2 ≦ x ≦ 1.2, x = 12- (2a + 3b), respectively, Me is Na, At least one selected from K, Li, Ca, Mg, and NH ₄ , and n represents the valence of Me. [Me] ^{n +} molar ratio of alkali metal ions to alkaline earth metal ions [(Na + K + Li ) / (Ca + Mg + NH ₄ )] is 1.0 or more.)   The detergent particle according to claim 1, wherein the surface modifier (B) contains a layered clay mineral (a) and a zeolite (b).   The detergent particle according to claim 2, wherein a mass ratio of [zeolite (b) / layered clay mineral (a)] in the surface modifier (B) is 1.66 or less.   The base detergent particles (A) are obtained by supporting a surfactant composition (e) on spray-dried particles (d) obtained by spray-drying a slurry of detergent particles substantially free of surfactant. The detergent particle according to any one of claims 1 to 3.   A detergent composition containing the detergent particles according to claim 1. The manufacturing method of the detergent particle which has the following process (1)-(4).
Step (1): Step of preparing a slurry of detergent particles substantially free of surfactant Step (2): Spray-drying the slurry obtained in Step (1) to prepare spray-dried particles (d) Step Step (3): Step of preparing base detergent particles (A) by supporting the surfactant composition (e) on the spray-dried particles (d) obtained in Step (2) Step (4): Step Step of surface-modifying the base detergent particles (A) obtained in (3) with a surface modifier (B) containing a layered clay mineral (a)