JP5213092B2 - Granular detergent composition for clothing, method for producing the same, and method for using the same - Google Patents

Description

  The present invention is suitable for washing textiles such as clothes, towels and sheets (hereinafter collectively referred to as “clothing” in the present invention), and particularly for clothing suitable for washing clothes using an electric washing machine. The present invention relates to a granular detergent composition, a method for producing the same, and a method for using the same.

  Conventionally, washing of clothes using an electric washing machine such as a fully automatic washing machine and a two-tank automatic washing machine has been widely performed. In washing using these electric washing machines, a powder detergent is generally used, and at the start of washing, the user puts the above powder detergent into the washing tub or a predetermined detergent supply port. It is supposed to be thrown in.

  However, since the powder of the cleaning agent is scattered when the powder cleaning agent is added, there is a concern that the powder cleaning agent may adhere to the skin of the worker or may be inhaled into the lungs, which is a concern in terms of hygiene management. In addition, the powder cleaning agent is dissolved using water or hot water poured into the washing tub, but it is difficult to dissolve the powder cleaning agent so that the concentration of each component is uniform. is there.

  Further, in order to prevent such powder scattering, it has been proposed that the powder cleaning agent is individually packaged with a water-soluble film such as polyvinyl alcohol, but there is a problem that the cost is high.

  On the other hand, it has been proposed to use a liquid detergent instead of the powder detergent. However, the liquid cleaning agent is hygienic because there is no risk of scattering like powder, but there is a problem that a relatively large amount of cleaning agent is required because the proportion of the solvent is high and the proportion of the active ingredient is low. . For this reason, an exchange unit becomes a heavy article, and exchange work is not easy, and a lot of space is required to store it. Moreover, since the thick polyethylene container generally used for storing the liquid cleaning agent is flame retardant and hardly decomposable, its disposal is a problem.

Therefore, it has been studied to suppress powder formation by granulating a powder detergent larger than before, for example, for high-density granular detergents comprising surfactants, builders, surface modifiers, extenders, and the like. A continuous granulation method and apparatus for high-density detergent particles in which detergent powder is continuously sized and taken out in a specially configured granulation chamber (see Patent Document 1) is proposed. Has been.
Japanese Patent No. 2636036

  However, since the high-density detergent particles of Patent Document 1 are coarsened while spraying relatively fine powders with a binder, the particles are sized and taken out as relatively large particles continuously. However, it is easy to mix fine powder and it cannot be said that powdering is sufficiently prevented. Moreover, the comparatively fine thing with an average particle diameter of 540-600 micrometers is only described as an Example, and when set to the particle | grain larger than it, a fine powder falls from the particle | grain surface by friction of particle | grains. There is also a risk, and further powdering is expected. Moreover, it is doubtful whether excellent dispersibility, solubility, storage stability and the like can be obtained.

  The present invention has been made in view of such circumstances. (1) Excellent cleaning performance and storage stability, especially those containing a chlorine bleach or an oxygen bleach are stored under conditions of high temperature and high humidity. Even if it is, the decomposition of the bleaching agent is minimized, it has the desired bleaching performance, (2) it has less dusting and is excellent in workability and safety during handling, (3) It is an object to provide an excellent granular detergent composition for clothing having the desired dissolution performance despite being granulated and having these performances. It is also an object of the present invention to provide a production method and a usage method thereof.

In order to achieve the above object, the present invention contains the following components (A) to (D) as essential components, and a raw material composition containing 0.1 to 9% by mass of water has the following (A ) To (D) are prepared in the form of a slurry and are not spray-dried or heated and melted, and supplied to a high-speed agitation granulator to be batch-granulated. JIS K-3362: The average particle size obtained from the particle size measured by the screening method described in 1998 “Synthetic detergent test method” is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0. The first gist of the present invention is a granular detergent composition for clothing comprising an aggregate of substantially spherical granular bodies set to 0.7 to 1.0.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combined [Equation 1]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]

In addition, the present invention contains the following components (A) to (D) as essential components and does not contain water, and at least one of these components (A) to (D) is a hydrate. In a state where the following components (A) to (D) are prepared in the form of a slurry and are not spray-dried or heated and melted, they are supplied to a high-speed agitation granulator and are batch-type. In addition, each component particle is bound and granulated with moisture derived from the hydrate, and is measured by a screening method described in JIS K-3362: 1998 “Synthetic detergent test method”. The average spherical particle size determined from the particle size is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is set to 0.7 to 1.0. Granular wash for clothing characterized by comprising an aggregate Cleaner composition.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combine [number 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]

Further, among these, the third aspect of the present invention is a granular detergent composition for clothing in which the sequestering agent of the component (B) is an alkali metal phosphate, and the component (B). The fourth gist of the present invention is a granular detergent composition for clothing in which the sequestering agent is a phosphorus-free sequestering agent.

And among the granular detergent composition for clothes which is the 4th gist of the present invention, the phosphorus-free sequestering agent is selected from aminocarboxylic acids, hydroxyaminocarboxylic acids, and salts thereof. A granular detergent composition for clothes that is at least one of the above is a fifth aspect .

In addition, among these, the sixth aspect of the present invention is a granular cleaning composition for clothing in which the surfactant of the component (C) is a nonionic surfactant, and the (D) Granules for clothing, wherein the component polyelectrolyte polymer is at least one selected from a polymer comprising at least one of acrylic acid and maleic acid as a monomer, a copolymer thereof, and a water-soluble alkali salt thereof the detergent composition as a seventh gist of, those natural polymer derivatives, starch derivatives, cellulose derivatives, acrylic acid derivatives, at least one binder selected from polyvinyl alcohol and polyethylene glycol were added during granulation A granular detergent composition for clothing is an eighth aspect .

Furthermore, the present invention includes a granular detergent composition for clothing, in which at least one of the following (F) component and (G) component is mixed with the aggregate of the substantially spherical granular materials. Let it be the 9th summary.
(F) Chlorine bleach or oxygen bleach with an average particle size of 0.5 to 3.0 mm. (G) Detergent enzyme having an average particle size of 0.5 to 3.0 mm.

Further, the present invention is a method for producing a granular detergent composition for clothing according to any one of the first to ninth aspects, wherein a raw material composition for preparing a substantially spherical granular material is used as each raw material. the ingredients and do not have or or melted by heating spray-dried after preparing a slurry, and subjected fed to a high-speed stirring granulator, the granulation step of the batch, JIS K-3362: 1998 "synthetic detergent test The average particle size obtained from the particle size measured by the screening method described in “Method” is 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0.7 to 1.0. A tenth aspect of the present invention is a method for producing a granular detergent composition for clothing that is granulated into a substantially spherical shape.
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]

Furthermore, the present invention has, in particular, the eleventh aspect of the method for producing a granular detergent composition for clothing, in which the high-speed stirring granulator is a granulator having a rotary stirring blade and a rotary crushing blade, A twelfth aspect of the present invention is a method for producing a granular detergent composition for clothing that is subjected to a reduced-pressure drying step after the granulation step in the high-speed stirring granulator.

In addition, the present invention is 25% of a 0.1% by mass aqueous solution obtained by diluting the granular cleaning composition for clothing according to any of the first to ninth aspects with water. A thirteenth aspect of the present invention is a method for producing a granular detergent composition for clothing that is prepared such that the pH at ℃ (according to JIS Z-8802: 1984 “pH measurement method”) is in the range of 8-12.

And this invention used the electric washing machine for the granular cleaning agent composition for clothes which is the summary of any one of the said 1st- 9th as a cleaning agent dilution liquid of 0.03-0.3 mass%. A fourteenth aspect of the present invention is a method for using a granular detergent composition for clothing that is used for washing clothing.

In the present invention, the term "substantially spherical", as shown in FIG. 1 (a), the major axis R1 and a minor axis R2 of the granulate (n = 20 cells) was measured, by the equation (1) above The calculated sphericity is 0.7 to 1.0. The closer this value is to 1.0, the closer to the sphere.

  In the present invention, the “hydrate” refers to a compound containing water in the form of a molecule.

The granular detergent composition for clothing of the present invention is a batch composition of a raw material composition containing specific essential components, which has a mean particle size of 0.8 to 3.0 mm. a will relatively large grains leave, and since sphericity is an aggregate of granules of a special shape close to a sphere of 0.7 to 1.0, fluidity, dispersibility, solubility Excellent and excellent cleaning performance. In addition, it has excellent storage stability, and in particular, even when a chlorine-based bleach, oxygen-based bleach, or a combination of detergent enzymes is stored under conditions of high temperature and high humidity, the above-mentioned bleaching agents and enzymes are decomposed. Since it can be minimized, it has the advantage of exhibiting desired bleaching performance and enzyme cleaning performance.

Moreover, since the granular detergent composition for clothes of the present invention is granulated into a substantially spherical shape having an average particle diameter of 0.8 to 3.0 mm and a sphericity of 0.7 to 1.0 , it prevents powdering. It has excellent workability and safety during handling. And although it is granulated to a comparatively big granule, it has desired melt | dissolution performance.

  And according to the manufacturing method of the granular cleaning composition for clothes of this invention, the granular cleaning composition for clothes of the said outstanding characteristic can be manufactured simply and at low cost.

  In addition, according to the method for using the granular detergent composition for clothes of the present invention, taking advantage of the excellent characteristics of the granular detergent composition for clothes of the present invention, it is excellent by washing the clothes using an electric washing machine. The cleaning power can be demonstrated.

  Next, the best mode for carrying out the present invention will be described in detail.

First, the granular cleaning composition for clothing of the present invention (hereinafter abbreviated as “particulate cleaning composition”) contains the following components (A) to (D) as essential components.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Coalescence

In the component (A), the alkali metal hydroxides, sodium water oxidation, potassium hydroxide, and the like. These are used alone or in combination of two or more thereof.

  Moreover, as said alkali metal silicate, what is shown by following Chemical formula (1) is suitable, and the following x: y is 1: 2-3: 1 from the point of washing | cleaning performance and dispersion | distribution performance especially. Particularly preferred is 1: 2 to 2: 1. For example, anhydrous sodium metasilicate, sodium metasilicate pentahydrate, sodium metasilicate 9 hydrate, and sodium orthosilicate are preferable. Also, anhydrous sodium metasilicate, sodium disilicate, layered sodium silicate (SKS-6, manufactured by Hoechst) and the like can be used. These may be used alone or in combination of two or more.

Said component (A) content of the content is not particularly limited with respect to the entire granular detergent composition, from 1 to 40 mass% (hereinafter, abbreviated as "%") is preferably set to, cry However, 5 to 25% is preferable. That is, if it is less than 1%, the detergency against protein and starch stains is poor, and conversely, if it exceeds 40%, the balance as a whole is deteriorated, storage stability is lowered, and synergistic effects with other components are exhibited. It cannot be obtained any more and is not preferable.

  As the sequestering agent of the component (B), either phosphorus-based or phosphorus-free can be used. These may be used alone or in combination of two or more.

  Examples of the phosphorous sequestering agent include alkali metal phosphates, and examples of the phosphoric acid used include orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, and hexametaphosphoric acid. And as an alkali metal combined with these phosphoric acids, sodium, potassium, etc. are mention | raise | lifted. Of these alkali metal phosphates, sodium tripolyphosphate is particularly preferred.

  Examples of phosphorus-free compounds include aminopolyacetic acid and alkali metal salts thereof, organic acids or alkali metal salts thereof, other organic builders, amino acids, or alkali metal salts thereof.

  Examples of the aminopolyacetic acid and alkali metal salts thereof include ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, polyethyleneimineacetic acid, methyl Aminopolyacetic acid such as glycine diacetic acid, diencoric acid and salts thereof, and alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof are used. And as an alkali metal combined with these, a sodium salt, potassium salt, etc. are mention | raise | lifted, Preferably a sodium salt is used.

  Examples of the organic acids or alkali metal salts thereof include citric acid, gluconic acid, tartaric acid, malic acid, succinic acid, lactic acid, oxalic acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyl succinic acid, carbohydrate. Organic acids such as shikimethyl tartaric acid and 3-hydroxy 2,2′-iminodisuccinic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof can be used.

  Examples of the other organic builder include ethane-1,1-diphosphonate, ethane-1,1,2-triphosphonate, ethane-1-hydroxy-1,1-diphosphonate and derivatives thereof, ethanehydroxy- Phosphonic acid compounds such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, 1-hydroxyethylidene-1,1-phosphonic acid, or the like Alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, etc. Phosphonocarboxylic acids or their alkali metal salts, alkaline earth metal salts, ammonium salts or amines Kanoruamin salt can be used.

  And as said amino acid or these alkali metal salts, alkali metal salts, such as aspartic acid and glutamic acid, alkaline-earth metal salt, ammonium salt, alkanol an salt, etc. can be used.

  Among them, sodium gluconate, sodium citrate, sodium succinate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, tetrasodium 3-hydroxy-2,2'-iminodisuccinate, trisodium methylglycine diacetate, glutamic acid-N, N '-Tetrasodium diacetate, sodium polyethylenimine acetate, sodium tripolyphosphate and 1-hydroxyethylidene-1,1-phosphonic acid are preferably used.

  The content of the sequestering agent that is the component (B) is not particularly limited, but is preferably set to 25 to 80% with respect to the entire granular detergent composition of the present invention. 30 to 60% is preferable. That is, if it is less than 25%, the detergency against oil and sebum soil becomes poor, and the ability to suppress scale formation decreases. Conversely, if it exceeds 80%, the balance as a whole deteriorates and the desired performance decreases. It is not preferable.

  Examples of the component (C) surfactant used in the granular detergent composition of the present invention include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants.

  For example, polyoxyethylene polyoxypropylene polymer (pluronic block polymer, reverse pluronic block polymer), phosphate ester, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, poly Nonionic surfactants such as oxyethylene sorbite fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene alkylamine, glycerin fatty acid ester, higher fatty acid alkanolamide, alkyl glucoside, alkylamine oxide, alkyl sulfate, alkyl Ether sulfate, α-olefin sulfonate, linear alkylbenzene sulfonate, polyoxy Anionic surfactants such as tylene alkyl ether sulfate, cationic surfactants such as benzalkonium chloride and didecyldimethylammonium chloride, and amphoteric surfactants such as amino acid type amphoteric surfactants and betaine type amphoteric surfactants can give. These may be used alone or in combination of two or more.

  Among these, nonionic surfactants are preferred from the viewpoint of low foam performance and emulsifying power of dirt, and in particular, pluronic block polymers, reverse pluronic block polymers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxypropylene trimethylpropanes. Ethylene polyoxypropylene adducts, glycerin polyoxyethylene polyoxypropylene adducts, sodium lauryl sulfate and sodium alkylbenzene sulfonate are preferred.

  The content of the surfactant as the component (C) is not particularly limited, but is preferably set to 5 to 40% with respect to the entire granular detergent composition of the present invention. Among these, 10 to 25% is preferable. That is, if it is less than 5%, the desired cleaning performance is poor, and the cleaning agent may not be compact and may be economically disadvantageous. On the other hand, if it exceeds 40%, the balance as a whole becomes worse, and a synergistic effect with other components cannot be obtained any more, which is not preferable.

  Further, as the polymer electrolyte polymer of component (D) used in the granular detergent composition of the present invention, polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, Poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer , Maleic anhydride ethylene cross-linked copolymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene copolymer, maleic anhydride isoprene Copolymer, with maleic anhydride Poly-β-ketocarboxylic acid derived from carbon oxide, ethylene itaconate copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, malonic acid methylene copolymer , Itaconic acid fumaric acid copolymer, ethylene glycol ethylene terephthalate copolymer, vinylpyrrolidone vinyl acetate copolymer and the like. These may be used alone or in combination of two or more. Among these, sodium polyacrylate, sodium polymaleate, maleic acrylate copolymer, sodium poly-α-hydroxy acrylate, maleic acrylate polyethylene glycol copolymer, sodium salt of olefin maleic acid copolymer The sodium salt of acrylic acid sulfonic acid copolymer is preferred.

  The content of the polymer electrolyte polymer as the component (D) is not particularly limited, but is preferably set to 0.1 to 20% with respect to the entire granular detergent composition of the present invention. Especially, 0.5 to 15% is suitable. That is, if it is less than 0.1%, sufficient cleaning performance is difficult to obtain from the balance with other components, and if it exceeds 20%, the balance as a whole deteriorates and storage stability decreases. A synergistic effect with the ingredients cannot be obtained any more, which is not preferable.

  In addition, it is preferable that at least 1 type of component is a hydrate among (A)-(D) component which is the said essential component. That is, when a hydrate is present in the composition, the moisture contained in the hydrate is dissociated from the crystal structure on the surface when the raw material composition is agitated and mixed and granulated as described later. Since each component particle is wetted out and bound to each other, it is not necessary to melt and solidify the raw material composition at a high temperature, and granulation can be performed without heating or at a relatively low temperature. And since it can make it bind | conclude in the state which left the fine clearance gap between the particle | grains of each component particle | grain, it has the advantage that the obtained granular cleaning composition becomes a thing excellent in solubility very much. Moreover, even if it mix | blends heat-sensitive components, such as an enzyme, it has the advantage that the effect is not impaired.

  In the granular detergent composition of the present invention, water can be blended as the component (E) together with the essential components (A) to (D). Examples of the water include pure water, ion exchange water, soft water, distilled water, and tap water. These may be used alone or in combination of two or more. Of these, tap water and ion-exchanged water are preferably used from the viewpoint of economy and storage stability. Note that “water” as used herein does not include crystal water derived from other components used in the granular detergent composition or water contained in the form of an aqueous solution, but only water added from the outside as a single component. It can be quantified by the heat loss method described in JIS K-3362: 1998 “Synthetic detergent test method”.

When mix | blending the water which is the said (E) component, the content is 0.1 to 9 % with respect to the whole granular cleaning composition. That is, it is preferable to add water in this range because the granulation property and scattering prevention property of the cleaning composition can be improved. In addition, when it mix | blends exceeding 15%, production efficiency falls and a desired granule cannot be obtained and it is unpreferable.

  In addition, the granular detergent composition of the present invention includes, if necessary, a cleaning builder such as an anhydrous or hydrated alkali metal sulfate, a water-soluble solvent, a fluorescent brightener, a hydrotrope, a silicone-based antifoaming agent. Well-known components such as fragrances, corrosion inhibitors, and preservatives can be optionally blended. As will be described later, when a bleaching agent is blended in the granular detergent composition, a bleaching activator can be blended together with the bleaching agent after granulation of the granular detergent composition.

  Among the above optional components, the water-soluble solvent includes monoethanolamine, diethanolamine, triethanolamine, N-methyl-2-pyrrolidone, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, triethylene glycol monoethyl ether, Triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether and the like can be used.

  Further, as the hydrotrope agent, polyethylene glycol, propylene glycol, glycerin and the like can be used.

In addition, a dye or pigment can be blended with the granular detergent composition of the present invention in order to enhance its aesthetic appearance. These are used when the water component (E) is blended and used by dissolving in this water or coloring the granulated granule surface by spraying or the like in the granulation step described later. Used. As such a dye or pigment, those having high solubility and dispersibility and excellent alkali resistance are preferred, and among them, food additive grades are more preferably used. Examples of such dyes or pigments include Blue No. 1, Red No. 3, Yellow No. 4, and naphthol green, which are used alone or in combination of two or more.

  The granular detergent composition of the present invention can be produced, for example, as follows using a raw material composition composed of the essential components (A) to (D) and the above optional components. That is, first, the raw material composition is charged into a high-speed agitation granulator and uniformly mixed, and then heated to a predetermined temperature to perform a batch granulation step. By this, the granular cleaning composition of this invention which is an aggregate | assembly of a substantially spherical granular material with an average particle diameter of 0.8-3.0 mm can be obtained.

  The granular detergent composition of the present invention thus obtained contains specific essential components, and as shown in FIG. 1 (b), the average particle size is relatively 0.8 to 3.0 mm. Since it is a large particle and an aggregate of particles having a special shape close to a true sphere, it is excellent in fluidity, dispersibility, and solubility and has excellent cleaning performance. In addition, it is excellent in storage stability, and in particular, even when a chlorine-based bleaching agent, an oxygen-based bleaching agent described later, or a compound containing a detergent enzyme is stored under high temperature and high humidity conditions, Since decomposition is minimized, it has the advantage of exhibiting desired bleaching performance and enzyme cleaning performance.

  In addition, since the granular detergent composition of the present invention is granulated into a substantially spherical shape having an average particle diameter of 0.8 to 3.0 mm, the powdering is suppressed (excellent in suppressing scattering) and is handled. Excellent workability and safety. And although it is granulated to a comparatively big granule, it has desired melt | dissolution performance.

  Furthermore, in the granular detergent composition of the present invention, the hydrated product is contained in some of the essential components (A) to (D), as described above, when granulating the raw material composition, Since the moisture contained in the hydrate wets the component particles and binds them to each other, it is not necessary to melt and solidify the raw material composition at high temperature, or to use a lot of water and binder at the time of granulation. Granulated at a relatively low temperature, leaving a fine gap between the particles. Therefore, it has the advantage that the effect is maintained even if it is very excellent in solubility and contains a heat-sensitive component such as an enzyme.

  In addition, as a high-speed stirring granulator used for said manufacturing method, what has both a rotation stirring blade and a rotation crushing blade does not have a dispersion | variation in a particle size, and is preferable when obtaining a substantially spherical granular material. Examples of such a granulator include, for example, trade name: High Speed Mixer (Fukae Powtech Co., Ltd.), trade name: Redige Mixer (Matsubo Co., Ltd.), trade name: Henschel Mixer (Mitsui Mining Co., Ltd.), product Name: Vertical granulator (manufactured by POWREC), trade name: Proshare mixer (manufactured by Taiheiyo Kiko Co., Ltd.), etc. Among them, a high speed mixer and a Ladige mixer are preferred.

  The operating conditions of the high-speed agitation granulator are appropriately adjusted so that the granular detergent composition obtained has a narrow particle size distribution and is as close to a sphere as possible. For example, in what has both a rotary stirring blade and a rotary crushing blade, it is preferable to set the tip peripheral speed of a rotary stirring blade to 3-12 m / sec, and it is preferable to set the rotation speed of a rotary crushing blade to 50-3000 rpm. . More preferably, the tip peripheral speed of the rotary stirring blade is 5 to 10 m / second, and the rotational speed of the rotary crushing blade is 1500 to 2500 rpm.

  Furthermore, the product temperature at the time of granulation is preferably set to 40 to 80 ° C., and more preferably 50 to 70 ° C. In order to perform such product temperature control, the high-speed agitation granulator used in the present invention preferably has a jacket for introducing a refrigerant / heat medium such as cold water, hot water, and steam. And it is preferable to set the said jacket temperature so that it may not exceed 100 degreeC, and it is more preferable to set to 90 degrees C or less considering the influence of the heat | fever to a raw material especially.

  Also, in the above production method, after the granulation process is completed, fine powder uptake and removal should be performed by appropriately adjusting the rotation speed of the rotary stirring blade and the rotary crushing blade in order to suppress fine powder scattering during handling and to regulate the size. Is desirable.

  Further, in the above production method, after the granulation step is completed, it is preferable to continue the drying step, but from the viewpoints of suppressing aggregation of the granular detergent composition, suppressing deterioration in quality, and improving productivity, drying under reduced pressure may be performed. More preferred. The pressure in the high-speed agitation granulator at the time of drying under reduced pressure is preferably set to 6 to 32 kPa, and in particular, it can be set to 13.3 to 20 kPa in terms of load on the vacuum pump and airtightness. More preferred.

  And in the said drying process, in order to dry the granulated granule, it is preferable that the nozzle for gas blowing is provided in the high speed stirring granulator used for this invention. In the drying step, an appropriate gas such as air or nitrogen is used as the gas blown from the nozzle, and the temperature is usually preferably set to 10 to 40 ° C. Further, the amount of gas introduced depends on the amount of the granular detergent composition granulated in one batch, but is usually preferably set to 1 to 40 liters / minute, and more preferably 5 to 20 liters / minute. It is more preferable to set to.

  In addition, the granular detergent composition of the present invention has the above-mentioned high-speed agitation for the purpose of improving caking resistance, improving solubility, improving productivity, etc. within the range not impairing the intended performance of the present invention. During granulation by a granulator, a binder can be added to the raw material composition. Moreover, the water which is the said (E) component can be added with this binder instead of a binder.

  As the binder, those showing a desired caking property are preferable. For example, sodium alginate, gum arabic, guar gum, gelatin, sodium carboxymethyl starch, dextrose, methyl cellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, acrylic acid amide polymer , Polyvinyl alcohol, polyvinyl ethyl ether, polyethylene glycol, polyvinyl pyrrolidone and the like. These may be used alone or in combination of two or more.

  When adding the said binder, it is suitable that the addition amount is normally set to 0.1 to 20% with respect to the whole granular cleaning composition. If it is below the above range, the effect of using the binder is poor, and conversely, if it exceeds the above range, not only the production efficiency is lowered, but also there is a problem that it is difficult to obtain a desired grain shape.

  Further, in the present invention, a chlorine-based bleaching agent or an oxygen-based bleaching agent may be mixed as the component (F) into the aggregate of the substantially spherical particles granulated by the granulation step (including the drying step). it can. Examples of the chlorine bleach include sodium dichloroisocyanurate, sodium trichloroisocyanurate, and calcium hypochlorite. Examples of the oxygen bleach include sodium percarbonate, sodium perborate, and sodium persulfate. It is done. These are used alone or in combination of two or more.

  In addition, as a chlorine bleach or oxygen bleach of the said (F) component, it is desirable to use that whose average particle diameter was set to 0.5-3.0 mm. This is in consideration of the balance with the average particle size of the granular cleaning composition as a base, and if the average particle size of the component (F) is less than 0.5 mm, the scattering effect may be impaired. On the other hand, if the average particle size exceeds 3.0 mm, homogeneous solubility cannot be obtained, and the desired cleaning performance is poor, which is not preferable.

  When the chlorine bleach or oxygen bleach that is the component (F) is mixed, the content is set to 0.1 to 10% as an effective chlorine amount or an effective oxygen amount with respect to the whole granular detergent composition. It is suitable to do, More preferably, it is 0.5 to 5%. That is, in this range, it is possible to further increase the cleaning power, particularly the cleaning power against strong dirt that easily becomes a stain. In addition, when it exceeds 10%, the storage stability is lowered, and a synergistic effect with other components cannot be obtained any more, which is not preferable.

  Moreover, in this invention, the enzyme for detergents can be mixed as a (G) component with the aggregate | assembly of the granulated substantially spherical granular material similarly to the said (F) component. Examples of the detergent enzyme include amylase, protease, lipase, cellulase, pullulanase, and pectinase, and these are also used alone or in combination of two or more. In addition, as for the said enzyme for detergents, it is desirable to use what the average particle diameter was set to 0.5-3.0 mm from the reason similar to (F) component.

  When mixing the enzyme for detergents which is the said (G) component, it is suitable to set the content to 0.1 to 10% with respect to the whole granular cleaning composition, More preferably, it is 1-7. %. That is, the cleaning power can be further increased within this range. In addition, when it mixes exceeding 10%, while the balance as a whole worsens, the synergistic effect with another component is not acquired any more, and it is not preferable also from the point of economical efficiency.

  And the granular detergent composition of the present invention thus obtained is prepared so that the pH of a 0.1% aqueous solution obtained by diluting it with water is in the range of 8-12. It is suitable for use in washing clothes with an electric washing machine.

  The granular detergent composition of the present invention can be filled into a bag such as a standing pouch, a paper container, a plastic container or the like for distribution.

  And the granular cleaning composition of this invention is used for washing | cleaning of the clothing using various electric washing machines regardless of household use and business use. Moreover, it is suitable to set the dilution concentration at the time of use to 0.03 to 0.3%.

Next, examples of the present invention will be described together with reference examples and comparative examples. However, the present invention is not limited to the following examples.

[Examples 1 to 106, Reference Examples 1 and 2 , Comparative Examples 1 to 6]
In accordance with the composition shown in Tables 1 to 16 below, the raw materials are sequentially added to a high speed mixer (model: FS / GS-100J, manufactured by Fukae Powtech Co., Ltd.) so that the total amount becomes 50 kg, and then heated uniformly. Then, granulation was performed when the product temperature reached a predetermined temperature. And the granular cleaning composition was manufactured by performing reduced pressure drying by a water seal pump (model: SW200S, Shinko Seimitsu Co., Ltd.).

About the obtained granular cleaning composition, while calculating | requiring an average particle diameter, the sphericity was computed according to above-mentioned Formula (1). In addition, according to the following test methods and the like, seven items of manufacturability, scatterability, solubility, pH, effective chlorine or effective oxygen stability, storage stability, and detergency were evaluated. The results are also shown in Tables 1 to 16 below. In Tables 1 to 16 below, the details of the components used and their effective pure content (%) are as follows, and the values in the table are shown in terms of 100% effective pure content. It is. “Water” in the table is not water contained in the form of crystal water or aqueous solution derived from each component constituting the granular detergent composition, but water added from the outside , and the entire granular detergent composition Is shown as a balance to be 100%.

〔Manufacturability〕
Test Method After granulation, whether or not the raw material cleaning composition becomes a granular compact was visually observed and evaluated according to the following criteria.
・ Evaluation criteria ○: After granulation, a granular compact was formed.
(Triangle | delta): The thing which does not become a granular molding after granulation was mixed partially.
X: After granulation, a granular molded body could not be formed.

[Spattering]
Test Method An acrylic cylindrical container having an inner diameter of 52 mm and a height of 1100 mm is set up vertically, and 200 g of the granular cleaning composition is naturally dropped from the upper part of the cylinder. Dust that soared after 1 second was sucked, and the scattering rate (%) was calculated from the amount collected at that time based on the following formula (2), and evaluated according to the following criteria.

[Equation 4 ]
Scattering rate (%) = S / 200 (g) × 100 (2)
S: Sample collection amount (g)

・ Evaluation criteria ◎: Scatter rate is less than 0.5% ○: Scatter rate is 0.5% or more and less than 1% △: Scatter rate is 1% or more and less than 1.5% ×: Scatter rate is 1.5% or more

[Solubility]
Test Method A 1 liter beaker containing 1 liter of hot water and a stir bar was immersed in a 60 ° C. water bath placed on a magnetic stirrer, and the hot water was rotated at a rotation speed of 500 rpm. 1 g of the granular detergent composition was put therein, the time until dissolution was measured, and evaluated according to the following criteria.
Evaluation criteria A: Dissolution time less than 60 seconds ○: Dissolution time 60 seconds or more and less than 120 seconds Δ: Dissolution time 120 seconds or more and less than 180 seconds X: Dissolution time 180 seconds or more

[PH]
Test Method According to JIS Z-8802: 1984, the pH of an aqueous solution of a granular detergent composition prepared to 0.1% was measured at 25 ° C. and evaluated according to the following criteria.
-Evaluation criteria (circle): pH is 8-12.
X: pH is less than 8 or more than 12.

[Stability of effective chlorine and effective oxygen]
Test method Put the granular detergent composition in a 250 ml polypropylene container, store it at 50 ° C. for 2 months, and measure the remaining effective chlorine or effective oxygen by the following method (1) or (2). Then, the effective chlorine before storage and the ratio to the effective chlorine were determined as the residual rate (%), and the stability was evaluated according to the following criteria.
(1) Effective chlorine measurement method Take 3 g of sample in a 200 ml Erlenmeyer flask, add 15 ml of 10% potassium iodide iodide solution and 10 ml of (1 + 1) sulfuric acid, and leave it in a cool dark place for 3 minutes to release iodine. The solution is titrated with 0.1N sodium thiosulfate normal solution until the yellow color of iodine disappears and calculated from the following formula (3).

[Equation 5 ]
Effective chlorine (%: as Cl) = 0.545 × A / S (3)
A: Titration volume of 0.1N sodium thiosulfate normal solution (ml)
S: Sample collection amount (g)

(2) Effective oxygen measurement method Take 1 g of a sample in a 200 ml Erlenmeyer flask, add 10 ml of 17% potassium iodide iodide solution, 15 ml of (1 + 9) sulfuric acid, 2 ml of 5% ammonium molybdate, and leave it in a cool and dark place for 3 minutes. Then, iodine is liberated, titrated with 0.1N sodium thiosulfate normal solution until the yellow color of iodine disappears, and calculated from the following formula (4).

[Equation 6 ]
Effective oxygen (%: H ₂ O ₂ ) = 0.17 × A / S (4)
A: Titration volume of 0.1N sodium thiosulfate normal solution (ml)
S: Sample collection amount (g)

・ Evaluation criteria ◎: Residual rate is 70% or more ○: Residual rate is less than 70% 50% or more △: Residual rate is less than 50% 30% or more ×: Residual rate is less than 30%

[Storage stability]
Test Method The granular detergent composition was placed in a 250 ml polypropylene container and stored for 3 months in a constant temperature and humidity chamber (model: IG47M, manufactured by Yamato Scientific Co., Ltd.) having a temperature of 40 ° C. and a humidity of 75%. The appearance was visually observed, and storage temperature stability was evaluated according to the following evaluation criteria.
-Evaluation criteria ○: After 3 months, no discoloration or consolidation was observed.
Δ: Slight discoloration or consolidation was observed after 3 months.
X: After 3 months, discoloration, consolidation and the like were remarkably recognized.

[Cleanability]
Test method An aqueous solution of a granular detergent composition adjusted to 0.1% according to JIS K-3362: 1998 is mixed into a stirring type detergency tester (model: TM4 Targotometer, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.). An object to be cleaned (wet artificially contaminated cloth, Association for Laundry Science) was introduced, and the cleaning power at 30 ° C. was evaluated according to the following criteria. The detergency is calculated from the following equation (5) by measuring the object to be cleaned with a differential meter (model: TC-1800MKII, manufactured by Tokyo Denshoku Co., Ltd.).

[Equation 7 ]
Detergency (%) = (Rw−Rs) / (R0−Rs) × 100 (5)
R0: reflectance of white cloth,
Rs: reflectance of wet artificially contaminated cloth before washing Rw: reflectance of wet artificially contaminated cloth after washing

* Operating condition Detergent concentration: 0.1%
Washing temperature: 30 ° C
Cleaning: Rotating speed 120 rpm, 10 minutes rinse temperature: 30 ° C
Rinse: Rotating speed 120 rpm, 3 minutes x 2 times Tap water hardness: (as CaCO ₃ ) 70-80 ppm
Object to be cleaned: A wet artificial contamination cloth having a length of 5 cm and a width of 5 cm was used.
・ Evaluation criteria ◎: 90% or more dirt removal ○: 70% or more and less than 90% dirt removal △: 50% or more and less than 70% dirt removal ×: Less than 50% dirt removal

  The details of various components used in Tables 1 to 16 below and their effective pure content (% by mass) are as follows.

[Component A]
・ Alkaline agent 1
Anhydrous sodium metasilicate
Product name: Sodium metasilicate anhydrous granule (Guangei Chemical Industry Co., Ltd.)
・ Alkaline agent 2
Sodium metasilicate / pentahydrate Product name: Sodium metasilicate / pentahydrate crystal (Guangei Chemical Industry Co., Ltd.)
・ Alkaline agent 3
Sodium metasilicate / Nine hydrate Product name: Sodium metasilicate / 9 hydrate (manufactured by Sanpo Chemical Co., Ltd.)
・ Alkaline agent 4
Sodium orthosilicate pure content: 65%
Product Name: Ortho 65 (Toyo Silica)
・ Alkaline agent 5
Sodium hydroxide
Product name: Tosoh Pearl (manufactured by Tosoh Corporation)
・ Alkaline agent 6
Potassium hydroxide Product name: Potassium hydroxide special make-up base material (manufactured by Toagosei Co., Ltd.)
・ Alkaline agent 7
sodium carbonate
Product Name: Light Soda Ash (Made by Tokuyama Soda)
・ Alkaline agent 8
sodium hydrogen carbonate
Product name: Sodium bicarbonate (made by Tokuyama Soda Co., Ltd.)

[B component]
・ Metal ion sequestering agent 1
Sodium gluconate Product name: Sodium gluconate (manufactured by Fuso Chemical Industries)
・ Metal ion sequestering agent 2
Sodium citrate Product name: Trisodium citrate (manufactured by Iwata Chemical Industries)
・ Metal ion sequestering agent 3
Ethylenediaminetetraacetic acid tetrasodium Product name: Trilon B (manufactured by BASF)
・ Metal ion sequestering agent 4
Nitrilotriacetic acid trisodium Product name: Trilon A92R (BASF)
・ Metal ion sequestering agent 5
Glutamic acid-N, N'-tetrasodium diacetate pure: 38%
Product name: Dissolvin GL-38 (manufactured by Akzo Nobel)
・ Metal ion sequestering agent 6
Sodium tripolyphosphate Product name: Sodium tripolyphosphate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Metal ion sequestering agent 7
Trisodium phosphate Product name: Trisodium phosphate (manufactured by Nippon Chemical Industry Co., Ltd.)
・ Metal ion sequestering agent 8
1-hydroxyethylidene-1,1-diphosphonic acid Product name: Diquest 2016D (manufactured by Solusia)
・ Metal ion sequestering agent 9
Zeolite trade name: Shilton B powder (manufactured by Mizusawa Chemical Industry Co., Ltd.)

[C component]
・ Surfactant 1
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 3,300
Product name: Epan 740 (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Surfactant 2
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 2,800
Product name: Pluronic RPE 1740 (BASF)
・ Surfactant 3
Polyoxyethylene (P = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14, 15) ether EO / PO weight ratio = 1.26
Prototype / Surfactant 4
Polyoxyethylene (P = 8) Polyoxypropylene (q = 6) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 1.01, Cloud point = 31 ° C.
Product name: Pepol AS-054C (manufactured by Toho Chemical Industry Co., Ltd.)
・ Surfactant 5
Polyoxyethylene (m = 4) Polyoxypropylene (q = 38) Linear alkyl (C = 16-18) ether EO / PO weight ratio = 0.08
Product name: Adecatol LG-299 (Asahi Denka Kogyo Co., Ltd.)
・ Surfactant 6
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,000, cloud point 24 ° C.
Product name: Pluronic PE6100 (manufactured by BASF)
・ Surfactant 7
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,800
Product name: Pluronic RPE2510 (manufactured by BASF)
・ Surfactant 8
Trimethylolpropane EO, PO adduct EO / PO weight ratio = 0.21, average molecular weight = 4,500
Prototype / Surfactant 9
Glycerin EO, PO adduct EO / PO weight ratio = 0.22, average molecular weight = 4,500
Prototype / Surfactant 10
Sodium lauryl sulfate Product name: Monogen Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Surfactant 11
Sodium alkylbenzenesulfonate Product name: Neoperex GS (manufactured by Kao Corporation)
・ Surfactant 12
Mixed fatty acid soap Product name: NONSAR PN-171 (manufactured by NOF Corporation)
・ Surfactant 13
Oleic acid complex soap Product name: Nonsal OK-2 (Nippon Yushi Co., Ltd.)

[D component]
・ Polyelectrolyte polymer 1
Sodium polyacrylate average molecular weight: 15,000
Product name: Socaran PA-40P (BASF)
・ Polyelectrolyte polymer 2
Acrylic acid-maleic acid copolymer Average molecular weight: 70,000
Product name: Socaran CP-45G (BASF)

[Cleaning builder ingredients]
・ Cleaning builder 1
Anhydrous sodium sulfate
Product name: Neutral anhydrous sodium sulfate A0 (manufactured by Shikoku Chemicals)
・ Cleaning builder 2
Potassium sulfate
Product name: Potassium sulfate (Otsuka Chemical Co., Ltd.)

(Binder component)
・ Binder 1
Sodium alginate Average molecular weight: 40,000
Product name: Sun Argin (Mitsubishi)
・ Binder 2
Sodium carboxymethyl starch Average molecular weight: 7,500,000
Product name: Glicolis-LV (manufactured by Rocket Japan)
・ Binder 3
Sodium carboxymethyl cellulose Average molecular weight: 10,000
Product name: Serogen PR (Daiichi Kogyo Seiyaku Co., Ltd.)
・ Binder 4
Acrylic acid amide polymer average molecular weight: 5,000,000
Product name: Reagent (Wako Pure Chemical Industries, Ltd.)
・ Binder 5
Polyvinyl alcohol Average molecular weight: 44,000
Product name: VC-10 (Nippon Vinegar-Poval)
・ Binder 6
Polyethylene glycol Average molecular weight: 20,000
Product name: PEG 20000 (manufactured by Sanyo Chemical Industries)

[F component]
・ Chlorine bleach 1
Sodium dichloroisocyanurate, pure: 60%
Product name: Neocrawl 60G (Shikoku Kasei Co., Ltd.)
・ Oxygen bleach 1
Sodium percarbonate Product name: PC-A (Nippon Peroxide)
・ Oxygen bleach 2
Sodium perborate Brand name: 15% Perbon (Daiichi Kogyo Seiyaku Co., Ltd.)

[Bleaching activator component]
・ Bleaching activator 1
Tetraacetylethylenediamine Product name: TAED (manufactured by Clariant Japan)

[Fluorescent brightener component]
・ Fluorescent brightener 1
4,4'-bis [sulfostyryl] biphenyl disodium Product name: Tinopearl CBS-X (Ciba Geigy)

[G component]
・ Enzyme 1
Amylase Product name: Termamyl 60TNT (Novozyme)
・ Enzyme 2
Protease Product name: Everase 8.0T (Novozyme)
・ Enzyme 3
Lipase Product name: Lipolase (Novozyme)

[Antifoaming ingredient]
・ Silicone-based antifoaming agent 1
Silicone Product name: KS-530 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[Comparative Examples 7 and 8]
As Comparative Example 7 having a shape different from that of the granular detergent composition of the present invention, as shown in FIG. 2 (a), as shown in FIG. 2 (a), a detergent composition comprising a very fine powder (trade names: Chopittokun, Tea Pole Diversity Prepared). Further, as Comparative Example 8, as shown in FIG. 2 (b), a detergent composition in which very fine powder and relatively large particles are mixed (trade name: New White Wash, manufactured by Tea Pole Diversity) Prepared.

  And also about the said 2 comparative example goods, it evaluated about the evaluation item similar to the above, and the result is shown in following Table 17. FIG. The characteristics of each comparative product are shown in Table 17.

From the results of Tables 1 to 17, although Examples 1 to 106 have some items that are slightly inferior depending on the composition, in general, sphericity, manufacturability, scatterability, solubility, pH, It turns out that it has the outstanding performance in any evaluation item of stability, storage stability, and detergency of effective chlorine or effective oxygen. On the other hand, Comparative Examples 1 to 4 lacking even one essential component and Comparative Examples 5 to 8 whose average particle diameter and shape of the particles are outside the scope of the claims have several bad evaluation items. It turns out that this is a practical problem.

(A) is explanatory drawing of how to obtain | require sphericity, (b) is typical explanatory drawing which shows the granular cleaning composition of this invention. (A) is typical explanatory drawing which shows the comparative example 7 goods, (b) is typical explanatory drawing which shows the comparative example 8 goods.

Claims (14)

While containing the following (A)-(D) component as an essential component, the raw material composition which contains 0.1-9 mass% of water, the following (A)-(D) component is prepared in the slurry form. In a state that is not spray-dried or heated and melted after that, it is supplied to a high-speed agitation granulator and granulated in a batch system. According to the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” An approximately spherical shape in which the average particle size obtained from the measured particle size is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is set to 0.7 to 1.0. A granular detergent composition for clothing, comprising an aggregate of granules.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combined [Equation 1]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material] A raw material composition containing the following components (A) to (D) as essential components and not containing water, and at least one of these components (A) to (D) is a hydrate. The following components (A) to (D) are prepared in the form of a slurry and are not spray-dried or heated and melted , supplied to a high-speed agitation granulator, and batch-derived, derived from the hydrated product. The average particle size determined from the particle size measured by the sieving method described in JIS K-3362: 1998 “Synthetic detergent test method”. The diameter is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is made of an aggregate of substantially spherical granular materials set to 0.7 to 1.0. A granular cleaning composition for clothing.
(A) One or more compounds selected from alkali metal hydroxides, alkali metal silicates, sodium carbonate and sodium hydrogen carbonate (B) sequestering agent (C) surfactant (D) polymer electrolyte heavy Combine [number 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]   The granular detergent composition for clothes according to claim 1 or 2, wherein the sequestering agent of the component (B) is an alkali metal phosphate.   The granular detergent composition for clothing according to claim 1 or 2, wherein the sequestering agent of the component (B) is a phosphorus-free sequestering agent.   The granular detergent composition for clothes according to claim 4, wherein the phosphorus-free sequestering agent is at least one selected from aminocarboxylic acids, hydroxyaminocarboxylic acids, and salts thereof.   The surfactant for the component (C) is a nonionic surfactant, The granular detergent composition for clothing according to any one of claims 1 to 5.   The polymer electrolyte polymer of the component (D) is at least one selected from a polymer having at least one of acrylic acid and maleic acid as a monomer, a copolymer thereof, and a water-soluble alkali salt thereof. The granular detergent composition for clothes according to any one of claims 1 to 6.   8. At least one binder selected from natural polymer derivatives, starch derivatives, cellulose derivatives, acrylic acid derivatives, polyvinyl alcohol and polyethylene glycol is added at the time of granulation. The granular cleaning composition for clothes as described. The granular detergent composition for clothes according to any one of claims 1 to 8, wherein at least one of the following (F) component and (G) component is mixed in the aggregate of the substantially spherical granular materials.
(F) Chlorine bleaching agent in which the average particle size determined from the particle size measured by the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” is set to 0.5 to 3.0 mm. Or oxygen bleach.
(G) A detergent enzyme having an average particle size determined from the particle size measured by the screening method described in JIS K-3362: 1998 “Synthetic detergent test method” set to 0.5 to 3.0 mm. A method for producing a granular detergent composition for clothing according to any one of claims 1 to 9, wherein a raw material composition for preparing a substantially spherical granular material is prepared, and each raw material component is prepared in a slurry form. the method 1998 "synthetic detergent test method" described sieving: in the state where no or spray-dried or heat-melted after, and subjected fed to a high-speed stirring granulator, the granulation step of the batch, JIS K-3362 The average particle size obtained from the particle size measured by the above is 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is granulated into a substantially spherical shape of 0.7 to 1.0. A process for producing a granular detergent composition for clothing, which is characterized in that
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]   The method for producing a granular detergent composition for clothing according to claim 10, wherein the high-speed stirring granulator is a granulator having a rotary stirring blade and a rotary crushing blade.   The manufacturing method of the granular cleaning composition for clothes of Claim 10 or 11 which was made to pass through a reduced pressure drying process after the granulation process in the said high speed stirring granulator.   PH (JIS Z-8802: 1984 "pH measurement) of a 0.1 mass% aqueous solution obtained by diluting the granular detergent composition for clothing according to any one of claims 1 to 9 with water. The manufacturing method of the granular cleaning composition for clothes as described in any one of Claims 10-12 which was prepared so that it might become the range of 8-12.   The granular detergent composition for clothes according to any one of claims 1 to 9 is prepared as a detergent diluent of 0.03 to 0.3% by mass and used for washing clothes by an electric washing machine. A method for using a granular detergent composition for clothing, characterized in that it is configured as described above.

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