JP5213091B2 - Granular detergent composition for automatic dishwasher, method for producing the same, and method for using the same - Google Patents

Description

  The present invention is a granular detergent composition for an automatic dishwasher suitable for washing hard surfaces such as metal, glass, ceramics, plastics, etc., and particularly suitable for washing dishes and cooking utensils using an automatic dishwasher, and the like. The present invention relates to a production method and a method of using the same.

  2. Description of the Related Art Conventionally, automatic dishwashers have been widely used in hotels, restaurants, catering companies, hospitals, company cafeterias, and the like to efficiently wash used dishes. Further, not only tableware, but also various food manufacturing factories, food processing factories, etc., automatic washing machines are used for washing food-related items such as utensils, containers, trays and containers. Conventionally, these automatic dishwashers (including automatic washing machines for washing the above-mentioned various food-related products) have been known to use a powder detergent.

  However, in the case of using the powder cleaning agent, the powder cleaning agent must be periodically added to the detergent injection device connected to the automatic dishwasher, and the powder of the cleaning agent is scattered at that time. There is a possibility that the powder cleaning agent may adhere to the skin of the worker or may be inhaled into the lungs. The powder cleaning agent is dissolved in water or hot water in the apparatus and injected as a liquid into the cleaning tank, but it is difficult to dissolve the powder cleaning agent so that the concentration of each component is uniform. There is also a problem.

  In the case of a method in which a powder cleaning agent is housed in a cartridge container, although there is no problem with the scattering of the cleaning agent and the uniformity of the dissolution concentration, the used container is often discarded, and resources are reused. It was a problem.

  Therefore, in recent years, a cleaning agent container having a shape in which an opening is provided at the bottom of a conventional cartridge type cleaning agent is attached to the cleaning agent dissolving apparatus, and is stored in the bag body from the upper surface opening of the cleaning agent storage unit. A method of using additional cleaning agents has been used. For this reason, when using a powder cleaning agent, the scattering will also be a problem at the time of the addition operation.

  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.

In addition, there has been proposed a cleaning agent that suppresses dusting by granulating the cleaning agent in a granular form instead of powder, or by forming it into a pellet form. For example, a powder mixture containing (a) alkali metal silicate hydrate and (b) sequestering agent without extrusion water or binder is obtained by extrusion molding under heating. The molded product includes a solid detergent having a predetermined breaking strength (see Patent Document 1), an alkali metal carbonate, an alkali metal silicate, a sequestering agent, and a surfactant as essential components. A pellet cleaning composition obtained by mixing a cleaning composition with a Henschel mixer and then extruding it using a disk pelleter or the like and cutting it into a predetermined length and a method for producing the same (see Patent Document 2) ) Has been proposed. Alternatively, the detergent powder for a high-density granular detergent consisting of a surfactant, a builder, a surface modifier, a bulking agent, and the like can be taken out after being sized to a certain particle size in a specially configured granulation chamber. A continuous granulation method and apparatus (see Patent Document 3) of high-density detergent particles that are continuously performed have been proposed.
JP 2004-149780 A JP 2004-269557 A Japanese Patent No. 2636036

  However, the solid detergent in Patent Document 1 is obtained by extruding a powder mixture under heating, and the pellet detergent composition in Patent Document 2 extrudes the material mixture into a cylindrical shape. And cut into a predetermined length. For this reason, these molded products are likely to be mixed with a powdery detergent composition that is generated at the time of cutting, and it is not possible to ensure sufficient dusting suppression performance. There is a problem that the solubility of the resin becomes worse.

  In addition, the high-density detergent particles of the above-mentioned Patent Document 3 are only described as examples in which the average particle size is 540 to 600 μm and the particles are relatively fine. It is doubtful whether the property, solubility, powdering suppression performance, etc. can be obtained.

  The present invention has been made in view of such circumstances, and (1) the cleaning performance, the finish of the object to be cleaned such as tableware, and the scale suppression performance are excellent, and the storage stability is excellent. Or, even when a blend containing an oxygen-based bleach is stored under conditions of high temperature and high humidity, decomposition of the bleach is minimized, and it has the desired bleaching performance. (2) Granular and fluid , Easy to fill cartridge type containers, etc., with little dusting, excellent workability and safety during handling, (3) desired dissolution performance despite granulation It is an object of the present invention to provide an excellent granular detergent composition for an automatic dishwasher that has 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 (E) as essential components, and a raw material composition containing 0.1 to 9% by mass of water has the following (A ) ~ (E)
In a state where the portion is not spray-dried or heated and melted after being prepared in a slurry state,
JIS K-3362: 1998, which is supplied to a high-speed agitation granulator and batch-granulated.
The average particle size determined from the particle size measured by the screening method described in “Synthetic detergent test method” is set to 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0. an automatic dishwasher particulate detergent composition comprising a substantially spherical granulate 0 aggregate set to 7 to 1.0 shall be the first aspect.
(A) One or more compounds selected from alkali metal hydroxides and alkali metal silicates
Compound (B) sequestering agent (C) surfactant (D) alkali metal carbonate (E) polymer electrolyte polymer [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 (E) as essential components and does not contain water, and at least one of these components (A) to (E) is a hydrate. The raw material composition is spray-dried after the following components (A) to (E) are prepared in a slurry state.
In a state where it is not heated and melted, it is supplied to a high-speed agitation granulator and is batch-typed, which is granulated by binding with each component particle leaving a gap due to moisture derived from the hydrate. , J
IS K-3362: 1998 The average particle size determined from the particle size measured by the screening method described in “Synthetic detergent test method” is set to 0.8 to 3.0 mm, and the following formula (1
The second gist is a granular detergent composition for an automatic dishwasher composed of an assembly of substantially spherical granular bodies having a sphericity calculated by (1) of 0.7 to 1.0.
(A) One or more compounds selected from alkali metal hydroxides and alkali metal silicates
Compound (B) sequestering agent (C) surfactant (D) alkali metal carbonate (E) polymer electrolyte polymer [Equation 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]

Furthermore, the present invention includes, among them, in particular (G) (G) and (G)
As) component, the automatic dishwasher granular detergent composition containing anhydrous alkali metal salt or an alkali metal salt hydride sulfate as a third aspect, the component (A), least also A <br/> The 4th summary is the granular detergent composition for automatic dishwashers containing a Lucari metal hydroxide . Moreover, let the 6th summary the granular detergent composition for automatic dishwashers whose metal ion sequestering agent of the said (B) component is an alkali metal phosphate.

And among the granular detergent composition for automatic dishwashing machine which is the said 6th summary, this invention is the said phosphorus-free metal ion sequestering agent especially aminocarboxylic acid and hydroxyaminocarboxylic acid, and its A granular detergent composition for an automatic dishwasher, which is at least one selected from salts, is a seventh aspect .

In addition, the present invention has an eighth aspect of the granular detergent composition for an automatic dishwasher, in which the surfactant of the component (C) is a nonionic surfactant, The polymer electrolyte polymer of component (E) 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. an automatic dishwasher granular detergent compositions as a ninth gist, the natural polymer derivative, starch derivatives, cellulose derivatives, acrylic acid derivatives, at least one binder selected from polyvinyl alcohol and polyethylene glycol, granulation A granular detergent composition for an automatic dishwasher, which is sometimes added, is defined as a tenth aspect .

Furthermore, the present invention provides a granular detergent for an automatic dishwashing machine, in which at least one of the following (H) component and (I) component is mixed with the aggregate of the substantially spherical granule, among them. The composition is the eleventh aspect .
(H) Chlorine bleach or oxygen bleach with an average particle size of 0.5 to 3.0 mm. (I) Detergent enzyme having an average particle size of 0.5 to 3.0 mm.

The present invention is also a method for producing a granular detergent composition for an automatic dishwasher according to any one of the first to eleventh aspects, comprising a raw material composition for preparing a substantially spherical granular material. , 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 "
The average particle size determined from the particle size measured by the screening method described in “Synthetic detergent test method” is 0.8 to 3.0 mm, and the sphericity calculated by the following formula (1) is 0.7 to 1.
. The method of automatic dishwasher particulate detergent composition in earthenware pots by granulating the substantially spherical becomes zero first
The gist of 2.
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material]

Furthermore, the present invention, among them, in particular, the high-speed stirring granulator, process the 13th gist of the automatic dishwashing machine granular detergent composition is a granulator having a rotating stirring blades and rotary crushing blade And the manufacturing method of the granular cleaning composition for automatic dishwashers made to go through a reduced pressure drying process after the granulation process in the said high-speed stirring granulator is made into the 14th summary.

Moreover, the present invention is a 0.1% by mass aqueous solution obtained by diluting the granular detergent composition for an automatic dishwasher, which is the gist of any one of the first to eleventh aspects, with water among them. No. 15 is a method for producing a granular detergent composition for an automatic dishwashing machine prepared so that the pH at 25 ° C. (according to JIS Z-8802: 1984 “pH measurement method”) is in the range of 8-12. The gist of

And this invention prepares the granular cleaning composition for automatic dishwashers which is the summary of any one of the said 1st- 11th as a 0.01-0.5 mass% washing | cleaning agent dilution liquid, and is automatic. A sixteenth aspect of the present invention is a method for using a granular detergent composition for an automatic dishwasher that is used for washing dishes, cooking utensils, and the like by a dishwasher.

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 automatic dishwashing machine of the present invention is a batch composition granulated raw material composition containing a specific essential component by a high-speed stirring granulator, the average particle size is 0.8 ~ since a will relatively large grains leave 3.0 mm, moreover sphericity is an aggregate of granules of a special shape close to a sphere of 0.7 to 1.0, cleaning performance, tableware finish It has excellent performance in terms of both properties and scale suppression 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.

The granular detergent composition for an automatic dishwasher of the present invention is granulated into a substantially spherical shape having an average particle size of 0.8 to 3.0 mm and a sphericity of 0.7 to 1.0 . Standing is suppressed (excellent in suppressing scattering), and it is excellent in 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 detergent composition for automatic dishwashers of this invention, the granular detergent composition for automatic dishwashers of the said outstanding characteristic can be manufactured simply and at low cost.

  Furthermore, according to the method of using the granular detergent composition for an automatic dishwasher of the present invention, taking advantage of the excellent characteristics of the granular detergent composition for the automatic dishwasher of the present invention, the tableware is prepared using the automatic dishwasher. By cleaning an object to be cleaned, etc., it is possible to exhibit excellent cleaning power and finish.

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

First, the granular detergent composition for automatic dishwashers of the present invention (hereinafter abbreviated as “granular detergent composition”) contains the following components (A) to (E) as essential components.
(A) One or more compounds selected from alkali metal hydroxides and alkali metal silicates
Compound (B) sequestering agent (C) surfactant (D) alkali metal carbonate (E) polymer electrolyte polymer

In the component (A), examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and these are used alone or in combination of two or more.

  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.

It said component (A) content of the content is not particularly limited with respect to the entire granular detergent composition, from 1 to 50% by weight (hereinafter, abbreviated as "%"), more preferably be set to, cry But 20
~ 45% is preferred. That is, if it is less than 1%, the detergency against protein and starch becomes poor. Conversely, if it exceeds 50%, the balance as a whole deteriorates, storage stability is lowered, and synergistic effects with other components are reduced. The above cannot be obtained 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 10 to 60% with respect to the entire granular detergent composition of the present invention. 25 to 55% is preferable. That is, if it is less than 10%, the detergency against oil stains becomes poor and the ability to suppress scale generation is reduced. Conversely, if it exceeds 60%, the overall balance is deteriorated, and the desired performance is reduced. 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 0.05 to 10% with respect to the entire granular detergent composition of the present invention. Among these, 2 to 7% is preferable. That is, if it is less than 0.05%, 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 10%, the balance as a whole becomes worse, and a synergistic effect with other components cannot be obtained any more, which is not preferable.

  Examples of the alkali metal carbonate (D) used in the granular detergent composition of the present invention include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium sesquicarbonate, sodium carbonate decahydrate and the like. These are also used alone or in combination of two or more. Of these, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, and potassium carbonate are preferably used.

  The content of the alkali metal carbonate that is the component (D) is not particularly limited, but is preferably set to 1 to 60% with respect to the entire granular detergent composition of the present invention. Among these, 15 to 40% is preferable. That is, if it is less than 1%, it is difficult to obtain sufficient detergency from the balance with other components. On the other hand, if it exceeds 60%, the balance as a whole is deteriorated and a synergistic effect with other components is further obtained. It is not preferable.

  Furthermore, as the polymer electrolyte polymer of the component (E) used in the granular cleaning 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, maleic anhydride Poly-β-ketocarboxylic acid derived from carbon monoxide, ethylene itaconate copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, methylene malonate copolymer Examples thereof include a copolymer, an itaconic acid fumaric acid copolymer, an ethylene glycol ethylene terephthalate copolymer, and a vinyl pyrrolidone vinyl acetate copolymer. 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 (E) is not particularly limited, but is preferably set to 0.1 to 10% with respect to the entire granular cleaning composition of the present invention. Especially, 0.5 to 5% is suitable. That is, if it is less than 0.1%, the desired effect of preventing recontamination and detergency are poor, and if it exceeds 10%, the balance as a whole deteriorates, storage stability decreases, and synergy with other components. The effect cannot be obtained any more, which is not preferable.

  Of the essential components (A) to (E), at least one component is preferably a hydrate. 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 cleaning composition of the present invention, water can be blended as the component (F) together with the essential components (A) to (E). 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 (F) 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.

  Moreover, an anhydrous alkali metal sulfate or an alkali metal sulfate sulfate hydrate can be mix | blended with the granular cleaning composition of this invention as (G) component. Examples of these include sodium sulfate, potassium sulfate, sodium sulfate decahydrate, magnesium sulfate, ammonium sulfate and the like. These can also be used alone or in combination of two or more. Of these, potassium sulfate, magnesium sulfate, ammonium sulfate, and sodium sulfate are preferable.

  When blending an anhydrous or hydrated alkali metal sulfate salt as the component (G), the content is preferably set to 1 to 50%, more preferably, based on the entire granular detergent composition. 3 to 25%. That is, it is because the detergency can be further enhanced by blending the alkali metal sulfate in this range. In addition, when it mixes exceeding 50%, while the balance as a whole worsens, the synergistic effect with another component is not acquired any more, and it is unpreferable.

  Furthermore, the granular detergent composition of the present invention may optionally contain known components such as a water-soluble solvent, a hydrotrope agent, a silicone-based antifoaming agent, a fragrance, a corrosion inhibitor, and a preservative. You can also.

  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 can be used by blending the water component (F) in the water or by 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 is produced using a raw material composition comprising the essential components (A) to (E) and the optional components (F) and (G), for example, as follows. can do. 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 has excellent performance in terms of cleaning performance, tableware finishing performance, and scale suppression 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 by comparatively big granule, it has the outstanding 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 (E), 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 said (F) 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.

  Furthermore, in the present invention, a chlorine-based bleach or an oxygen-based bleach can be mixed as the component (H) 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 the chlorine bleach or oxygen bleach of the component (H), it is desirable to use one having an average particle size set to 0.5 to 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 (H) 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 (H) is mixed, the content is set to 0.1 to 10% as the effective chlorine amount or the 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 tea astringent dirt. 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.

  In the present invention, as in the component (H), a detergent enzyme can be mixed as the component (I) into the aggregate of granulated substantially spherical particles. 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 (H) component.

  When mixing the enzyme for detergent which is the said (I) 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 an automatic dishwasher.

  The granular detergent composition of the present invention can be filled in various bags and containers such as cartridge type detergent containers and standing pouches for distribution.

  The granular cleaning composition of the present invention is diluted to a predetermined concentration via a cleaning agent supply device incorporated in or attached to various types of automatic dishwashers, and the cleaning agent diluted solution is added to the automatic tableware. It is used to clean food-related items such as dishes, cooking utensils, trays, bottles, and cans in washing machines.

  The automatic dishwasher that can use the granular cleaning composition of the present invention is not particularly limited, for example, door type, under counter type, rack conveyor type, flight conveyor type, fill and dump type, etc. Various automatic dishwashers can be used. And as a cleaning agent supply apparatus for dissolving the granular cleaning composition of the present invention and supplying it to an automatic dishwasher, for example, a supply apparatus described in Japanese Patent No. 3145918, or JP-A-2002-255198 The supply device and the like are preferably used as described in FIGS.

  In addition, it is suitable to set the dilution density | concentration at the time of using the granular cleaning composition of this invention with an automatic dishwasher to 0.01 to 0.5%. Moreover, as temperature conditions in an automatic dishwashing machine, a washing temperature is 40-70 degreeC, Preferably it is 55-65 degreeC, and a rinse temperature is 80-95 degreeC, Preferably it is 85-90 degreeC.

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 108, Reference Examples 1 and 2 , Comparative Examples 1 to 8]
In accordance with the composition shown in Tables 1 to 19 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, in accordance with the following test methods, etc., manufacturability, scattering properties, solubility, pH, stability of effective chlorine or effective oxygen, storage stability, ability to suppress scale formation, cleanability, ability to suppress reattachment, and finish after cleaning 10 items were evaluated. The results are also shown in Tables 1 to 19 below. In Tables 1 to 19 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.

[Scale generation suppression ability]
Test method Using artificial hard water (total hardness: 250 ppm as CaCO ₃ ), the granular detergent composition is diluted to 0.05%, 50 ml is poured into a colorimetric tube having a capacity of 100 ml, and kept at 60 ° C. for 24 hours. After that, the amount of scale produced was visually determined according to the following criteria.
Evaluation criteria A: No scale was generated.
○: There was almost no scale generation.
Δ: Scale was generated.
X: Scale adhesion was remarkable.

[Cleanability]
Test Method The prepared granular detergent composition was put into a commercial automatic dishwasher (model: DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. And the ceramic dish which is the following to-be-cleaned object was wash | cleaned as 10 sheets 1 set, and the washing | cleaning performance was evaluated by the evaluation criteria of a postscript. In addition, beef tallow, curry, and egg yolk were prepared as dirt, and cleaning evaluation was performed on each dirt.
* Operating condition Detergent concentration: 0.1%
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70-80 ppm (as CaCO ₃ )
Beef tallow dirt: Refined beef tallow was used.
Curry dirt: A commercially available retort curry (bon curry) was used.
Egg yolk stain: Only egg yolk was used, especially, with good mixing.
Object to be cleaned: A ceramic dish having a diameter of 10 cm was attached to the above-mentioned soil so as to be 4 g / sheet, and dried at normal temperature for 1 hour.
・ 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

[Reattachment inhibiting ability]
·Test method
30 g of salad oil colored with oil red together with the prepared granular detergent composition is put into a commercial automatic dishwasher (model: DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. The degree of dirt adhering to the clean dish made was visually judged according to the following criteria.
* Operating condition Detergent concentration: 0.1%
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Total hardness of tap water: 70-80 ppm (as CaCO ₃ )
-Evaluation criteria (double-circle): Dirt did not adhere to a clean dish at all.
○: Dirt was hardly adhered to the clean dish.
Δ: Dirt adhered to the clean dish.
X: Dirt was considerably adhered to the clean dish.

[Finishability test after cleaning]
Test Method The prepared granular detergent composition was put into a commercial automatic dishwasher (model: DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following conditions. And the glass cup which is a to-be-cleaned object shown later was wash | cleaned as 1 set, and the finished performance after washing | cleaning was evaluated by the evaluation criteria of a postscript.
* Operating condition Detergent concentration: 0.1%
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing 15 seconds)
Total hardness of water used: 70-80 ppm (as CaCO ₃ )
Objects to be cleaned: Milk was poured into an 8 ounce glass cup (manufactured by Sasaki Glass Co., Ltd.) and allowed to stand for 5 minutes. Next, after discarding the milk, it was air-dried for 30 minutes without rinsing with water.
・ Evaluation criteria A: No water spots are seen.
○: 1 to 2 water spots are seen.
Δ: 3 to 5 water spots are seen.
X: Six or more water spots are seen.

  The details of various components used in Tables 1 to 19 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.)

[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)

[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 (C16-C18) 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)

[D component]
・ Alkali metal carbonate 1
sodium carbonate
Product Name: Light Soda Ash (Made by Tokuyama Soda)
・ Alkali metal carbonate 2
sodium hydrogen carbonate
Product name: Sodium bicarbonate (made by Tokuyama Soda Co., Ltd.)

[E component]
・ Polyelectrolyte polymer 1
Sodium polymaleate average molecular weight: 1,800
Prototype / Polyelectrolyte Polymer 2
Sodium polyacrylate average molecular weight: 15,000
Product name: Socaran PA-40P (BASF)
・ Polyelectrolyte polymer 3
Acrylic acid-maleic acid copolymer Average molecular weight: 70,000
Product name: Socaran CP-45G (BASF)

[G component]
・ 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)

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

[I 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 9 to 11]
As Comparative Example 9 having a shape different from that of the granular detergent composition of the present invention, as shown in FIG. 2 (a), a detergent composition comprising a very fine powder (trade names: Deterfine Super MC, Johnson Diversity) Prepared). Further, as Comparative Example 10, as shown in FIG. 2 (b), a cleaning composition (trade name: Justpack PKLW, manufactured by Niitaka Corp.) in which very fine powder and relatively large particles are mixed is prepared. did. Furthermore, as Comparative Example 11, as shown in FIG. 2 (c), a detergent composition (trade name: Peretta A, manufactured by Lion Hygiene Co., Ltd.) composed of cylindrical pellets was prepared.

  And also about the said 3 comparative example goods, it evaluated about the evaluation item similar to the above, and the result is shown in following Table 20. The characteristics of each comparative example product are also shown in Table 20.

From the results of Table 1 to Table 20, although Examples 1 to 108 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, such as stability of effective chlorine or effective oxygen, storage stability, scale formation inhibitory ability, washing | cleaning property, reattachment inhibiting ability, and finishing property after washing | cleaning. In contrast, Comparative Examples 1-5, which lack even one essential component, and Comparative Examples 6-11, whose average particle diameter and shape are outside the scope of claims, have some 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 nine comparative examples, (b) is typical explanatory drawing which shows ten comparative examples, (c) is typical explanatory drawing which shows eleven comparative examples.

Claims (16)

While containing the following (A)-(E) component as an essential component, water is 0.1-9 mass%
The raw material composition to be contained is spray-dried after the following components (A) to (E) are prepared in the form of a slurry.
It is supplied to a high-speed agitation granulator in a state where it is not dried or melted by heating, and is granulated in a batch manner, and is measured by a sieving method described in JIS K-3362: 1998 “Synthetic detergent test method”. The average particle size determined from the particle size is set to 0.8 to 3.0 mm,
And the granular detergent composition for automatic dishwashers characterized by consisting of the aggregate | assembly of the substantially spherical granular material by which the sphericity calculated by following formula (1) was set to 0.7-1.0 .
(A) One or more compounds selected from alkali metal hydroxides and alkali metal silicates
Compound (B) sequestering agent (C) surfactant (D) alkali metal carbonate (E) polymer electrolyte polymer [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 (E) as essential components and not containing water, and at least one of these components (A) to (E) is a hydrate. , following
(A) to (E) are prepared in a slurry form and then spray-dried or melted by heating.
In a state where it is not fed, it is fed to a high-speed agitation granulator and is batch-typed, and is bound and granulated with the moisture derived from the hydrate leaving a gap between the component particles. JIS K- 336
2: The sphericity calculated by the following formula (1), in which 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. It consists of the aggregate | assembly of the substantially spherical granular material set to 0.7-1.0, The granular cleaning composition for automatic dishwashers characterized by the above-mentioned.
(A) One or more compounds selected from alkali metal hydroxides and alkali metal silicates
Compound (B) sequestering agent (C) surfactant (D) alkali metal carbonate (E) polymer electrolyte polymer [Equation 2]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material] The granular detergent composition for automatic dishwashers of Claim 1 or 2 which contains an anhydrous alkali metal sulfate or an alkali metal sulfate sulfate hydrate as (G) component with said (A)-(E) component. Claim containing as component (A), least A alkali metal hydroxides 1 or 2
The granular detergent composition for automatic dishwashers as described. The granular detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the sequestering agent of the component (B) is an alkali metal phosphate. The granular detergent composition for an automatic dishwasher according to any one of claims 1 to 4, wherein the sequestering agent of the component (B) is a phosphorus-free sequestering agent. The granular detergent composition for an automatic dishwasher according to claim 6, wherein the phosphorus-free sequestering agent is at least one selected from aminocarboxylic acids, hydroxyaminocarboxylic acids, and salts thereof. The particulate detergent composition for an automatic dishwasher according to any one of claims 1 to 7, wherein the surfactant of the component (C) is a nonionic surfactant. The polymer electrolyte polymer of the component (E) 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 automatic dishwashers as described in any one of Claims 1-8. The 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 detergent composition for automatic dishwashers as described. The granular detergent for automatic dishwashers according to any one of claims 1 to 10, wherein at least one of the following (H) component and (I) component is mixed in the aggregate of the substantially spherical granules. Composition.
(H) 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.
(I) An enzyme for detergents 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. It is a method of manufacturing the granular detergent composition for automatic dishwashers as described in any one of Claims 1-11, Comprising: The raw material composition for preparing a substantially spherical granular material, slurry each raw material component In shape
And it does not have or or heat melted spray drying after prepared, and subjected fed to a high-speed stirring granulator, the granulation step of the batch, JIS K-3362: 1998 "synthetic detergent test method"
The average particle size determined from the particle size measured by the described sieving method is 0.8 to 3.0.
The granular detergent composition for an automatic dishwasher, characterized by being granulated into a substantially spherical shape with a sphericity calculated by the following formula (1) of 0.7 to 1.0. The manufacturing method.
[Equation 3]
Sphericality = R2 / R1 (1)
[R1: major axis of granular material, R2: minor diameter of granular material] 13. The granulator having a high-speed stirring granulator having a rotary stirring blade and a rotary crushing blade.
The manufacturing method of the granular cleaning composition for automatic dishwashers of description. The granulated step in the high-speed stirring granulator is followed by a reduced-pressure drying step.
A process for producing a granular detergent composition for an automatic dishwasher according to 2 or 13. A pH at 25 ° C. (JIS Z-8802: 198) of a 0.1% by mass aqueous solution obtained by diluting the granular detergent composition for an automatic dishwasher according to claim 1 with water.
4 (according to “pH measurement method”) is prepared so as to be in the range of 8-12.
The manufacturing method of the granular cleaning composition for automatic dishwashers as described in any one of 2-14. The granular detergent composition for automatic dishwashers according to any one of claims 1 to 11,
Use of a granular detergent composition for an automatic dishwasher characterized in that it is prepared as a 01-0.5% by weight diluent and used for washing dishes, cooking utensils, etc. by an automatic dishwasher Method.

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