JP2013035999A - Composite particle - Google Patents

Abstract

Provided are composite particles containing an alkali metal silicate exhibiting excellent solubility even after storage, and a detergent composition containing the same.
Composite particles containing alkali metal silicate particles (A) and aldonate (B). Moreover, it is related with the detergent composition containing the composite particle | grains of this invention, and detergent components other than (A) and (B). Water-insoluble matter after storage is reduced, and composite particles containing alkane metal silicate particles having excellent solubility after storage, and a detergent composition containing the same are obtained.
[Selection figure] None

Description

  The present invention relates to composite particles and a detergent composition containing the same.

  It is known that an alkali metal silicate is blended in a cleaning agent as an alkali agent, and a crystalline alkali metal silicate is blended as an agent combining an alkali agent and a cation exchanger. For example, as described in Patent Document 1, high-concentration of sodium metasilicate, which is a crystalline alkali metal silicate, in the field of industrial automatic dishwashing that efficiently cleans hard surfaces such as metal, glass, ceramics, and plastics Powdered and solid detergents have been proposed. Usually, alkali metal silicates can be used as a skeletal agent when spray-dried and powdered by blending a small amount in a detergent slurry, but there is concern that the solubility of the particles themselves will be affected when blended in large amounts. Is done. Therefore, a method of blending separately instead of spray-dried particles is also employed. For example, it is blended by granulating detergent components other than alkali metal silicate and then mixing alkali metal silicate with powder, or mixing with spray-dried detergent particles and stirring and granulating with a binder such as nonionic surfactant. ing.

  However, amorphous alkali metal silicates have a problem that silica is formed by moisture and carbon dioxide in the air, and water-insoluble components are easily formed. On the other hand, a detergent composition in which crystalline alkali metal silicate (hereinafter sometimes referred to as crystalline alkali metal silicate) is blended with detergent particles is also known (Patent Document 2). In the case of crystalline, the formation of water-insoluble substances can be suppressed as compared with amorphous, but it is not sufficient. Furthermore, it absorbs moisture and carbon dioxide in the air to form kanemite, causing deterioration in performance and quality.

  Regarding crystalline alkali metal silicate, Patent Document 3 discloses particles having excellent water dispersibility obtained by granulating crystalline alkali metal silicate using polyethylene glycol, nonionic surfactant and / or anionic surfactant paste. Is disclosed. Patent Documents 4 and 5 disclose a technique for improving storage stability by coating or granulating a crystalline alkali metal silicate with a fatty acid and a nonionic surfactant or carboxymethylcellulose. However, these methods have not been able to suppress a decrease in solubility due to storage of alkali metal silicate.

  On the other hand, a crystalline alkali metal silicate has a property of exhibiting higher alkalinity than an amorphous one when dissolved in water. Crystalline alkali metal silicates are superior to amorphous ones in the formation of water-insoluble denatured materials, but they absorb water and carbon dioxide in the air to become amorphous and become silica as described above. A water-insoluble component is formed or anodized to cause performance / quality degradation.

  Patent Document 6 describes a method of suppressing solidification of a crystalline alkali metal silicate by coating with an organic substance containing substantially no water. In Patent Document 7, an inorganic acid, an organic acid, an acidic polycarbonate, or the like is reacted with an alkali metal salt particle surface to perform coating or the like, thereby imparting appropriate solubility and disintegration to the obtained particle. It is described that various problems that occur during dissolution of can be solved. Patent Document 8 includes an additive for a powdered garment detergent containing a specific structure alkali metal silicate, a carboxylic acid polymer, a water-soluble inorganic salt, and an aluminosilicate with reduced generation of water-insoluble matter. Agents are described.

  Although the techniques as described above are known, alkali metal silicate particles having excellent storage stability and less problem of decrease in solubility after storage are desired. Since the problem of the decrease in solubility after storage becomes more apparent as the content of alkali metal silicate particles in the detergent increases, it becomes a more important solution in a system with a high content of alkali metal silicate particles.

Japanese Patent Laid-Open No. 11-5998 Japanese Patent Laid-Open No. 2-178398 JP-T 6-502445 WO 97/033968 pamphlet International Publication No. 97/034978 Pamphlet JP-A-9-208218 JP-A-10-251686 JP 2009-144116 A

  The subject of this invention is providing the composite particle containing the alkali metal silicate which shows the outstanding solubility after a preservation | save, and the detergent composition containing this.

  The present invention relates to composite particles containing alkali metal silicate particles (A) and aldonates (B).

  Moreover, this invention relates to the detergent composition containing the composite particle | grains of the said invention, and detergent components other than an alkali metal silicate particle | grain (A) and an ardonate salt (B).

  In the present invention, “composite” for composite particles refers to alkali metal silicate (A), aldonate (B), and other compounds, particularly organic compounds, or organic compounds and inorganic substances. It means that a compound adheres to each other or is adsorbed or absorbed to form a solid.

  ADVANTAGE OF THE INVENTION According to this invention, the water-insoluble content after a preservation | save is reduced and the composite particle containing the alkali metal silicate particle | grains excellent in the solubility after a preservation | save is provided. In addition, the detergent composition containing the composite particles of the present invention also has a reduced water-insoluble content after storage and excellent solubility after storage.

<Alkali metal silicate (A)>
The alkali metal silicate particles (A) are amorphous or crystalline powders having an average particle diameter of preferably 1 to 1000 μm, preferably 1 to 500 μm. In particular, an alkali metal silicate whose composition is represented by the following formula (1) is preferable.
xM ₂ O.ySiO ₂ .zH ₂ O (1)
[In formula, M shows Na and / or K, and is y / x = 0.5-1.9 (molar ratio) z = 0-10. ]

The alkali metal silicate represented by the general formula (1) may contain other elements and / or compounds in an amount of up to 1% by mass. Examples of other elements include aluminum, iron, and titanium, and examples of other compounds include Al ₂ O ₃ and Fe ₂ O ₃ .

  Examples of the alkali metal silicate represented by the general formula (1) include sodium metasilicate anhydrate, sodium metasilicate pentahydrate, sodium metasilicate nonahydrate, etc. Among them, sodium metasilicate 5 Hydrates and sodium metasilicate nonahydrate are preferably used.

<Aldonate (B)>
The aldonic acid which is an acid type compound of the aldonic acid salt used in the present invention is a polyoxycarboxylic acid corresponding to a carboxylic acid group obtained by oxidizing an aldehyde group of aldose and represented by the general formula (2). .
HOCH ₂ (C * HOH) _n COOH (2)
(However, n represents an integer of 0 or more, and C * represents an asymmetric carbon atom.)

  Since aldonic acid has an asymmetric carbon atom represented by C * as described above, there are many optical isomers. As for n in General formula (2), 0-5 are preferable.

  Aldonic acids are classified by the number of carbon atoms, those having 4 carbon atoms (n = 2 in the general formula (2)) are tetronic acids, those having 5 carbon atoms (n = 3 in the general formula (2)) are those Pentonic acid having 6 carbon atoms (n = 4 in the general formula (2)) is generically called hexonic acid. Specific examples of the aldonic acid include, for example, glycolic acid having 2 carbon atoms (n = 0 in the general formula (2)) (also known as hydroxyacetic acid), 3 carbon atoms (in the general formula (2), n = 1) Glyceric acid, erythronic acid having 4 carbon atoms (n = 2 in the general formula (2)), threonic acid, ribbon acid having 5 carbon atoms (n = 3 in the general formula (2)), arabon Acid, xylonic acid, lyxonic acid, 6 carbon atoms (n = 4 in the general formula (2)) gluconic acid, aronic acid, altronic acid, mannonic acid, gulonic acid, idic acid, galactonic acid, talonic acid, carbon There are several glucoheptonic acids and the like of 7 (n = 4 in the general formula (2)), and there are D-form, L-form and DL-form each.

  Preferred among the aldonic acids are xylonic acid having 5 carbon atoms, gluconic acid having 6 carbon atoms, or an optical isomer of gluconic acid described later. In particular, gluconic acid is preferable. Gluconic acid is rarely present alone in an aqueous solution. Usually, a part of gluconic acid forms a lactone ring with a hydroxyl group at the γ-position or δ-position, and becomes γ-gluconolactone or δ-gluconolactone, respectively. And δ-gluconolactone is said to exist as an equilibrium mixture of the three. There are D-form, L-form and DL-form gluconic acid, and any of them may be used, but generally D-gluconic acid of D-form can be easily obtained. In addition, as optical isomers of gluconic acid, for example, there are, for example, alloic acid, altronic acid, mannonic acid, gulonic acid, idonic acid, galactonic acid, talonic acid, etc. These may be used.

  Examples of aldonic acid salts include alkali metal salts, alkaline earth metal salts, iron salts, copper salts and the like, and alkali metal salts are preferred from the viewpoint of solubility. Among the aldonic acid salts, examples of the gluconate include lithium gluconate, sodium gluconate, potassium gluconate, magnesium gluconate, calcium gluconate, barium gluconate, iron (II) gluconate, copper gluconate (II ) And the like. Of these, lithium gluconate, sodium gluconate, and potassium gluconate are preferably used. Ardonates, especially gluconates, can be used alone or in combination of two or more.

  The aldonic acid salt (B) used for the composite particles of the present invention preferably has an average particle size as a raw material of 1 to 1000 μm, more preferably 1 to 500 μm, and still more preferably 1 to 300 μm.

  The composite particles of the present invention are [aldonate (B) content] / [alkali metal silicate particle (A) content + aldonate (B) content] (where alkali metal silicate particles The mass ratio of (A) is an anhydrous salt content) is 0.05 to 0.75, more preferably 0.1 to 0.70, and further 0.2 to 0.6. Is preferable from the viewpoint of storage stability and washing performance.

  In the composite particles of the present invention, the total content of alkali metal silicate particles (A) and aldonates (B) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. The upper limit value can be selected from 100% by mass or less, further 99.9% by mass or less, and more preferably 99% by mass or less. The composite particles of the present invention may contain components other than alkali metal silicate particles (A) and aldonates (B) in a range that does not impair solubility after storage, but are substantially alkali metal silicates. Particles (including crystal water) (A) and aldonate (B), that is, the content of alkali metal silicate particles (A) (including crystal water) and aldonate (B) in the composite particles The total is preferably 100% by mass. In addition, when other components are included, the composite particles of the present invention have a total content of alkali metal silicate particles (including crystal water) (A) and aldonate (B) of 70 in the composite particles. It is preferably at least mass%, more preferably at least 80 mass%, and even more preferably at least 90 mass%. Moreover, 99.9 mass% or less is preferable and 99 mass% or less is more preferable. When the component (A) is converted to an anhydrous salt, the total content of the component (A) and the component (B) is preferably 40% by mass or more, more preferably 45% by mass or more in the composite particles. 55 mass% or more is more preferable. Moreover, 99 mass% or less is preferable, 95 mass% or less is more preferable, and 90 mass% or less is more preferable.

  When the alkali metal silicate absorbs carbon dioxide during storage, it is decomposed by carbon dioxide and the silicate gel is released. When it is dehydrated and condensed, it becomes water-insoluble silica and a water-insoluble matter is generated. However, since the composite particles of the present invention contain an aldonic acid salt having moisture retention, dehydration condensation of the silicate gel is suppressed, so that it is considered that the generation of silica is suppressed and the water-insoluble content is reduced.

  As components other than the alkali metal silicate particles (A) and the aldonate (B), a part of them will be described later. For example, surfactants, other high molecular polymers such as binders, other water carbonates, sulfates and the like. Inorganic salts and the like.

  The form of the composite particles of the present invention is not particularly limited, but the aldonic acid salt (B) is allowed to contact the surface of the alkali metal silicate particles (A), and the alkali metal silicate particles (A) are in direct contact with each other. From the viewpoint of making it difficult, a form in which there are preferably 2 or more, more preferably 3 or more, particularly preferably 4 or more aldonic acid (B) particles on the surface of one alkali metal silicate particle (A). It is desirable that For example, the form of the aggregate (form A) in which the alkali metal silicate particles (A) and the aldonate (B) are in intimate contact with each other, the alkali metal silicate particles (A) exist as single particles, and the surface The form (form B) in which two or more aldonic acid salts (B) are present in contact with each other is mentioned. In the case of Form B, the average particle size of the aldonate (B) is preferably smaller than the average particle size of the alkali metal silicate particles (A). In particular, in the form B, a form in which the alkali metal silicate particles (A) are substantially covered with the aldonic acid salt (B) is particularly preferable. In addition, when the composite particles are granules, the particle shape thereof preferably has a small surface area from the viewpoint of enhancing storage stability (moisture absorption resistance / moisture retention). Specifically, it is preferably spherical and preferably has a smooth surface. Furthermore, it is preferable for improving the storage stability that the alkali metal silicate particles (A) and the aldonate (B) in the granules are uniformly dispersed and form granules in contact with each other alternately. . For example, in order to increase smoothness and sphericity, a processing apparatus such as a Malmerizer manufactured by Fuji Paudal Co., Ltd., a wet / dry granulator Comil manufactured by Powrec Co., Ltd., or the like can be used.

  The composite particles of the present invention can be obtained by combining alkali metal silicate particles (A) and aldonates (B). From the viewpoints of dispersibility and storage stability, the average particle size of the composite particles of the present invention is preferably 10 to 3000 μm, more preferably 50 to 600 μm, and still more preferably 100 to 500 μm. The average particle diameter of the alkali metal silicate particles (A) in the composite particles of the present invention is preferably 1 to 1000 μm, more preferably from the viewpoints of dispersibility, storage stability, and dispersibility in water. 1 to 500 μm. Moreover, from the same viewpoint, the average particle diameter of the aldonic acid salt (B) in the composite particles of the present invention is preferably 1 to 1000 μm, more preferably 5 to 500 μm, and still more preferably 20 to 300 μm. . Further, in the composite particles of the present invention, the composite particles have a form in which the average particle size of the aldonate (B) is smaller than the average particle size of the alkali metal silicate particles (A), and the form of the composite particles is alkali metal silicate particles ( Since it becomes easy to become the form which the aldonic acid salt (B) contacted the surface of A), it is preferable.

  The average particle diameter of the composite particles and the average particle diameters of the alkali metal silicate particles (A) and aldonates (B) in the composite particles can be measured by the methods described in the examples.

The composite particles of the present invention can be obtained by mixing alkali metal silicate particles (A) and aldonate (B) while applying mechanical force. Specific production methods include the following methods (i) to (iii).
(I) A method in which the alkali metal silicate particles (A) and the aldonate (B) each having a particle diameter in a certain range are mixed by a mixer to be combined.
(Ii) A method in which alkali metal silicate particles (A) and aldonate (B) are added to a pulverizer and mixed while being pulverized.
(Iii) A method in which alkali metal silicate particles (A) and aldonate (B) are mixed and granulated by a granulator.

  In this case, the average particle size before pulverization of the alkali metal silicate particles (A) and the aldonic acid salt (B) is not particularly limited as long as the obtained composite particles fall within a predetermined range. It is preferable that it is the said range.

  As a mixing apparatus used for producing the composite particles of the present invention, (1) a mixer having a stirring shaft in the mixing tank and having a stirring blade attached to the shaft to mix powders, for example, Fukae Industry High speed mixer, Henschel mixer, etc. manufactured by Co., Ltd. (2) It consists of a vertical cylinder with a powder inlet and a main shaft with a mixing blade. The main shaft is supported by an upper bearing and the discharge side is free. (3) The raw material is put into the upper part of a disk having a stirring pin, and the disk is rotated at a high speed to perform mixing by a shearing action. Continuous mixers, for example, flow jet mixers manufactured by Powder Research Powtex Co., Ltd., spiral pin mix manufactured by Taiheiyo Kiko Co., Ltd. Chromatography, and the like.

  After the alkali metal silicate particles (A) and the aldonate (B) are combined, it is preferable to perform a pulverization treatment in order to control the particle size. The crushing apparatus that can be used is not particularly limited. For example, a pulverizer described in pages 826 to 838 of Chemical Engineering Handbook (5th revised edition) (edited by Chemical Society of Japan, published by Maruzen Co., Ltd.) is used. Specific examples include (1) devices for crushing by pressure and impact force, such as jaw crusher, gyre crusher, roll crusher, roll mill, etc. (2) A striking plate is fixed around the rotor rotating at high speed, and the rotor and the impact Equipment for crushing processed material by shearing force with a plate, such as hammer mill, impact crusher, pin mill, etc. (3) A device that rotates while a roll or a ball is pressed on a ring and pulverizes the processed material between them , For example, a ring roller mill, a ring ball mill, a centrifugal roller mill, a ball bearing mill, etc. (4) A cylindrical grinding chamber is provided, and a ball or rod is placed as a grinding medium in the grinding chamber and rotated or vibrated. Grinding devices for pulverizing processed materials, such as ball mills, vibration mills, planetary (5) Equipped with a cylindrical pulverization chamber, and a pulverization medium such as balls or beads is placed in the pulverization chamber, and processed by shearing and frictional action by a disc type or annular type stirring mechanism inserted in this medium For example, a tower mill, an attritor, and a sand mill.

  When the composite particles of the present invention are prepared by mixing treatment, when the average particle size of the aldonic acid salt (B) is 1/10 or less of the average particle size of the alkali metal silicate particles (A), the alkali metal silicate It becomes easy to take the form which coat | covers the surface of a salt particle (A) with an aldonic acid salt (B). The composite particles having such a form are preferable because they are highly effective in increasing the storage stability of the alkali metal silicate particles (A). Examples of a mixing apparatus suitable for forming such a particle form include a hybridizer manufactured by Nara Machinery Co., Ltd., a mechanofusion, nobilta manufactured by Hosokawa Micron Corporation, and the like.

  In the present invention, the composite particles obtained above can be further granulated. Here, “granulation” is an operation of making an aggregate of particles having a substantially uniform shape and size (for example, an average particle diameter of 200 to 3000 μm) from a powdery raw material. As granulators, Fukae Pautech Co., Ltd. High Speed Mixer, High Flex Grall, Powrec Co., Ltd. Vertical Granulator, Taiheiyo Kiko Co., Ltd. Apex Granulator, Pro-Share Mixer Co., Ltd. Julia Mixer, Matsubo's Readyge Mixer, Japan Eirich Co., Ltd. Intensive Mixer, Fuji Powdal Co., Ltd. Malmerizer, Pelleter Double, Dalton Co., Ltd. Twin Dome Gran, Fine Disc Petter Examples include a briquette manufactured by East Industrial Co., Ltd., a briquetting machine manufactured by Hosokawa Micron Co., Ltd., a roller compactor manufactured by Freund Sangyo Co., Ltd. and turbo industrial Co., Ltd.

  During granulation, for the purpose of increasing the strength of the composite particles, a binder may be added within a range that does not impair dispersibility. As the binder, a known water-soluble binder or water-insoluble binder can be used. The binder is preferably used in an amount of 0.1 to 30% by mass, more preferably 1 to 10% by mass, based on the composite particles.

  Water-soluble binders include starch, dextrin, sodium alginate, gum arabic, casein, carboxymethylcellulose, calcium lignin sulfonate, carboxymethyl starch, sodium phosphate ester, glycerin, polyethylene glycol, polyvinyl alcohol, polyacrylamide, poly Examples include sodium acrylate and various surfactants.

  In addition, examples of the water-insoluble binder include sodium aluminate metasilicate, slaked lime, gypsum, cement, glue and the like. Among these, from the viewpoint of achieving both improvement in granule strength and dispersibility, sodium polyacrylate, polyethylene glycol, and sodium aluminate metasilicate are preferable, and sodium polyacrylate and sodium aluminate metasilicate are more preferable.

  From the viewpoint of solubility, the composite particles of the present invention preferably have a small amount of water-insoluble content by the measurement methods described in the examples. The amount of water-insoluble content (%) is preferably 2% or less, more preferably 1% or less, and even more preferably 0.5% or less in the measurement method described in the examples. The lower limit is 0%.

<Uses of composite particles>
The application of the composite particles of the present invention is not particularly limited. It can utilize in the system which mix | blends an alkali metal silicate. The composite particles themselves can be used as a detergent, and can be used as a detergent composition by adding to the base detergent described later.

<Detergent composition>
Since the composite particles of the present invention have high storage stability and contain components that function as an alkaline agent, they are suitable as a builder for detergents. When used as a detergent builder, the composite particles of the present invention are prepared in advance, and a detergent composition can be obtained by mixing a base detergent described later and other detergent additives as optional components.

  Base detergents include surfactants, alkali agents (such as alkali metal carbonates such as sodium carbonate) and sequestering agents (metal ion exchangers such as zeolite, organometallic chelating agents such as methylglycine diacetate) It contains a builder for detergents, and optionally contains a binder substance such as polyethylene glycol used for granulation, an extender such as sodium sulfate, and an organic solvent when used as a base. Optional other detergent additives include enzymes, bleaches (percarbonates, perborate, bleach activators, etc.), recontamination inhibitors (polyacrylates, carboxymethylcellulose, etc.), softeners , Reducing agents (sulfites, etc.), fluorescent brighteners, foam inhibitors (silicones, etc.), fragrances and the like. Other detergent additives may be granulated or particles composed of two or more components. Further, a fluorescent dye, a fragrance, or the like may be added to the entire particle by adding it to a mixture of a plurality of particles as long as the stability is not impaired.

  The detergent composition obtained by mixing the base detergent with the composite particles of the present invention and optional other additives for detergent is the composite particles of the present invention [preferably, from the viewpoint of cleaning performance, The total content of alkali metal silicate particles (A) (including crystal water) and aldonate (B)] is preferably 1% by mass or more, and preferably 5% by mass or more. It is more preferable that 10% by mass or more is mixed. Further, from the viewpoint of suppressing the generation of water-insoluble matter, it is preferably 70% by mass or less, more preferably 50% by mass or less, and further preferably 30% by mass or less. In addition, according to the present invention, even if the content of the alkali metal silicate (A) is increased, the generation of water-insoluble matter due to storage can be suppressed. Product can be prepared. Specifically, the content of the alkali metal silicate (A) in the detergent composition is 0.5% by mass or more, further 1% by mass or more, and further 3% by mass or more in terms of anhydrous salt. From the viewpoint of the effect of suppressing water-insoluble matter, it is preferably 30% by mass or less, more preferably 26% by mass or less.

  Further, the content of alkali metal silicate (except for the crystalline layered silicate) other than the composite particles in the detergent composition is preferably 0.5% by mass or less, more preferably 0, in terms of anhydrous salt. .1% by mass or less, more preferably substantially not contained.

  Examples of the surfactant include an anionic surfactant and a nonionic surfactant. Anionic surfactants include sulfates of higher alcohols or ethoxylates thereof, alkylbenzene sulfonates, paraffin sulfonates, α-olefin sulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid alkyls. Examples include salts of esters and fatty acid salts. Here, the salt is preferably an alkali metal salt such as a sodium salt or a potassium salt. Nonionic surfactants include higher alcohol ethylene oxide adducts, ethylene oxide / propylene oxide adducts, fatty acid alkanolamides, alkyl polyglycosides, and the like.

  As a builder, in addition to the composite particles of the present invention, an inorganic builder such as alkali metal carbonate, zeolite, amorphous aluminosilicate, phosphate, borate, nitrilotriacetate, ethylenediaminetetraacetate, Examples include organic builders such as tartrate, citrate, and acrylic acid (co) polymers.

  The use of the detergent composition of the present invention is not particularly limited, and is suitably used as a garment detergent, dish detergent, residential detergent, automobile detergent, body detergent, toothbrush, metal detergent and the like. In particular, a detergent for clothing is suitable.

  As an example of a composition preferable as a detergent for clothing, 1 to 30% by mass of the composite particles of the present invention (preferably as a total content of alkali metal silicate particles (A) and aldonate (B)), zeolite 10 Examples include 50% by mass, 1 to 50% by mass of a surfactant, 1 to 50% by mass of sodium carbonate, and 0.1 to 5% by mass of other components (enzyme, bleach, clay particles, etc.).

  The detergent composition of the present invention is preferably a powder detergent composition, and the average particle size is preferably 125 to 1000 μm.

  The detergent composition of the present invention has a water-insoluble content of 2% by mass or less, and further 1% immediately after preparation, as measured by the method described in the examples below (wherein the composite particles are replaced with the detergent composition for testing). % Is preferably 3% or less after 7 days of storage, further 2% or less, and further preferably 1% or less.

In the following Examples and Comparative Examples, the average particle diameter and the amount of water-insoluble matter were measured or calculated by the following methods. Moreover, the base detergent was manufactured by the following manufacturing examples.

(1) Measurement of average particle size of raw material The average particle size of the alkali metal silicate (A) and aldonate (B) as the raw material was measured as follows according to the range of the average particle size.
(1-1) Measurement of average particle diameter of 200 μm or more Opening is small on a saucer using a 9-stage sieve and a saucer of 125 μm, 180 μm, 250 μm, 355 μm, 500 μm, 710 μm, 1000 μm, 1400 μm, 2000 μm Stack in order from the sieve, add 100 g of granules from the top of the top 2000 μm sieve, cover and roll tap sieve shaker (manufactured by Heiko Seisakusho, tapping 156 times / minute, rolling: 290 times / And the mass of the particles remaining on each sieve and the saucer was measured, and the mass ratio (%) of the particles on each sieve was calculated. The mass ratio of the particles on the sieve with small openings is accumulated in order from the saucer. When the opening of the first sieve with a mass frequency of 50% or more is a μm, and the opening of the sieve that is one step larger than a μm is b μm, the cumulative mass frequency from the tray to the a μm sieve is c%, When the mass frequency on the a μm sieve is defined as d%, the average particle diameter can be obtained from the following equation.

(1-2) Measurement of average particle diameter of less than 200 μm Using a laser diffraction / scattering particle size distribution measuring apparatus (“LA920” manufactured by Horiba, Ltd.), ethanol was used as a dispersion medium, and after ultrasonic irradiation for 3 minutes. The volume median particle size (D50) when the particle size distribution was measured at a relative refractive index of 1.5 was taken as the average particle size.

(3) Measurement of the amount of water-insoluble matter The amount of water-insoluble matter is measured by (i) composite particles immediately after preparation, (ii) after preparation for 7 days under conditions of temperature 30 ° C., humidity 70%, CO ₂ concentration 0.3%. The preparation was carried out on the composite particles stored (iii) and after the preparation, the composite particles stored for 12 days under conditions of a temperature of 30 ° C., a humidity of 70%, and a CO ₂ concentration of 0.3%. Fill a 1-liter beaker (inner diameter 105 mm, height 150 mm, for example, manufactured by Iwaki Glass Co., Ltd.) with tap water adjusted to 5 ° C., and stir while keeping the water temperature at 5 ° C. constant in a water bath. Stirring was performed at a rotational speed (1000 rpm) at which the depth of the vortex with respect to the water depth was approximately 1/3 with a child (length: 35 mm, diameter: 8 mm, for example, model: ADVANTEC, manufactured by Teflon (registered trademark) round thin type). The composite particles weighed to 0.5 g were added and dispersed in water with stirring, and stirring was continued. Ten minutes after the addition, a 400-mesh wire mesh was passed through and dried at 105 ° C. for 30 minutes. The residue on the wire mesh was weighed, and [the remaining amount of wire mesh / 0.5 × 100] was defined as the water-insoluble content (%).

(4) Production Example of Base Detergent Ion exchange water was added to a mixing tank (capacity: 180 L) having a stirring blade having a length of 200 mm and heated while stirring. After the water temperature reached 55 ° C., sodium carbonate (Dense Ash, manufactured by Central Glass Co., Ltd.) was added, and then sodium sulfate (anhydrous neutral bow glass, manufactured by Shikoku Kasei Co., Ltd.) was added and stirred for 15 minutes. Thereafter, a 40% by mass sodium polyacrylate aqueous solution (weight average molecular weight 10,000, manufactured by Kao Corporation) was added, then sodium chloride (yaki salt, manufactured by Nippon Shiosha Co., Ltd.) was added, and the mixture was stirred for 15 minutes. Zeolite was added and stirred for 30 minutes to obtain 60 kg of a homogeneous slurry (water content 53 mass%). This slurry was spray-dried to obtain base granules having a water content of 1.2% by mass. The composition of the obtained base granule was composed of 8% by mass of sodium chloride, 12% by mass of sodium polyacrylate, 28% by mass of sodium carbonate, 26% by mass of sodium sulfate, and 26% by mass of zeolite. Next, base detergent particles were obtained by adding a surfactant or the like to the base granules as follows.

  36 parts by mass of the above base granule was charged into a 5 L readyge mixer (lab mixer M-5, manufactured by Matsuzaka Trading Co., Ltd.), and stirring was started at 100 rpm. 20 parts by mass of a 70 ° C. surfactant mixture (a liquid composed of 39% by mass of nonionic surfactant, 46% by mass of anionic surfactant, 2% by mass of polyethylene glycol and 13% by mass of water) The mixture was added in 3 minutes and stirred for 5 minutes. Furthermore, 1 part by mass of palmitic acid [trade name: LUNAC P-95, manufactured by Kao Corporation] was added to this mixer in 30 seconds, and then stirred for 3 minutes. Furthermore, 24 parts by mass of soda ash and 17 parts by mass of zeolite are added to this mixer, surface coating is performed, and the detergent particles are classified using a sieve having an opening of 1180 μm to obtain base detergent particles having a particle diameter of less than 1180 μm. It was. The average particle size of the base detergent particles was 320 μm.

Example 1 and Comparative Example 1
(1) Example 1-1 to Example 1-4
Alkali metal silicate particles (Na ₂ SiO ₃ .5H ₂ O, Nippon Chemical Industry Co., Ltd.) having an average particle size of 680 μm and Na gluconate (Wako Pure Chemical Industries) having an average particle size of 190 μm are mixed in the ratios shown in Table 1. A composite particle was obtained. Table 1 shows the water-insoluble content of the obtained composite particles. In Table 1, (B) / [(A) + (B)] (mass ratio) is [content of ardonate (B)] / [content of alkali metal silicate particles (A) + The content ratio of the ardonate (B)], and the content of the alkali metal silicate particles (A) is a content in terms of anhydrous salt. Moreover, the ratio of (A) + (B) in the composite particles is based on the content when the alkali metal silicate particles (A) contain crystal water (solid) and the content when converted to anhydrous salt, respectively. Based on that.

(2) Example 1-5 to Example 1-8
Alkali metal silicate particles (Na ₂ SiO ₃ .9H ₂ O, Nippon Chemical Industry Co., Ltd.) having an average particle size of 614 μm and Na gluconate (Wako Pure Chemical Industries) having an average particle size of 190 μm are mixed in the ratios shown in Table 1. A composite particle was obtained. Table 1 shows the water-insoluble content of the obtained composite particles.

(3) Comparative Examples 1-1 to 1-2
Alkali metal silicate particles (Na ₂ SiO ₃ .5H ₂ O, Nippon Chemical Industry) (Comparative Example 1-1) or alkali metal silicate particles (Na ₂ SiO ₃ .9H ₂ O, Nippon Chemical Industry) (Comparative Example 1) -2) only was used as composite particles for convenience. Table 1 shows the amounts of water-insoluble components.

* Mass ratio in which the content of alkali metal silicate particles (A) is converted into anhydrous salt **% by mass in which the content of alkali metal silicate particles (A) is converted into anhydrous salt

  From Table 1, Examples 1-1 to 1-8 using the aldonic acid salt of the component (B) are more water than Comparative Examples 1-1 to 1-2 not containing the aldonic acid salt of the component (B). It can be seen that the insoluble content is very small. According to the present invention, it is clear that the formation of water-insoluble matter can be suppressed by combining the alkali metal silicate particles (A) and the aldonate (B).

Example 2 and Comparative Example 2
The composite particles of Example 1-6 or Comparative Example 1-2 and the base detergent obtained in the above production example were mixed to obtain a powder detergent composition. The mixing of the composite particles and the commercial powder detergent was performed by placing both in a polyethylene bag with a chuck (Unipack, size F) and shaking by hand for 15 seconds. The obtained powder detergent composition was measured for the amount of water-insoluble components immediately after preparation and stored for 7 days (provided that the composite particles are a powder detergent composition) in the same manner as in Example 1 and the like. The results are shown in Table 2.

* Mass ratio in which the content of alkali metal silicate particles (A) is converted into anhydrous salt **% by mass in which the content of alkali metal silicate particles (A) is converted into anhydrous salt

  From the results of Table 2, the powder detergent compositions of Examples 2-1 to 2-7 containing the composite particles of Example 1-6 are Comparative Examples 2-1 to 2-1 containing the composite particles of Comparative Example 1-2. It is clear that the water-insoluble content after storage is reduced as compared with the powder detergent composition of 2-7.

Formulation Example In Examples 1-1 to 1-8, when using xylonic acid Na or mannonic acid Na instead of Na gluconate, composite particles of the present invention are obtained.

  Further, composite particles using Na xylonic acid instead of Na gluconate of Example 1-6 were prepared, and the composite particles were mixed with a base detergent in the same manner as in Example 2-1, whereby the powder detergent of the present invention. A composition is obtained.

  Further, with respect to 100 parts by mass of the powder detergent composition of Example 2-1, sodium percarbonate coated with sodium silicate as one or more of three kinds of enzyme particles of protease, cellulase and amylase as other detergent additives Particles, bleach activator particles containing sodium alkanoyloxybenzenesulfonate, and granulated particles of sodium carbonate and bentonite, each having the same average particle size as the composite particles, and other detergent additives. When one or more kinds are mixed at a ratio of 1 part by mass, 5 parts by mass or 10 parts by mass under the condition that the total does not exceed 50 parts by mass, the powder detergent composition of the present invention is obtained.

Claims (4)

  Composite particles containing alkali metal silicate particles (A) and aldonate (B).   [Content of Ardonate (B)] / [Content of Alkali Metal Silicate Particles (A) + Content of Ardonate (B)] (Here, the content of alkali metal silicate particles (A) is 2. The composite particle according to claim 1, wherein the mass ratio of the content in terms of anhydrous salt is from 0.05 to 0.75.   The composite particles according to claim 1 or 2, wherein the total content of the alkali metal silicate particles (A) and the aldonate (B) is 70% by mass or more.   A detergent composition comprising the composite particles according to any one of claims 1 to 3 and a detergent component other than alkali metal silicate particles (A) and aldonates (B).