JP5525126B2 - Detergent particles - Google Patents

Description

  The present invention relates to detergent particles and detergent compositions containing the same.

In powder detergents, detergent particles bind to each other during long-term storage and cause caking to become a solid state.The main cause is that the detergent particles absorb external components such as moisture and carbon dioxide during storage. It has become. When moisture is absorbed, caking occurs due to the absorbed moisture liquid-crosslinking between the detergent particles or by partially dissolving the detergent particle surface components to form sticky parts on the detergent particle surface. Let The absorbed carbon dioxide gas reacts with alkali components and moisture in the detergent, and generates needle-like crystals such as sodium hydrogencarbonate and sodium sesquicarbonate in the shape of a chestnut on the surface of the detergent particles. The acicular crystals are entangled with the acicular crystals on the surface of the adjacent chestnut-shaped detergent particles to cause caking.
The caking that occurs due to the above causes a problem that the usability of the detergent is remarkably impaired, for example, not only the appearance is remarkably impaired but also accurate measurement is impossible. Various studies have been made to solve such problems.

For example, Patent Document 1 discloses a technique for obtaining free fluidity by mixing a granular detergent composition and a liquid binder substance and then coating with zeolite X. However, in this technology, the surface modifier Z is not sufficiently adherent, and the surface modifier is peeled off due to the stress that the detergent particles receive during transportation of the manufacturing process. There is a problem that sometimes sufficient effects cannot be obtained.
For the purpose of improving caking resistance and the like, Patent Document 2 discloses a method in which a surfactant is supported on a base granule, and then a fine powder and an acid precursor of an anionic surfactant are mixed and surface-coated. A method for producing detergent particles, Patent Document 3 discloses detergent particles having a surface layer formed on the surface of the detergent particles and then coated with a surface modifier, and Patent Document 4 discloses a base detergent particle surface having an anionic surfactant. A detergent particle obtained by performing the same operation as in Patent Document 3 after neutralization with an acid precursor is disclosed. However, these detergent particles are not fully satisfactory in terms of suppressing the occurrence of stains such as surfactants.
Moreover, like patent documents 1-4, when devising the surface modification process and improving the caking resistance of the detergent particles, there is also a problem that the solubility of water-insoluble matter in the detergent is remarkably lowered. Therefore, there is a need for technological development to improve the caking resistance while maintaining the solubility.

Japanese Patent No. 2965905 JP 2001-3095 A JP 2004-143394 A JP 2006-291139 A

  It is an object of the present invention to provide detergent particles having excellent solubility, caking resistance, and excellent storage stability such as suppression of stains such as surfactants, and a detergent composition containing the detergent particles. To do.

That is, the present invention provides the following [1] and [2].
[1] Detergent particles obtained by coating 100 parts by mass of base detergent particles (a) with 10 to 50 parts by mass of a surface modifier containing lamellar clay mineral (b) and zeolite (c), Detergent particles having a mass ratio of clay mineral (b) / zeolite (c) of 0.1 to 0.6.
[2] A detergent composition containing the detergent particles of [1].

  According to the present invention, it is possible to provide a detergent particle having excellent solubility, caking resistance, and excellent storage stability such as suppression of stains such as a surfactant, and a detergent composition containing the detergent particle. it can.

The detergent particles of the present invention are detergent particles obtained by coating 100 parts by mass of the base detergent particles (a) with 10 to 50 parts by mass of a surface modifier containing the layered clay mineral (b) and zeolite (c). The mass ratio of [layered clay mineral (b) / zeolite (c)] is 0.1 to 0.6.
The amount of the surface modifier used is the base detergent particle (from the viewpoint of improving the storage stability such as caking resistance, suppressing the occurrence of stains such as surfactants, and giving a good usability to the fluidity and the consumer. a) Preferably it is 15-45 mass parts with respect to 100 mass parts, More preferably, it is 20-40 mass parts.

<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. Means the particles before the surface modification by the layered clay mineral (b) and the zeolite (c).
(Surfactant)
As the surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, and a cationic surfactant can be blended 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 surfactant, cleaning builder, 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-mixing separate particles obtained by a spray drying method or a dry neutralization method. 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. That is, the production method is not limited for each particle used for mixing. However, those obtained by supporting the surfactant composition (e) on the spray-dried particles (d) described later are particularly preferable because the solubility is good and the effects of the present invention become remarkable.

(Spray-dried particles (d))
In the present invention, 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 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 respect to the ability to support spray-dried particles, 100 g of a sample was placed in a cylindrical mixing vessel having an inner diameter of 5 cm and a height of 15 cm equipped with a stirring blade inside, and the stirring blade was stirred at 350 rpm, Oxyethylene alkyl ether (“Emulgen 106” manufactured by Kao Corporation) was charged into the tank at a rate of 10 mL / min, and the amount of polyoxyethylene alkyl ether added when the power required for stirring was the highest To do.
Further, from the viewpoint of suppressing the spray-dried particles from collapsing during the mixing operation described later, the spray-dried particles are preferably harder, specifically, expressed in terms of particle strength, preferably 100 kg / cm ² or more, More preferably, it is 200 kg / cm ² or more.
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.

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 substances 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 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 have the structure (A), in the process in which the detergent particles are dissolved 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. When a large amount of water intrudes into the particle, the particle itself collapses (self-disintegration), and not only dissolution from the vicinity of the surface but also dissolution and disintegration from the inside of the particle occur, so that the detergent particles have high solubility. . 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 size of the spray-dried particles is preferably 1/10 to 4/5, more preferably 1/5 to 4/5 of the particle size. The pore size is calculated by cutting the surface including the maximum particle size with a scalpel or the like so as not to break the spray-dried particles, observing the cut surface with a scanning electron microscope, and the equivalent circle diameter (γ μm) of the cut surface of the cut particles. ), And the presence of pores inside the particles, the equivalent circle diameter (δ μm) of the pores is measured, and the ratio of the pore diameter to the particle diameter (δ / γ) can be obtained. When a plurality of pores are confirmed, the equivalent circle diameter of the largest pore is δ μm.

Further, by having the structure (B) spray-dried particles, the water-soluble component near the surface dissolves faster in water, and exhibits a dissolution behavior that promotes disintegration of the detergent particles from the particle surface, 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 to be measured and a pulverized product in which the spray-dried particle is sufficiently pulverized with an agate mortar or the like to prepare a uniform state are prepared. A method using both Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) under the condition that information from the surface of the spray-dried particles and the pulverized product to about 10 μm is obtained. (Hereinafter referred to as “FT-IR / PAS”). When the amount of the former water-soluble polymer and / or water-soluble salt is larger than that of the latter, the spray-dried particles to be measured have a structure in which they are present in the vicinity of the surface more than the inside. As measurement conditions for obtaining information from the surface of the spray-dried particles and the pulverized product of the spray-dried particles to about 10 μm, for example, conditions of a resolution of 8 cm ⁻¹ , a scanning speed of 0.63 cm / s, and a total of 128 times can be 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 and powders and / or granules (hereinafter referred to as “alkali buffering agent”) having an alkali buffering ability can be mixed in advance and used for supporting the surfactant composition. 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.
10-50 mass parts is preferable with respect to 100 mass parts of spray-dried particles, and, as for the compounding quantity of the alkaline buffer mixed beforehand with spray-dried particles, 20-40 mass parts is more preferable. 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 composition is mentioned. The composition is preferably liquid when mixed with spray-dried particles. More preferably, it is preferably 0 to 300 parts by weight, more preferably 20 to 200 parts by weight, and even more preferably 30 to 180 parts by weight with respect to 100 parts by weight of the nonionic surfactant (a) 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). This is particularly preferable because it can suppress the appearance of stains. When an anionic surfactant having a sulfuric acid group or a sulfonic acid group is blended, it is further advantageous in improving the flow characteristics of the detergent particles and suppressing the occurrence of stains on the surfactant composition during storage (at room temperature).
Here, the nonionic surfactant immobilizing agent (c) means that the fluidity of the nonionic surfactant that is liquid at room temperature is suppressed, and the hardness in a state where the surfactant composition loses fluidity is remarkably increased. It means a base that can be enhanced. 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, and still more preferably from the viewpoint of exerting detergency. It is 10-60 mass parts, Most preferably, it is 20-60 mass parts.

<Layered clay mineral (b)>
The layered clay mineral (b) constitutes a surface modifier together with the zeolite (c), forms a surface layer of the base detergent particles (a), and has effects such as caking resistance and suppression of stains such as surfactants. Demonstrate.
Layered clay minerals (b) include talc, pyrophyllite, smectite (saponite, hectorite, saconite, stevensite, montmorillonite, beidellite, nontronite, etc.), vermiculite, mica (phlogopite, biotite, chinwald mica, Muscovite, paragonite, ceradonite, sea chlorite, etc.), chlorite (clinochlore, chamosite, nimite, penantite, sudowite, dombasite, etc.), brittle mica (clinintite, margarite, etc.), sulite, serpentine mineral (anti Examples include golite, lizardite, chrysotile, amicite, clonstedite, burcherin, greenerite, garnierite, and kaolin minerals (kaolinite, dickite, nacrite, halloysite, etc.). Among these, talc, smectite, swellable mica, vermiculite, chrysotile, kaolin mineral, and the like are preferable, smectite is more preferable, and montmorillonite is further preferable in terms of flexibility. These can be used alone or in combination of two or more.

The layered clay mineral (b) is preferably a smectite type layered clay mineral from the viewpoint of caking resistance and finished feeling. Smectite-type layered clay minerals have swelling and caking properties and are excellent in the ability to absorb liquid components between layers, so that it is possible to suppress the above-described smearing of the liquid surfactant and the like. Here, “swellability” refers to the property that the layer structure of clay expands in a liquid medium.
The layered clay mineral (b) is preferably composed mainly of a material represented by the following formula (I).
Here, the main component means that the layered clay mineral represented by the following formula (I) is 90% by mass or more, preferably 95% by mass or more, more preferably 98% by mass or more.
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · Me X + (I)
In the formula (I), a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12− (2a + 3b), and Me ^{X +} is Na, K, Li, Ca, Mg and It is a charge balancing cation of at least one metal selected from NH ₄ or ammonium.
Me ^{X +} 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 following 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.

In addition, from the viewpoint of storage stability and solubility, among the cations, a mole of alkali metal ions (total of Na ions, K ions, Li ions) and alkaline earth metal ions (total of Ca ions, Mg ions). The ratio [(Na ion + K ion + Li ion) / (Ca ion + Mg ion)] is preferably 1.0 or more, more preferably 1.5 or more, and still more preferably 2.0 or more.
As a metal ion (Me) between layers, an alkali metal ion is preferable, and Na ion is more preferable.
In order to obtain a clay mineral with a high ratio of alkali metal ions, it is only necessary to select the production area if it is a natural product, and when producing a granulated granule, it can be adjusted 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. And (ii) a method including a step of adding an alkali metal salt powder such as sodium carbonate or an aqueous solution when granulating the clay mineral pulverized into a powder form with a granulator.
The ratio of alkali metal ions to alkaline earth metal ions in the layered clay mineral (b) was determined by pulverizing the clay mineral with a mortar and passing 0.1 g of the sample that passed through a sieve with an opening of 125 μm into 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”, “Detasoft GIS”, “Detasoft GIB”, “Detasoft GISW” manufactured by Raviossa, “Odosolve” manufactured by Kurosaki Shirato Kogyo Co., Ltd. "K-400", "Round rosyl DGA212", "Round rosyl PR414", "Round rosyl DG214", "Round rosyl DGA powder", "Hulasoft-1 powder" manufactured by Sud Kemi, Pure bentonite, standard bentonite manufactured by CSM, Premium bentonite etc. are 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.
When using said layered clay mineral (b), it is preferable to crush beforehand until it becomes a suitable particle size as a surface modifier. 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 addition amount of the layered clay mineral (b) is preferably 2 parts by mass or more, more preferably 2.5 parts by mass or more, with respect to 100 parts by mass of the base detergent particles (a), from the viewpoint of sufficiently obtaining the effects of the present invention. More preferably, it is 3 parts by mass or more. Moreover, the upper limit is preferably 20 parts by mass or less, more preferably 18 parts by mass or less, and still more preferably 16 parts by mass or less. The layered clay mineral (b) contains a small amount of impurities such as quartz, cristobalite, calcite, feldspar, etc., particularly in the case of natural, but the addition amount of the layered clay mineral (b) includes those impurities. means.
The median particle diameter of the layered clay mineral (b) is preferably 1 to 40 μm, more preferably 3 to 35 μm, still more preferably 5 to 30 μm, and particularly preferably 5 to 25 μm.
Here, the median particle diameter of the layered clay mineral (b) can be measured using, for example, a laser diffraction / scattering particle diameter distribution measuring apparatus having a dry measurement unit. Specifically, measurement can be performed by optionally connecting a dry measurement unit “G0310630” to “Partica LA-950” manufactured by Horiba, Ltd. using the Mie scattering method. The setting of compressed air for powder dispersion is normal, and the obtained median diameter is the median particle diameter of the layered clay mineral (b).

<Zeolite (c)>
The zeolite (c) used for the surface modification of the present invention is a fine powder, and the average primary particle diameter is preferably 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.).
Moreover, it is preferable that the zeolite fine powder has high ion exchange ability and high alkali ability from a viewpoint of washing | cleaning performance.

<Other ingredients>
The surface modifier used in the present invention contains the layered clay mineral (b) and the zeolite (c) as essential components, 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.
In the present invention, when the base detergent particles (a) contain a liquid surfactant, water or the like, the layered clay mineral (b) 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 in order to further improve the adhesion of the layered clay mineral (b) and zeolite (c), it is preferable to add a binder component.
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>
The method for producing the detergent particles of the present invention is not particularly limited, but the step [1] for producing the base detergent particles (a), the base detergent particles (a) obtained in the step [1] are converted into the layered clay mineral (b) and It can be produced through the step [2] of surface modification with zeolite (c).
When the layered clay mineral (b) and zeolite (c), which are surface modifiers, are added in step [2], at the same time as the binder component is added at any stage before or after the addition, or at all stages, the surface modification is performed. The effect of adding the agent is preferred.
The step [1] for producing the base detergent particles (a) includes the step [A] for preparing a slurry of base detergent particles, the step [B] for preparing spray-dried particles by spray-drying the slurry, and the surface activity. It is preferable to go through the step [C] of preparing the agent composition (e) and the step [D] of adding and supporting the surfactant composition (e) to the spray-dried particles.
Hereinafter, the steps [A] to [D] will be described, but this is only an example, and the base detergent particles (a) used in the present invention can be produced by, for example, a dry neutralization method or the like, or spray-dried. It can also be obtained by dry-mixing the separate particles obtained by the method or the dry neutralization method. 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 step-Step [A]>
The slurry prepared in the step [A] is a base detergent particle (a) containing at least one component selected from a surfactant, a cleaning builder, an alkaline agent, and other detergent components used in ordinary powder detergents. ) Slurry that is pumpable and non-curable.
In addition, when a slurry containing substantially no surfactant is prepared, it is preferable because spray-dried particles having high particle strength and high bulk density can be obtained, and thus base detergent particles having excellent solubility can be obtained. On the other hand, when a slurry containing a surfactant is prepared from the viewpoint of cleaning performance, it is preferable in that the amount of the surfactant to be supported in the step [D] is reduced.
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 increase in slurry viscosity. Moreover, since the amount of water evaporated in the step [B] 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, all or almost all of the water is initially added to the mixing vessel, 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 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 the components have been added. In order to finally obtain a homogeneous slurry, after all the components are added to the slurry, it is preferably mixed for 10 minutes or more, more preferably 30 minutes or more.

<Process [1] -Process [B]>
In step [B], the slurry obtained in step [A] is spray-dried to prepare spray-dried particles. 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 thermal efficiency and particle strength of the spray drying particles. 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 after spray drying may be further dried by an air flow dryer, a fluidized bed dryer, a rotary dryer or the like.

<Process [1] -Process [C]>
The surfactant composition (e) to be prepared in the step [C] 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. 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.

<Process [1] -Process [D]>
In the step [D], the surfactant composition (e) obtained in the step [C] is added to and supported on the spray-dried particles obtained in the step [B].
The amount of the surfactant composition (e) to be carried on the spray-dried particles 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, from the viewpoint of exerting detergency. Preferably, 10-60 mass parts is 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 [A].
Examples of the method for supporting the surfactant on the spray-dried particles 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. (1) Add the spray-dried particles to the mixer and then add the surfactant while operating the mixer. (2) Spray the mixer. The dry particles and the surfactant are charged little by little. (3) After a part of the spray-dried particles is charged into the mixer, the remaining spray-dried particles and the surfactant are charged little by little. it can.
Among these methods, the above (1) 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.

As a mixing apparatus preferably used in the step [D], a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), a high speed mixer (Fukae Kogyo Co., Ltd.), a vertical granulator (Paulec Co., Ltd.), a Redige mixer ( Matsusaka Giken Co., Ltd.), Pro-Share Mixer (manufactured by Taiheiyo Kiko Co., Ltd.), Nauter Mixer (manufactured by Hosokawa Micron Co., Ltd.), and the like.
As a preferable mixing device, a strong shearing force is not easily applied to the spray-dried particles from the viewpoint of producing the base detergent particles (a) containing many mononuclear detergent particles having excellent solubility (the spray-dried particles are not easily broken down). And a device having good mixing efficiency from the viewpoint of 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 and more preferably 3 parts by mass or less with respect to 100 parts by mass of the spray-dried particles.
The step [D] includes a step of drying excess water while mixing and / or mixing with a mixer when an aqueous solution of a surfactant or the like is added in the slurry adjustment step [A]. 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, from the viewpoint of maintaining mononuclearity of the detergent particles, high-speed solubility, and particle diameter control, and 5 to 70 parts. A mass part is more preferable and 10-60 mass parts is still more preferable.

<Step [2]: Surface modification step>
In step [2], in order to modify the surface of the base detergent particles (a) obtained in step [1], a surface modifier containing layered clay mineral (b) and zeolite (c) is added. The surface modification step can be performed by repeating one step or two steps.
As described above, the median particle size of the layered clay mineral (b) is preferably 1 to 40 μm, and the average particle size of the primary particles of the zeolite (c) is preferably 10 μm or less. Is within the above range, a sufficient effect of improving caking resistance can be expected after avoiding a decrease in solubility.
The addition method of the surface modifier is not particularly limited, but the batch type or continuous type known mixer used in the step [D] is not easily applied with a strong shearing force (the base detergent particles are not easily disintegrated), And since mixing efficiency is high (dispersibility is high), since a surface modifier can be disperse | distributed moderately on the surface of a base detergent particle | grain, it is preferable.
Moreover, it is preferable to add a binder component in the step [2] because the adhesion of the surface modifier 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 batch-wise, (1) Add the surface modifier and the binder component separately or simultaneously while operating the mixer, (2) Add the surface modifier and the binder component alternately little by little, etc. Can be taken. 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.
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 the step [2] include the mixing apparatus described in the step [D].
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. 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. Moreover, the physical properties of the spray-dried particles, the surfactant composition 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 diameter: After vibrating for 5 minutes using a standard sieve (mesh size: 2000 to 125 μm) of JIS Z8801, the median diameter was calculated from the mass fraction depending on the size of the sieve mesh.
(3) Bulk density: Measured by the method defined in JIS K3362.
(4) Water-insoluble matter The total mass [a] of the aluminum foil and the mesh net (110 mmφ: 400 mesh or 200 mesh) cut into 150 mm × 150 mm was measured with a precision balance.
Add 1 L of 5 ° C. tap water to a 1 liter beaker, add a stirrer piece (35 mm × 8 mmφ), stir at 800 rpm with a magnetic stirrer, add 1.000 g of the weighed detergent particles and continue stirring for 10 minutes. After a minute, it was filtered through a mesh net fixed to a holder. The used beaker, stirrer piece and holder were rinsed with water at 5 ° C., and the residue was collected on the mesh.
The used mesh net is placed on a filter paper, removed excess water and bubbles, wrapped in aluminum foil cut to 150 mm x 150 mm, so that no residue is lost, dried at 105 ° C for 30 minutes, and then placed in a desiccator. After cooling for 10 minutes, the mass [c] was measured with a precision balance.
Water-insoluble content (%) = (mesh after operation + aluminum foil [c] −mesh before operation + aluminum foil [a]) / (sample mass [b] to be tested)

(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 opened on a sieve (4760 μm opening according to 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 A to D ranks were used.
Rank A: The surface of about 1/4 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 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.

Production Example 1 (Preparation of spray-dried particles)
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 obtained spray-dried particles 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)
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.

Example 1 (Preparation of detergent particles)
50 parts of the spray-dried particles 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), 6.5 parts of sodium carbonate, crystallinity 2 parts of sodium silicate (manufactured by Tokuyama Siltec Co., Ltd., pulverized pre-feed 6N and used with an average particle size of 10 μm) are charged, and the main shaft (stirring blade, rotation speed: 60 rpm, peripheral speed: 1.6 m / s) ), And 21.3 parts of the surfactant composition obtained in Production Example 2 (effective portion 19.1 parts, moisture 2.2 parts, 80 ° C.) was added in 2 minutes. Stirring was performed for 5 minutes, and the surfactant composition was supported on the spray-dried particles to obtain base detergent particles.
Layered clay mineral (Radiosa, smectite-type layered clay mineral, “bentonite”, average 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) particle size: 12 [mu] m, the main _{component: [Mg a Al b (Si} 2 O 5) 4 (OH) 4] X- · Me X +) after the addition of the zeolite 5 parts and 6 parts, the spindle (rotation speed: 120 rpm, (Circumferential speed: 3.1 m / s) and chopper (rotation speed: 3600 rpm, peripheral speed: 28 m / s) were 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 adding 10 parts of the zeolite, the main shaft (rotation speed: 120 rpm, (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 detergent particles. The moisture content of the obtained detergent particles was 1.4%, and the water evaporation rate of the surfactant composition was 35%. Table 1 shows the composition and physical properties of the resulting detergent particles.

Examples 2-4 and Comparative Examples 1-2 (Preparation of detergent particles)
In Example 1, detergent particles were obtained in the same manner as in Example 1 except that the input amounts of sodium carbonate particles and layered clay mineral were changed to the amounts shown in Table 1. Table 1 shows the composition and physical properties of the resulting detergent particles.
Comparative Example 3 (Preparation of detergent particles)
In Example 1, detergent particles were obtained in the same manner as in Example 1 except that the timing of adding the layered clay mineral was changed so as to be added simultaneously with spray-dried particles, sodium carbonate, and crystalline sodium silicate. The obtained detergent particles were not coated with a surface modifier composed of layered clay mineral (b) and zeolite (c). 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 are excellent in solubility and storage stability. On the other hand, in Comparative Example 1, since the ratio of the layered clay mineral to the zeolite is small, the caking resistance after storage and the stain resistance are significantly inferior to those of the Examples. Since Comparative Example 2 has a large ratio of the layered clay mineral to the zeolite, the solubility at both the initial stage and after storage is significantly inferior to that of the Example. Comparative Example 3 is blended with the same amount of layered clay mineral as in Example 1 and is not inferior to the Example regarding caking resistance and stain resistance, but the layered clay mineral is not a component of the surface modifier. Since it is used as a component of the base detergent particles, contact with the surfactant composition is likely to occur, and the solubility is remarkably inferior to the examples.
Based on the above results, when the mass ratio of [layered clay mineral (b) / zeolite (c)] is within the scope of the present invention, it is possible to achieve extremely excellent solubility and storage stability at the same time. Obviously you can. Moreover, the detergent particles of Examples 1 to 4 have a bulk density and an average particle size suitable for a compact detergent.

Claims (4)

A detergent particle obtained by coating 100 parts by mass of base detergent particles (a) with 10 to 50 parts by mass of a surface modifier containing lamellar clay mineral (b) and zeolite (c), wherein lamellar clay mineral (b ) Median particle size of 1 to 40 μm, the average particle size of primary particles of zeolite (c) is 0.1 to 10 μm , and the mass ratio of [layered clay mineral (b) / zeolite (c)] is 0.1. 0.6 der is, base detergent particles (a) is, with respect to the spray dried particles of median size containing a surface active agent more than 10% by weight 180~350μm (d) 100 parts by weight of the surfactant composition Detergent particles obtained by supporting 5 to 60 parts by mass of the product (e) . The detergent particle according to claim 1, wherein the layered clay mineral (b) is a smectite type layered clay mineral. The detergent particle according to claim 1 or 2 , wherein the layered clay mineral (b) is mainly composed of the one represented by the following formula (I).
_{[Mg a Al b (Si 2} O 5) 4 (OH) 4] X- · Me X + (I)
(Wherein a, b and x are 0 <a ≦ 6, 0 <b ≦ 4, x = 12- (2a + 3b), and Me ^{X +} is Na, K, Li, Ca, Mg and NH _4. At least one metal or ammonium charge-balance cation selected from the above, wherein the molar ratio of alkali metal ions to alkaline earth metal ions [(Na + K + Li) / (Ca + Mg)] is 1.0 or more. .) A detergent composition comprising the detergent particles according to any one of claims 1 to 3 .