JP2007332243A - Detergent composition for automatic dish washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a detergent composition for an automatic dish washer, having an excellent inhibitory effect on water spot formation and no problems of storage stability and cleaning performance after storage. <P>SOLUTION: The detergent composition for an automatic dish washer comprises a particle (A) which is obtained by mixing a polymer compound (a) having a cationic group-containing monomer constituent unit and an anionic group-containing monomer constituent unit in a specific range of the molar ratio of [the total mole number of the cationic groups]/[the total mole number of the anionic groups], water (b), one or more kinds of water-soluble compounds (c) selected from a water-soluble inorganic salt and a solid water-soluble organic acid or its salt, adjusting the mixture to ≤10 mass% water content, mixing the mixture with water-insoluble inorganic powder (d) in the mass ratio (a)/(c) in a specific range. The content of the polymer compound (a) in the composition is 0.05-1.5 mass%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cleaning composition for an automatic dishwasher.

The technique which applies the high molecular compound which has a cationic group and an anionic group to the cleaning composition for automatic dishwashers is already known, and patent documents 1-5 can be referred to.
WO99 / 58633 pamphlet International Publication No. 03/99980 Pamphlet International Publication No. 02/20709 Pamphlet Special table 2003-505535 Special table 2005-527686

  In recent years, automatic dishwashers have rapidly become widespread, and washing machines that reduce the amount of washing water used from the viewpoint of energy saving and resource saving and increase the amount of tableware to be washed at one time have become mainstream. is occupying. However, when washing dishes with a large amount of dirt with such a washing machine, there is a problem that white deposits known as water spots are often formed on the dishes after washing / drying. Is strongly demanded.

Patent Document 1 discloses a technique of applying a cationic polymer compound or an amphoteric polymer compound as a cleaning agent technique for suppressing the formation of water spots. Patent Document 2 discloses a technique of applying a cationic polymer compound or an amphoteric polymer compound as a phosphoric acid scale formation inhibitor and Patent Document 3 as a fading or corrosion inhibitor. Patent Publication 4 and Patent Publication 5 disclose a technique using a diallylammonium-type monomer, a monomer having an acidic functional group, and a copolymer of other monomers as a stain redeposition preventing agent. Detergents for machine cleaning of kitchen utensils and tableware are described which are formulated as solid pre-blended products containing the polymer adsorbed and / or absorbed in a water-soluble inorganic carrier.
However, these publications do not solve the problem in the case where a predetermined polymer compound is present in the cleaning composition in a solid, granular or powder in detail.

  On the other hand, when a cationic polymer compound or an amphoteric polymer compound is blended into a powdery or granular detergent composition for an automatic dishwasher, the storage stability of the composition such as caking is significantly reduced, There is a problem that the storage stability of generally used inorganic peroxides is adversely affected and the cleaning performance after storage is significantly reduced.

  Therefore, the problem of the present invention is that the water spot formation suppression effect is excellent, there is no problem in storage stability such as caking, and the cleaning performance after storage, particularly the cleaning performance after storage of a composition containing an inorganic peroxide. It is an object of the present invention to provide a detergent composition for an automatic dishwasher that is free from problems.

  The present invention has a monomer constituent unit having a cationic group and a monomer constituent unit having an anionic group, and a molar ratio [total number of moles of cationic groups] / [total number of moles of anionic groups]. A polymer compound (a) having a ratio of 10/90 to 90/10, water (b), one or more water-soluble compounds (c) selected from water-soluble inorganic salts and solid water-soluble organic acids or salts thereof. After mixing and adjusting the water content of the mixture to 10% by mass or less, (a) / (c) obtained by mixing the water-insoluble inorganic powder (d) is 5/95 to 50/50 by mass ratio. The present invention relates to a cleaning composition for an automatic dishwasher, which contains certain particles (A), and the content of the polymer compound (a) in the composition is 0.05 to 1.5% by mass. A monomer structural unit having a cationic group and a monomer structural unit having an anionic group The polymer (a), water (b), and water-soluble inorganic having a molar ratio [total number of moles of cationic groups] / [total number of moles of anionic groups] of 10/90 to 90/10 One or more water-soluble compounds (c) selected from a salt and a solid water-soluble organic acid or a salt thereof are mixed, the water content of the mixture is adjusted to 10% by mass or less, and the water-insoluble inorganic powder (d) is then added. A step of preparing particles (A) in which (a) / (c) is 5/95 to 50/50 by mixing, and if necessary, the particles (A) and other particles are mixed. The manufacturing method of the cleaning composition for automatic dishwashers of the said this invention which has a process.

  According to the present invention, the water spot formation suppressing effect is excellent, there is no problem in storage stability such as caking, and the cleaning performance after storage, particularly the cleaning performance after storage of a composition containing an inorganic peroxide is problematic. A detergent composition for an automatic dishwasher is provided.

  In the present invention, a polymer compound (a) containing a monomer constituent unit having a cationic group [hereinafter referred to as monomer constituent unit (a1)] and a monomer constituent unit having an anionic group [hereinafter referred to as monomer constituent unit (a2)]. ) [Hereinafter referred to as component (a)].

  As the monomer structural unit (a1), monomer structural units represented by the following general formula (1) and / or general formula (2) are preferable.

[Wherein, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrogen atom, a methyl group, or a hydroxy group, and R ¹³ is an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms. X is —COOR ¹⁴ —, —CON (R ¹⁵ ) R ¹⁶ —, wherein R ¹⁴ and R ¹⁶ are alkylene groups having 2 to 5 carbon atoms, and R ¹⁵ is a hydrogen atom or a methyl group. R ²¹ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, and n is a number of 0 or 1. Y ^- is an anionic group. ]

In the general formula (1), R ¹¹ is preferably a hydrogen atom, and R ¹² is preferably a hydrogen atom or a methyl group. X is preferably —CON (R ¹⁵ ) R ¹⁶ —, and R ¹⁵ is preferably a hydrogen atom. R ¹³ is preferably a methyl group, Y ^- is a halogen ion, sulfate ion, alkyl sulfate ion having 1 to 3 carbon atoms, phosphate ions, fatty acid ion having 1 to 12 carbon atoms, an alkyl group having 1 to 3 carbon atoms 1 A benzenesulfonic acid ion which may be substituted by 3 is preferable, and a chloro ion is particularly preferable.

In general formula (2), R ²¹ is preferably a methyl group, and Y ⁻ is substituted by 1 to 3 halogen ions, sulfate ions, phosphate ions, fatty acid ions having 1 to 12 carbon atoms, and alkyl groups having 1 to 3 carbon atoms. Benzenesulfonic acid ions which may be present are preferred, and chloro ions are particularly preferred. n is preferably 0.

  As the monomer structural unit (a2), a monomer structural unit represented by the following general formula (3) is preferable.

[Wherein, R ³¹ represents a hydrogen atom, a methyl group, or —COOM, and R ³² represents a hydrogen atom, a methyl group, or a hydroxy group. Z is -COOM, a -ph-SO ₃ M. Here, M is a hydrogen atom, an alkali metal or an alkaline earth metal, and ph represents a benzene ring. ]

  The component (a) of the present invention may be a structure (a12) having a cationic group and an anionic group in one monomer constituent unit. Specifically, the monomer structural unit of the following general formula (4) or general formula (5) is preferable.

[Wherein R ⁴¹ and R ⁵¹ are a hydrogen atom or a methyl group, and R ⁴² and R ⁵² are a hydrogen atom, a methyl group or a hydroxy group. X, Y ⁻ and M have the same meaning as described above, R ⁴³ and R ⁵³ are an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, and R ⁵⁴ is —CH ₂ COO—, —C ₃ H _6. It is a group selected from SO ₃ ⁻ and —CH ₂ CH (OH) CH ₂ —SO ₃ ^— . ]
Specific examples of the monomer corresponding to the monomer structural unit represented by the general formula (1) include acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 5 carbon atoms) -N, N, N— Trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 5 carbon atoms) -N, N, N-trialkyl (1 carbon atom) -3) A quaternary ammonium salt can be mentioned. As the salt, a salt corresponding to the above-mentioned Y- is preferable.

  N, N-diallyl-N, N-dialkyl (C1-3) quaternary ammonium salt can be used as the monomer corresponding to the general formula (2). In addition, a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, or propylene oxide is used for the monomer structural unit obtained by polymerizing N, N-diallyl-N-alkyl (carbon number 1 to 3) amine. It can also be produced by alkylation.

  As monomers corresponding to the general formula (3), acrylic acid or a salt thereof, methacrylic acid or a salt thereof, crotonic acid or a salt thereof, α-hydroxyacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, Mention may be made of styrene sulfonates.

  The polymer compound having the monomer structural unit of the general formula (4) is an aminoalkyl (2 to 5 carbon atoms) dialkyl (1 to 3 carbon atoms) amine, or N, N -Dialkyl (1 to 3 carbon atoms)-N-alkanol (2 to 5 carbon atoms) amine is reacted, followed by alkylation using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide Can also be manufactured.

  As a monomer corresponding to the general formula (5), N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) 3) -N-carboxymethyl ammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)] -N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 carbon atom) -3) -N-sulfopropyl] ammonium Betaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-carboxymethyl ammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium Sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-sulfopropyl] ammonium sulfone Named betaine Kill.

  In the present invention, as a monomer structural unit having a cationic group, a monomer structural unit obtained by polymerizing an N, N-diallyl-N, N-dialkyl (C 1-3 quaternary ammonium salt), or N, Monomer composition in which N-diallyl-N-alkyl (1 to 3 carbon atoms) monomer structural unit is alkylated using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide. Monomer constituent unit obtained by polymerizing a monomer selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, or maleic anhydride as a monomer constituent unit having an anionic group. Is preferred.

  Component (a) of the present invention has a molar ratio of [total moles of cationic groups] / [total moles of anionic groups] of 10/90 to 90/10, preferably 30/70 to 80 /. 20, More preferably, a polymer compound of 40/60 to 70/30 is used. Moreover, when the anionic group is a carboxylic acid group, the preferred molar ratio is preferably 40/60 to 70/30.

  The component (a) of the present invention comprises a monomer constituent unit having a cationic group and a monomer constituent unit having an anionic group, preferably a monomer constituent unit selected from the general formulas (1) to (5). A polymer having a total of 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol% in all monomer constituent units constituting the component (a) Compounds are preferred.

  In the present invention, in addition to the monomer structural unit having a cationic group and the monomer structural unit having an anionic group, preferably the monomer structural unit selected from the general formula (1) to the general formula (5), the effect of the present invention. It may contain a monomer constituent unit obtained by copolymerizing a single monomer copolymerizable with these to such an extent that it is not impaired.

  In the present invention, a compound obtained by copolymerizing 1 to 15 mol% of sulfur dioxide in the component (a) is most preferable.

  The component (a) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred.

  The component (a) of the present invention preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 100,000, particularly preferably. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance with a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent.

  The detergent composition for an automatic dishwasher of the present invention is selected from the above-mentioned component (a), water (b) [hereinafter referred to as component (b)], a water-soluble inorganic salt, and a solid water-soluble organic acid or a salt thereof. By mixing one or more water-soluble compounds (c) [hereinafter referred to as the component (c)], the component (c) is loaded with the component (a), and the water content is adjusted to 10% by mass or less. Further, it contains particles (A) obtained by mixing water-insoluble inorganic powder (d) [hereinafter referred to as component (d)]. Moreover, the composition of this invention contains (a) component, (b) component, (c) component, and (d) component, (a) / (c) mass ratio is 5 / 95-50 / 50 and It is a detergent composition for an automatic dishwasher containing particles (A) having a moisture content of 10% by mass or less, and having a component (a) content in the composition of 0.05 to 1.5% by mass. .

  The mass ratio of component (a) / component (c) in the particles (A) is 5/95 to 50/50, preferably 5/95 to 40/60, more preferably 10/90 to 30/70. is there.

  In the particle (A), the component (b) is used so that the component (a) is supported on the component (c) as uniformly as possible. Since the localization of the component (a) on the surface of the component (c) can be suppressed by producing the particles (A) using the component (b), the cleaning composition for an automatic dishwasher according to the present invention. The storage stability is improved, which is preferable.

  The mass ratio (a) / (b) of the component (a) to the component (b) when the particles (A) are produced is preferably 5/95 to 95/5, more preferably 5/95 to 80. / 20, in particular 20/80 to 50/50. In this mass ratio range, the production efficiency of the particles (A) is good, and the storage stability of the cleaning composition is also good. Moreover, it is preferable because the component (a) is easily supported on the component (c).

  In the cleaning composition of the present invention, the component (a) is 0.05 to 1.5% by mass, preferably 0.2 to 1.5% by mass, more preferably 0.3 to 1.0%, in the composition. Contains by mass%. The particles (A) are used so that the content of the component (a) falls within this range.

  The water-soluble inorganic salt and solid water-soluble organic acid or salt thereof as the component (c) of the present invention is a compound having a 1% by weight aqueous solution having a pH of 3 to 12, more preferably 4 to 10, particularly 5 to 10 at 20 ° C. Is preferred.

  As the water-soluble inorganic salt as component (c), sulfates, hydrochlorides and phosphates are preferable, and salts that can have crystal water are particularly preferable. Specifically, sodium sulfate, potassium sulfate, and sodium tripolyphosphate are preferable.

  As the solid water-soluble organic acid or salt thereof as component (c), a water-soluble organic acid having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, particularly two or more in the molecule, preferably Is preferably a polyvalent carboxylic acid having 2 to 6 carboxylic acid groups or a salt thereof. Specifically, formic acid, acetic acid, gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid, fumaric acid, carboxylic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methylglycine diacetic acid, glutamic acid 2 Aminocarboxylic acids selected from acetic acid, serine diacetic acid, aspartic acid diacetic acid, and salts thereof are preferred, and citric acid, succinic acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, and diethylenetriaminepentaacetic acid are particularly preferred. The salt is preferably a sodium salt or a potassium salt.

  The mass ratio of the solid water-soluble organic acid or its salt / water-soluble inorganic salt is preferably 90/10 to 10/90, more preferably 70/30 to 10/90, and particularly preferably 50/50 to 10 /. 90 is preferred. When the water-soluble inorganic salt is a phosphate, the mass ratio of the solid water-soluble organic acid or its salt / water-soluble inorganic salt is preferably 0/100 to 20/80, particularly preferably 0/100. Is preferred.

  In the present invention, the content of the component (c) in the particles (A) is preferably 45 to 95% by mass, more preferably 50 to 90% by mass, after satisfying the above (a) / (c) mass ratio. %, More preferably 60 to 85% by mass.

  In the present invention, the particles (A) are obtained through the mixture containing the components (a) to (c). For the purpose of improving the particle properties, the mixture and the water-insoluble inorganic powder (d) [hereinafter referred to as the component (d) Mix]. Component (d) has a primary particle size of 5 nm to 200 μm, preferably 20 nm to 100 μm, particularly preferably 20 nm to 50 μm, and specifically, crystalline layered silicate, aluminosilicate, silica, and alumina are preferable. In the present invention, the content of the component (d) in the particles (A) is preferably 0.05 to 5% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 3% by mass. It is.

  When silica is used as the component (d), Aerosil (trademark) (manufactured by Nippon Aerosil Co., Ltd.), Toxeal (trademark), Fine Seal (trademark), Leolosil (trademark) (manufactured by Tokuyama Corporation), Silo Pure It is preferable to use (trademark) (made by Fuji Silysia Co., Ltd.).

  In the present invention, the addition of component (d) is such that the amount of water after mixing components (a) to (c) is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less. Sometimes added. Therefore, when the water content of the mixture exceeds 10% by mass, the component (d) is added after drying to 10% by mass or less. Considering the adhesion of the component (d), it is preferable that the water content does not become less than 0.5% by mass.

  In obtaining the particles (A), a binder substance may be used. The binder is preferably an organic compound other than the component (c), and polyethylene glycol and nonionic surfactants are common. The binder may be a liquid at room temperature, and a binder having at least a melting point is used. The binder affects not only the particle preparation but also the solubility.

  In the present invention, a known mixer such as Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.) or the like can be used for the mixing step. In particular, it is preferable to use a Nauter mixer that does not require much shearing force during stirring.

  Moreover, when manufacturing particle | grains (A) accompanying a drying process, the (c) component is circulated with warm air with a fluidized-bed granulation dryer etc., and the aqueous solution containing (a) component and (b) component Spraying and removing the moisture by drying while supporting the component (a) on the component (c), and adding the component (d) when the water content is 10% by mass or less, Can be manufactured.

  The average particle diameter of the particles (A) is preferably 50 to 1000 μm, more preferably 100 to 800 μm, and particularly preferably 100 to 600 μm.

  The amount of water in the particles (A) is 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less in consideration of addition of the component (d) and other components.

  Japanese Unexamined Patent Publication No. 2005-527686 (Patent Document 5) already discloses a technique for producing particles (A) by impregnating or supporting component (c) at a predetermined mass ratio with component (c). However, in the present invention, the component (c) is supported on the component (c) using water and the moisture content is adjusted, and then the component (d) is further mixed to improve the physical properties of the particles (A). This is essentially different from the prior art.

  The detergent composition for an automatic dishwasher of the present invention uses the particles (A), so that the component (a) exhibits excellent solubility, so that the effect can be expressed with a smaller addition amount. . Moreover, the effect excellent also in storage stability, such as caking, is exhibited by mixing (d) component.

  In the present invention, from the viewpoint of storage stability and the like, it is preferable that a strong alkaline agent or the like is blended as separate particles. In addition, enzymes and bleaching agents are preferably blended as separate particles from the viewpoint of stability and handling. Specifically, as particles other than the particles (A), particles (B) containing an alkali metal carbonate, particles (C) containing an aluminosilicate, silicate, particles containing an inorganic peroxide (D ), It is preferable to contain one or more particles selected from the enzyme-containing particles (E), and it is particularly preferable to contain all of the particles (B) to (E). Moreover, you may contain arbitrary particles (F) other than these particles.

  As the particles (B), sodium carbonate (light ash or dense ash) can be used, and it is particularly preferable to use dense ash having an average particle diameter of 100 to 500 μm. The content of the particles (B) in the composition is preferably 5 to 40% by mass.

The particles (C) are particles used for the purpose of improving the cleaning effect, and are clearly different from the water-insoluble inorganic powder (d) that can function as a powder physical property modifier for the particles (A). Used in. Silicates are amorphous sodium silicates such as Nos. 1-3 sodium silicate, and crystals marketed by Tokuyama Siltech Co., Ltd. under the trade name “Prefeed ™” (δ-Na ₂ Si ₂ O ₅ ). Layered sodium silicate is preferred. As the aluminosilicate, amorphous aluminosilicate is preferable.

  As the particles (C), crystalline layered sodium silicate having an average particle diameter of 5 to 800 μm is most preferable.

  Moreover, content in the composition of particle | grains (C) becomes like this. Preferably it is 3-10 mass%.

  The particles (D) are particles containing an inorganic peroxide. Specifically, it is percarbonate, preferably sodium percarbonate (hereinafter sometimes referred to as PC), perborate, preferably sodium perborate. Moreover, when employ | adopting a percarbonate, it is suitable to use the coated percarbonate from the point of storage stability.

  The coated percarbonate is preferably one coated with a water-soluble polymer or inorganic salt.

Among these, (i) sodium borate, preferably sodium metaborate, percarbonate coated with sodium orthoborate in a proportion of 0.1 to 30% by mass with respect to the percarbonate, (ii) orthoboric acid Percarbonate, preferably 1 to 8% by mass of boric acid selected from metaboric acid and tetraboric acid with respect to the percarbonate, and (iii) and (ii) further sodium metasilicate, sodium orthosilicate, water Glass No. 1, No. 2, No. 3 sodium salt, potassium metasilicate, ortho orthosilicate, preferably water glass No. 1, No. 2, No. 3 sodium salt converted to SiO ₂ with respect to the percarbonate, 0 Percarbonate with 3-5% by weight coated is preferred. In particular, sodium percarbonate is preferred from the viewpoint of storage stability.

  The coated percarbonate preferably has an average particle size of 250 to 1000 μm from the viewpoint of the bleaching washing effect.

  Moreover, content in the composition of particle | grains (D) becomes like this. Preferably it is 5-50 mass%.

  In the present invention, it is preferable to contain an enzyme-containing particle (E), and examples include cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase, and protease and amylase are particularly preferable. In the present invention, it is preferable to use a protease and amylase in combination.

  In the present invention, these enzymes are preferably contained as granulated particles. The amount of enzyme protein in the granulated product is preferably 2 to 25% by mass in the particle (E). The average particle diameter of the particles (E) is preferably 150 to 800 μm.

  Moreover, content in the composition of particle | grains (E) becomes like this. Preferably it is 0.2-5 mass%.

  The detergent composition for an automatic dishwasher of the present invention can contain a surfactant. The surfactant content in the composition is preferably 10% by mass or less, more preferably 5% by mass or less.

  In the present invention, it is preferable to add polypropylene glycol having a weight average molecular weight of preferably 2000 to 4000 to the composition because it provides a cleaning effect and can suppress the residual fragrance of the tableware after cleaning. The polypropylene glycol is preferably contained in the composition in an amount of 0.5 to 5% by mass.

  In addition, a pigment | dye, a fragrance | flavor, an antifoamer, polyacrylic acid and its salt, an acrylic acid / maleic acid copolymer, and its salt can be mention | raise | lifted as arbitrary components.

The cleaning composition for an automatic dishwasher of the present invention preferably has an average particle size of 200 to 700 μm. Moreover, it is preferable that the bulk density of a composition is 0.8-1.2 g / cm < ³ >.

The measurement of water content, average particle size, primary particle size and bulk density described in the present invention is as follows.
<Method for measuring moisture content>
Place about 2 g of sample on a petri dish as flat as possible, weigh the sample (Xg), dry with a dryer at 105 ° C. for 2 hours, weigh the sample after drying (Yg), Ask for.
Water content (%) = (X−Y) × 100 / X

<Measuring method of average particle size>
The average particle diameter is a median diameter, and is determined using a sieve specified in JIS Z 8801. For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 180 μm, and 125 μm, Rotap Machine (trademark) (manufactured by HEIKOSEI KUSHO, tapping: 156 times / minute, (Rolling: 290 times / min), a 100 g sample was vibrated for 5 minutes, and then the ratio of particles of each particle size was measured from the mass fraction according to the size of the sieve openings, and the average particle size was determined.

<Measurement method of primary particle size>
The particle size of 3,000 particles is measured with a scanning or transmission electron microscope, and the average particle size is obtained.

<Method for measuring bulk density>
The bulk density is measured by a method defined by JIS K 3362.

The most preferred embodiment of the present invention is shown below.
-Particle | grain (A): It contains in the quantity used as 0.4-1.0 mass% in a composition as (a) component. However, the particles (A) have an average particle size of 100 to 500 μm, and an aqueous solution containing 20 to 50% by mass of the polymer compound (a) is a water-soluble inorganic substance selected from sodium sulfate, sodium tripolyphosphate, and potassium sulfate. With respect to a mixture (c) of a water-soluble organic acid salt selected from a salt and sodium citrate, sodium succinate, sodium methylglycine diacetate, and sodium ethylenediaminetetraacetate, (a) / (c) is 10 / After mixing at a ratio of 90 to 30/70 and drying the mixture to a moisture content of 3% by mass or less, a water-insoluble inorganic powder (d) selected from crystalline silicate, aluminosilicate, silica and alumina is mixed. Thus, the content of (d) covering the particles (A) is 0.5 to 3% by mass, and the water content is 1 to 3% by mass.
-Particle | grain (B): Content in a composition is 5-40 mass%.
However, the particles (B) are light ash or dense ash having an average particle size of 100 to 500 μm.
-Particle | grain (C): Content in a composition is 3-10 mass%.
However, the particles (C) are crystalline layered sodium silicate having an average particle diameter of 5 to 800 μm.
-Particle | grain (D): Content in a composition is 5-50 mass%.
However, the particles (D) are sodium percarbonate having an average particle diameter of 250 to 1000 μm.
-Particle | grain (E): Content in a composition is 0.2-5 mass%.
However, the particles (E) are amylase-containing particles or protease-containing particles, each having an average particle size of 150 to 800 μm.
-Particle | grain (F): Content in a composition is 0-5 mass%.
However, the particles (F) are arbitrary particles and have an average particle diameter of 50 to 1500 μm, and are particles for enhancing other auxiliary agents and added values. For example, perfume particles that exhibit properties of deodorizing performance, Particles exhibiting the ability to disperse soils such as acrylic acid / maleic acid copolymer salts can be proposed. Furthermore, it contains particles having different properties as described above, and the particles (A) to (F) are preferably other particles as much as possible in order to prevent the particles from being separated into layers by vibration or the like (generally classification). And a detergent composition for an automatic dishwasher that is formulated as a uniform particle size.

  According to the present invention, the component (a), the component (b) and the component (c) are mixed, and after adjusting the water content of the mixture to 10% by mass or less, preferably the water content is dried to 10% by mass or less. Then, by mixing the component (d), the mass ratio of the polymer compound (a) and one or more water-soluble compounds (c) selected from water-soluble inorganic salts and solid water-soluble organic acids or salts thereof is used. There is provided a method for producing a cleaning composition for an automatic dishwasher according to the present invention, comprising the step of producing particles (A) in which (a) / (c) is 5/95 to 50/50.

<Method for Producing Particle (A)>
(1) Production of particles (A-1) 7.8 kg of sodium sulfate was charged into a fluidized bed granulator and circulated in warm air, and N, N-diallyl-N, N-dimethylammonium as a synthetic polymer compound. An aqueous solution of 2 kg of a copolymer (weight average molecular weight 450,000) obtained by polymerizing chloride and acrylic acid in a molar ratio of 69.5: 30.5 and 3 kg of water is sprayed, and the synthetic polymer compound is supported on sodium sulfate. While drying, the water content was removed to 2% by mass. Next, 0.2 kg of Toxeal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210 to 270 mL / 100 g, primary particle diameter of about 20 nm) is added, circulated and mixed as a water-insoluble inorganic powder to produce particles (A-1 ) In addition, as for the obtained particle (A-1), the mass ratio (a) / (c) of the component (a) and the component (c) is about 20/80, the water content is 2% by mass, and the average particle size. Was 280 μm.

(2) Production of particles (A-2) 7.8 kg of sodium sulfate was charged in a fluidized bed granulator and circulated in warm air, and N, N-diallyl-N, N-dimethylammonium as a synthetic polymer compound An aqueous solution composed of 2 kg of a copolymer (weight average molecular weight 20,000) and 6 kg of water polymerized at a molar ratio of chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6 was sprayed onto sodium sulfate. While supporting the synthetic polymer compound, the moisture was removed by drying until it became 2% by mass. Next, 0.2 kg of Toxeal NR as a water-insoluble inorganic powder was added, circulated and mixed to obtain particles (A-2). In addition, as for obtained particle | grains (A-2), mass ratio (a) / (c) of (a) component and (c) component is about 20/80, the moisture content is 2 mass%, and average particle diameter Was 260 μm.

(3) Production of particles (A-3) 7.8 kg of sodium sulfate was charged into a fluidized bed granulation dryer and circulated in warm air to produce N, N-diallyl-N, N-dimethylammonium as a synthetic polymer compound. Spray an aqueous solution consisting of 2 kg of copolymer (weight average molecular weight 1,500,000) polymerized at a molar ratio of chloride / acrylic acid / acrylamide = 36/32/32 and 18 kg of water, and support the synthetic polymer compound on sodium sulfate. While drying, the water content was removed to 2% by mass. Next, 0.2 kg of Toxeal NR as a water-insoluble inorganic powder was added, circulated, and mixed to obtain particles (A-3). The obtained particles (A-3) had a mass ratio (a) / (c) of the component (a) to the component (c) of about 20/80, the water content was 2% by mass, and the average particle size. Was 290 μm.

(4) Production of Particles (A-4) 5 kg of sodium sulfate and 2.8 kg of trisodium citrate are charged into a fluidized bed granulator / dryer and circulated in warm air to produce N, N-diallyl-- as a synthetic polymer compound. An aqueous solution comprising 2 kg of a copolymer (weight average molecular weight 20,000) polymerized at a molar ratio of N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6 and 6 kg of water. Spraying was performed, and the moisture content was removed by drying until the synthetic polymer compound was supported on sodium sulfate and trisodium citrate until the concentration became 2% by mass. Next, 0.2 kg of Toxeal NR as a water-insoluble inorganic powder was added, circulated and mixed to obtain particles (A-4). The obtained particles (A-4) had a mass ratio (a) / (c) of the component (a) to the component (c) of about 20/80, the water content was 2% by mass, and the average particle size. Was 290 μm.

(5) Production of particles (A-5) 8.6 kg of sodium sulfate was added to a Nauter mixer, and N, N-diallyl-N, N-dimethylammonium chloride and acrylic acid were added as synthetic polymer compounds to 69.5: An aqueous solution comprising 0.5 kg of a copolymer (weight average molecular weight 450,000) polymerized at a molar ratio of 30.5 and 0.75 kg of water was added and mixed for 15 minutes. As a water-insoluble inorganic powder, 0.2 kg of Toxeal NR was added and further mixed for 3 minutes to obtain particles (A-5). In addition, as for the obtained particle | grains (A-5), mass ratio (a) / (c) of (a) component and (c) component is about 5.5 / 94.5, and the moisture content is 7 mass%. The average particle size was 300 μm.

(6) Production of Particles (A-6) (Comparative Product) 7.8 kg of sodium sulfate was charged into a fluidized bed granulation dryer and circulated in warm air, and a synthetic polymer compound [component (a) in Table 1 for convenience] Sprayed with an aqueous solution consisting of 2 kg of N, N-diallyl-N, N-dimethylammonium chloride polymer (weight average molecular weight 150,000) and 3 kg of water, and dried while supporting the synthetic polymer compound on sodium sulfate. The water was removed until 2% by mass. Next, 0.2 kg of Toxeal NR as a water-insoluble inorganic powder was added, circulated and mixed to obtain particles (A-6). The obtained particles (A-6) had a mass ratio of the component (a) to the component (c) of about 20/80, a moisture content of 2% by mass, and an average particle size of 260 μm.

(7) Production of particles (A-7) (comparative product) 7.8 kg of sodium sulfate was added to a Nauter mixer, and N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / as a synthetic polymer compound An aqueous solution consisting of 2 kg of a copolymer (weight average molecular weight 20,000) polymerized at a molar ratio of sulfur dioxide = 66.7 / 26.7 / 6.6 and 6 kg of water was added and mixed for 15 minutes. As a water-insoluble inorganic powder, 0.2 kg of Toxeal NR was added and further mixed for 3 minutes to obtain particles (A-7). The obtained particles (A-7) had a mass ratio of the component (a) to the component (c) of about 20/80, a water content of 38% by mass, and an average particle size that could not be measured.

(7) Production of Particles (A-8) (Comparative Product) 8.0 kg of sodium sulfate was charged into a fluidized bed granulation dryer and circulated in warm air, and N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = sprayed with an aqueous solution consisting of 2 kg of copolymer (weight average molecular weight 20,000) and 6 kg of water polymerized at a molar ratio of 66.7 / 26.7 / 6.6. Then, while the synthetic polymer compound was supported on sodium sulfate, the moisture was removed by drying until 2% by mass to obtain particles (A-8). The obtained particles (A-8) had a mass ratio of the component (a) to the component (c) of about 20/80, a moisture content of 2% by mass, and an average particle size of 260 μm.

<Production method of cleaning composition>
Examples 1-5 and Comparative Examples 2-4
Sodium sulfate and trisodium citrate were mixed in a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min) for 1 minute at the blending ratio shown in Table 1, followed by particles (A) and particles (B). , Particles (C) and particles (F) were added and mixed for another minute. Polypropylene glycol was then added and mixed for 3 minutes, the surface modifier was added and mixed for an additional minute. Next, particles (D) and particles (E) were added, a fragrance was added, and the mixture was further mixed for 3 minutes to obtain 30 kg of a cleaning composition. In addition, although particle | grains (A-6)-(A-8) are other particle | grains, in Table 1, it showed as particle | grains (A) for convenience.

Comparative Example 1
In the same manner as in Examples 1 to 5 and Comparative Examples 2 to 4, 30 kg of a cleaning composition was obtained without adding particles (A).

Comparative Example 5
In the same manner as in Examples 1 to 5 and Comparative Examples 2 to 4, N, N-diallyl-N, N dimethylammonium chloride / acrylic acid = 30/70 (mass ratio) polymer instead of particles (A) ( A weight average molecular weight of 450,000) was added as a powder to obtain 30 kg of a detergent composition.

<Cleaning conditions>
Washing machine used: An automatic dishwasher (model NP-60SS5) manufactured by Matsushita Electric Industrial Co., Ltd. was used, and the following tableware and the detergent composition shown in Table 1 were put in and operated on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of a type that dries after warming and rinsing).
Contaminated dishes: 10 (prepared by the following method)
Uncontaminated glass cup: 9 Uncontaminated slide glass: 3 Water used: Water at 3.5 ° DH Detergent composition added amount: 6 g

<Preparation of contaminated dishes>
The half-boiled fried egg was ground and filtered through a 1 mm diameter net, and the filtrate was applied as uniformly as possible to a magnetic dish having a diameter of 11 cm, and 1.8 g per piece was allowed to stand for 1 hour.

<Finished glass cup evaluation method>
The number of water spots formed on the washed glass cup was counted over a fluorescent lamp and evaluated according to the following criteria. The results are shown in FIG.
A: The average value of the number of water spots in nine glass cups is within 25. ○: The average value of the number of water spots in nine glass cups is 26 to 40. Δ: Water spots of nine glass cups. The average value of the numbers of 41 to 100 ×: The average value of the number of 9 glass cup water spots is 100 or more

<Measurement of contact angle>
After washing, the contact angle of distilled water for 3 slide glasses was measured, and the average value was calculated.

<Storage stability>
700 g of the detergent composition shown in Table 1 is put in a box-type container (a kitchen quill container manufactured by Kao Corporation), stored in a thermostatic bath at 40 ° C. and 80% humidity for 30 days, and the state of the composition after storage is observed. ◎ when the storage is unchanged and ◎, slightly aggregated composition particles are observed, ○ if there is no problem in performance, △ slightly aggregated composition particles, if there is a decrease in performance △, considerably The case where aggregation of the composition particles was observed was evaluated as x.

(note)
1) Sodium percarbonate whose surface is coated with 3% sodium metaborate. Average particle size 700μm
2) Duramil 60T (trademark) (Novo Nordisk Bio Industry Co., Ltd.), average particle size 600 μm
3) Sabinase 18.0T (trademark) (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm
4) Socaran CP45 (trademark) (BASF), weight average molecular weight 70,000, average particle size 400 μm
5) Weight average molecular weight of about 3000, average degree of condensation of about 50, diol type, (Wako Pure Chemical Industries, Ltd.)
6) Toxeal NR (trademark) (manufactured by Tokuyama Corporation), amorphous silica, oil absorption: 210-270 mL / 100 g, primary particle diameter of about 20 nm

Claims (3)

It has a monomer structural unit having a cationic group and a monomer structural unit having an anionic group, and the molar ratio [total mole number of cationic group] / [total mole number of anionic group] is 10/90. A polymer compound (a) which is ˜90 / 10, water (b), a water-soluble inorganic salt and one or more water-soluble compounds (c) selected from solid water-soluble organic acids or salts thereof, and a mixture (A) / (c) is a particle having a mass ratio of 5/95 to 50/50, obtained by mixing the water-insoluble inorganic powder (d) after adjusting the water content to 10% by mass or less. A detergent composition for an automatic dishwasher, comprising A) and having a content of the polymer compound (a) in the composition of 0.05 to 1.5% by mass. The cleaning composition for an automatic dishwasher according to claim 1, wherein the water content in the particles (A) is 10% by mass or less. It has a monomer structural unit having a cationic group and a monomer structural unit having an anionic group, and the molar ratio [total mole number of cationic group] / [total mole number of anionic group] is 10/90. A polymer compound (a) which is ˜90 / 10, water (b), a water-soluble inorganic salt and one or more water-soluble compounds (c) selected from solid water-soluble organic acids or salts thereof, and a mixture After adjusting the water content to 10% by mass or less, by mixing the water-insoluble inorganic powder (d) component, the polymer compound (a) is selected from a water-soluble inorganic salt and a solid water-soluble organic acid or a salt thereof. The automatic tableware of Claim 1 or 2 which has the process of manufacturing the particle | grains (A) whose mass ratio (a) / (c) of the 1 or more types of water-soluble compound (c) which is 5 / 95-50 / 50 is manufactured. A method for producing a cleaning composition for a cleaning machine.