JP2008038023A - Cleanser composition for automatic dish washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleanser composition for automatic dish washers, excellent in a water spot formation-inhibiting effect. <P>SOLUTION: This cleanser composition for automatic dish washers comprises a polymer (a) having cationic group-having monomer-constituting units and anionic group-having monomer-constituting units in a molar ratio (the total mole number of the cationic groups)/(the total mole number of the anionic groups) of 30/70 to 90/10, and methyl glycine diacetic acid (salt) (b). <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 1-3 can be referred to. Patent Documents 4 and 5 can be referred to for the detergent composition containing an aminocarboxylic acid chelating agent.
WO99 / 58633 pamphlet International Publication No. 02/20709 Pamphlet European Patent Application No. 0998548 Japanese Patent Laid-Open No. 11-071595 JP 2004-210812 A

  In recent years, automatic dishwashers have rapidly spread, 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 a dish with a large amount of dirt is washed by such a washing machine, there is a problem that white deposits known as water spots are often formed on the dish 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. These publications do not disclose the use of a predetermined polymer compound in the detergent composition.

  On the other hand, it is known to apply aminocarboxylic acid type chelating agents to detergents, and Patent Documents 4 and 5 disclose techniques of detergents containing methylglycine diacetic acid. However, these do not suggest a specific means for obtaining an excellent water spot formation suppressing effect.

  Therefore, the subject of this invention is providing the cleaning composition for automatic dishwashers excellent in the water spot formation inhibitory effect.

  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]. The present invention relates to a cleaning composition for an automatic dishwashing machine, comprising a polymer compound (a) having a ratio of 30/70 to 90/10, and methylglycine diacetic acid (salt) (b).

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for automatic dishwashers which is excellent in the water spot formation inhibitory effect 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)].

  The component (a) of the present invention can be produced by subjecting a monomer corresponding to the monomer structural unit constituting the component (a) to a normal polymerization reaction. Or you may finally obtain (a) component by performing a post-process to a high molecular compound. For example, in the case of a polymer compound having a quaternary ammonium group as a cationic group, it has an amino group in addition to a method of obtaining a monomer having a quaternary ammonium group in the initial monomer by a polymerization reaction. The component (a) may be obtained by subjecting a product subjected to a polymerization reaction using a monomer to quaternization treatment. Of course, the same applies to anionic groups. Naturally, the monomer used for obtaining the polymer compound that requires post-treatment is selected to have a structure that takes post-treatment into consideration.

Specific monomers corresponding to the monomer structural unit (a1) 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 to 3 carbon atoms) 4 Class ammonium salts can be mentioned. Salts corresponding to the preferred ^- above Y is a salt. In addition, acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) amine, acryloyl (or methacryloyl, α-hydroxyacryloyl, or Crotonoyl) oxyalkyl (2 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) monomer structural unit obtained by polymerizing methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide, etc. It can also be produced by alkylating with a classifier. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).

  In addition to the above monomers, diallyl type monomers can also be used. As a specific monomer, N, N-diallyl-N, N-dialkyl (C1-3) quaternary ammonium salt can be used. 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. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).

  Specific examples of the monomer corresponding to the monomer structural unit (a2) include 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. Mention may be made of salts, maleic anhydride, styrene sulfonates. The monomer structural unit obtained by polymerizing styrene sulfonate is neutralized by sulfonating a compound obtained by polymerizing styrene with a sulfonating agent such as sulfur trioxide, chlorosulfonic acid, sulfuric acid or the like. Can also be obtained.

  In addition to the monomer structural unit (a1) and the monomer structural unit (a1), the component (a) of the present invention has a structure having a cationic group and an anionic group in one monomer structural unit [hereinafter, monomer structural unit (Referred to as (a12)). As a monomer corresponding to the monomer structural unit (a12), N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (carbon number) 1-3) -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) 3) -N- [2-hydroxysulfopropyl] ammonium sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (carbon) Formula 1-3) -N-sulfopropyl] Nmmonium sulfobetaine, 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 carbo Betaine, 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 sulfobetai It can be mentioned.

  In addition to the above, the polymer compound having the monomer structural unit (a12) may be an aminoalkyl (2 to 5 carbon) dialkyl (1 to 3 carbon) amine, or a monomer structural unit obtained by polymerizing maleic anhydride in advance. N, N-dialkyl (1 to 3 carbon atoms) -N-alkanol (2 to 5 carbon atoms) amine is reacted, followed by quaternizing agents such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide and the like. It can also be produced by alkylation using. In addition, when using ethylene oxide and / or propylene oxide, it is necessary to neutralize and react an amino group with the acid shown by YH (Y is the said anionic compound).

  In the present invention, as the monomer structural unit (a1) having a cationic group, a monomer structural unit obtained by polymerizing, in particular, an N, N-diallyl-N, N-dialkyl (C 1-3 quaternary ammonium salt), Or, alkylate a monomer structural unit obtained by polymerizing N, N-diallyl-N-alkyl (1 to 3 carbon atoms) amine using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, or propylene oxide. 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 is polymerized as a monomer constituent unit (a2) having an anionic group. A monomer structural unit obtained in this manner is preferred.

  Component (a) of the present invention has a molar ratio of [total number of moles of cationic groups] / [total number of moles of anionic groups] of 30/70 to 90/10, preferably 35/65 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 30/70 to 70/30.

  The component (a) of the present invention is the sum of the monomer structural unit (a1) having a cationic group and the monomer structural unit (a2) having an anionic group in all monomer structural units constituting the component (a). 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% of the polymer compound.

  In the present invention, in addition to the monomer structural units (a1), (a2) and (a3), a monomer structural unit obtained by copolymerizing a monomer copolymerizable with these to such an extent that the effects of the present invention are not impaired. The monomer structural unit (a3)] may be included. Specific examples of the monomer corresponding to the monomer structural unit (a3) include acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N , N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, acrylic acid ( Or alkyl methacrylate (carbon number 1 to 5), acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (carbon number 1 to 5), vinyl acetate , Ethylene, propylene, N-butylene, isobutylene, N-pentene, isoprene, -Methyl-1-butene, N-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, α- Mention may be made of methylstyrene, allylamine, N, N-diallylamine, N, N-diallyl-N-alkyl (1 to 5 carbon atoms) amine, ethylene oxide, propylene oxide and sulfur dioxide. The component (a) of the present invention can be obtained by a known polymerization method.

  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 5,000 to 60,000. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.

  In the present invention, methylglycine diacetic acid or a salt thereof is used as the component (b). As the salt, a sodium salt, potassium salt, or alkanolamine salt can be used. Even when the above component (a) is used alone, it has an effect of suppressing water spot formation, but in a scene washed with water with high hardness, especially in a scene where dishes with a large amount of dirt are washed, a satisfactory finish is achieved. It may not be obtained. In such a situation, the combined use of the component (b) of the present invention works effectively. When a powdery or granular component is used as the component (b), the average particle size is preferably 50 to 1000 μm, more preferably 100 to 800 μm.

  The detergent composition for an automatic dishwasher of the present invention is a particle in which the component (a) and the component (b) are present in the same particle, that is, a particle containing the component (a) and the component (b) [hereinafter referred to as particle (Referred to as (A)). In this case, (b) component mix | blends the above-mentioned powdery thru | or granular thing.

  The particles (A) are solid water-soluble having a pH of 3 to 12, preferably 4 to 10, more preferably 5 to 10 at 20 ° C. in a 1% by mass aqueous solution in addition to the components (a) and (b). Particles containing an organic compound (however, excluding component (b), hereinafter referred to as component (c1)) or a water-soluble inorganic salt (hereinafter referred to as component (c2)) are preferred. The content of the component (c1) and / or the component (c2) is preferably 60 to 99.5% by mass, preferably 70 to 99% by mass, particularly preferably 70 to 98.5% by mass in the particles (A). is there.

  The component (c1) is a water-soluble organic acid having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, particularly a polyhydric group having 2 or more, preferably 2 to 6 carboxylic acid groups in the molecule. Divalent carboxylic acids or their salts are preferred. Specifically, a carboxylic acid selected from formic acid, acetic acid, gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid and fumaric acid and salts thereof are preferred, and citric acid is particularly preferred. The salt is preferably a sodium salt or a potassium salt.

  As the component (c2), sulfates, hydrochlorides, and phosphates are preferable, and salts that can have water of crystallization are particularly preferable. Specifically, sodium sulfate, potassium sulfate, and sodium tripolyphosphate are preferable.

  In the particle (A) of the present invention, the component (c1) and the component (c2) may be used in combination, and the mass ratio of the component (c1) / (c2) is preferably 90/10 to 10/90, 70/30 to 10/90 is more preferable, and 50/50 to 10/90 is particularly preferable. When the component (c2) is a phosphate, the mass ratio of the component (c1) / (c2) is preferably 0/100 to 20/80, and particularly preferably 0/100.

  In the present invention, the particle (A) can be obtained by mixing the component (a), the component (b), the component (c1), the component (c2), or a mixture thereof. From the viewpoint of the inhibitory effect, an aqueous solution containing 5 to 80% by mass, preferably 8 to 50% by mass, particularly preferably 20 to 50% by mass of component (a), component (b), component (c1) and / or ( It is preferable to produce the particles (A) by a method of mixing the component c2). When the component (a) is used as an aqueous solution, the pH at 25 ° C. of the aqueous solution containing 5 to 80% by mass of the component (a) is adjusted to 8 or less, particularly 2 to 7 for use in blending suitability and cleaning performance. In addition, it is preferable from the viewpoint of water spot formation suppression effect and stability. The amount of water in the aqueous solution containing the component (a) affects the effect of the present invention. When the concentration of the component (a) in the aqueous solution is not more than the above range, the storage stability decreases and the cleaning effect after storage decreases. In addition, when the concentration of the component (a) exceeds the above range, the cleaning effect tends to decrease.

  Usually, a binder substance is used for formulation of an active substance, but in the present invention, a small amount of water in the aqueous solution (a) acts as a binder.

  In the present invention, the aqueous solution of the component (a) is mixed with the component (b) and the component (c1) and / or the component (c2), and then the mixture and the water-insoluble inorganic powder are mixed for the purpose of improving particle properties. It is preferable to do. The water-insoluble inorganic powder preferably has a primary particle size of 5 nm to 200 μm, preferably 20 nm to 100 μm, particularly preferably 20 nm to 50 μm. Specifically, crystalline silicate, aluminosilicate, silica and alumina are preferable. .

  In the particle (A) of the present invention, the component (a) is 0.05 to 10% by mass, preferably 0.3 to 10% by mass, more preferably 0.4 to 8% by mass, and the component (b) is 0.00. 3 to 30% by mass, preferably 0.5 to 20% by mass, more preferably 0.7 to 10% by mass, (c1) component and / or (c2) component 60 to 99.5% by mass as anhydrous conversion, Preferably it is 70-99 mass%, Most preferably, it is 70-98.5 mass%, 0.1-3 mass% of water-insoluble inorganic powder, Preferably it is 0.5-2.5 mass%, Most preferably, it is 0.8. The particles contain 7 to 2% by mass, and the water content is 0.05 to 15% by mass, preferably 0.3 to 15% by mass, and particularly preferably 0.3 to 10% by mass. is there.

  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 particles (A) have an average particle diameter of 50 to 1000 μm, more preferably 100 to 800 μm, as the component (b), preferably an average particle diameter of 10 to 800 μm, more preferably 50 to 800 μm, particularly preferably 100 to 500 μm. It is preferable to be obtained from particles containing the component (c1), the component (c2) or a mixture thereof.

  The particle (A) may be a particle in which the component (a) is attached to the particle surface of the component (c1) or the component (c2), and the surface is coated with the above water-insoluble inorganic powder ( It is ideal because it has a high fluidity. Depending on the type of component (c1) and component (c2) or the type and concentration of the binder, after addition of the aqueous solution containing component (a) or when the binder material is added, the component (a) is aggregated. In some cases, the aggregated particles are included. Further, the surface of the aggregated particles may be covered with a water-insoluble inorganic powder.

  In the cleaning composition of the present invention, the component (a) is preferably 0.05 to 1.5 mass%, more preferably 0.2 to 1.5 mass%, and still more preferably 0.3 to 0.5 mass% in the composition. 1.4 mass%, (b) Preferably it contains 0.3-30 mass%, More preferably, it contains 0.5-20 mass%, More preferably, it contains 0.7-10 mass%. For the purpose of effectively obtaining the effects of the present invention, in the composition of the present invention, the mass ratio of component (a) / component (b) is 0.01 to 30, more preferably 0.05 to 10, and particularly preferably 0.00. 1-5 are suitable, and the sum total of (a) component and (b) component is 0.5-35 mass% in a composition, Furthermore, 0.7-25 mass%, Especially 1-15 mass% Is preferred. The particles (A) are used so that the content of the component (a) and the component (b) falls within this range. Of all the components (a) and (b) in the composition, 80% by mass or more, more preferably 90% by mass or more, and particularly substantially 100% by mass is preferably present in the particles (A). .

  When producing the particles (A), the component (a) is preferably added as an aqueous solution. In that case, although there is a possibility that a small amount of the component (a) and / or the component (b) migrates to other particles after mixing the particles (A) with other particles, the particles (A) of the present invention are the present invention. It should just exist in the range.

  The cleaning composition for an automatic dishwashing machine of the present invention may be composed only of the particles (A). In that case, as the component (c1) or the component (c2), the substance (A) It is preferable to mix in the above. For example, phosphate exhibits alkalinity and buffering capacity in addition to excellent chelating ability. In order to increase the alkalinity of the cleaning liquid, an alkali agent can be additionally used. It is also proposed to use an organic chelating agent such as citric acid (salt) as the component (c1) and an alkali agent such as carbonate as the component (c2). However, in the present invention, from the viewpoint of storage stability and the like, it is preferable to blend a strong alkaline agent or the like as separate particles. In addition, enzymes and bleaching agents are preferably blended as separate particles from the viewpoint of stability and handling. Specifically, particles other than the particles (A) include particles (B) containing an alkali metal carbonate, particles (C) containing an aluminosilicate and / or silicate, and particles containing an inorganic peroxide. It is preferable to contain one or more particles selected from (D) and enzyme-containing particles (E), and it is particularly preferable to contain all the particles (B) to (E). Moreover, you may contain arbitrary particles (F) other than these particles.

  As the particles (B), sodium carbonate (light ash, dense ash) can be used, and it is particularly preferable to use dense ash having an average particle diameter of 50 to 600 μm, preferably 100 to 500 μm. Moreover, content in the composition of particle | grains (B) becomes like this. Preferably it is 1-80 mass%, More preferably, it is 5-70 mass%, Most preferably, it is 5-40 mass%.

The particle (C) is a particle used for the purpose of improving the cleaning effect, and is used for a purpose that is clearly different from the water-insoluble inorganic powder that can function as a powder physical property modifier or the like of the particle (A). . Silicates are amorphous sodium silicates such as No. 1-3 sodium silicate, and crystalline sodium silicate commercially available from Tokuyama Siltech Co., Ltd. under the trade name “Prefeed” (δ-Na ₂ Si ₂ O ₅ ). Is preferred. As the aluminosilicate, amorphous aluminosilicate is preferable.

  As the particles (C), crystalline sodium silicate having an average particle diameter of 1-1000 μm, preferably 5-800 μm is most suitable.

  The content of the particles (C) in the composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by 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.

  The average particle size of the percarbonate is preferably 100 to 2000 μm, more preferably 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 5-70 mass%, More preferably, it is 5-60 mass%, Most 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, these enzymes are preferably contained as granulated particles. The amount of enzyme protein in the granulated product is 1 to 30% by mass, preferably 2 to 25% by mass in the particles (E). Moreover, the average particle diameter of particle | grains (E) is 50-1000 micrometers, Preferably it is 150-800 micrometers.

  The content of the particles (E) in the composition is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and particularly preferably 0.2 to 5% by mass.

  The cleaning composition for an automatic dishwashing machine of the present invention can contain a surfactant. In the case of containing a surfactant, it is preferable to reduce it as much as possible from the viewpoint of the water spot formation suppressing effect, and the content of the surfactant is preferably 10% by mass or less, more preferably 5% by mass in the composition. % Or less is preferred. In the surfactant, the copolymer type nonionic surfactant of oxypropylene and oxyethylene is preferably less than 0.01% by weight.

  In the present invention, it is preferable to add polypropylene glycol having a weight average molecular weight of 600 to 5,000, preferably 2,000 to 4,000, to the composition because it provides a cleaning effect and can suppress the remaining fragrance of the tableware after the cleaning. Polypropylene glycol is preferably contained in the composition in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, particularly 1 to 5% by mass.

  In addition, bleaching activators such as dyes, fragrances, antifoaming agents, polyacrylic acid and salts thereof, acrylic acid / maleic acid copolymers and salts thereof, and tetraacetylethylenediamine (TAED) can be listed as optional components. .

  These arbitrarily compoundable compounds may be added to each particle to such an extent that the stability and properties of the component are not impaired, or may be added separately as particles (F). Alternatively, after mixing the particles (A) to (F), they may be added by spraying as a liquid, or added as fine particles (or powder).

The detergent composition for an automatic dishwasher according to the present invention preferably has an average particle size of 100 to 1000 μm, more preferably 200 to 700 μm. Further, it is preferable that the bulk density of the composition is 0.8 to 1.5 g / cm ^3, a further 0.8~1.2g / cm ^3.

The average particle diameter, primary particle diameter, and bulk density described in the present invention are measured as follows.
<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 saucer with openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 180 μm, and 125 μm, a low-tapping machine (made by HEIKOSEISAKUSHO, tapping: 156 times / min, rolling: 290 And a 100 g sample is vibrated for 5 minutes, and then the proportion of particles of each particle size is measured from the mass fraction according to the size of the sieve opening to determine the average particle size.

<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 (A): contained in the composition as component (a) in an amount of 0.4 to 1.0% by mass and as component (b) in an amount of 0.5 to 20% by mass.
However, the particles (A) have an average particle size of 100 to 500 μm, the polymer compound (a) is 0.5 to 8% by mass, and the component (b) having an average particle size of 50 to 1000 μm is 0.3 to 30. Citric acid (c1) selected from 7% to 50% by mass and 100 to 500 μm in average particle size of at least one component (c2) having a mean particle size of 100 to 500 μm, selected from mass%, sodium sulfate, sodium tripolyphosphate and potassium sulfate 7 to 50% by mass of the component, 0.5 to 2% by mass of water-insoluble inorganic powder covering particles (A) selected from crystalline silicate, aluminosilicate, silica and alumina, ) Component / (c2) component particles having a mass ratio of 50/50 to 10/90.
-Particle | grain (B): Content in a composition is 5-40 mass%.
However, the particles (B) are light ash and 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) contain amylase and protease and have 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, the particles (A) to (F) contain particles having different properties as described above, and the particles (A) to (F) are prevented from being divided into layers by vibration or the like (generally referred to as classification). It is a detergent composition for an automatic dishwasher that is blended as much as possible with other particles.

<Production method of particles (A)>
Example: Methylglycine diacetic acid trisodium salt (component (b)), sodium sulfate and trisodium citrate salt were added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min) and mixed for 1 minute. did. Next, an aqueous solution of the polymer compound (a) was added and mixed for 5 minutes. Next, a surface modifier (half the amount to be added to the cleaning composition) was added and further mixed for 1 minute to obtain particles (A). In addition, the addition amount of each component was made into the quantity calculated from the mixture ratio shown in Table 1 corresponding to 30 kg of cleaning composition.

Comparative Example: Sodium sulfate and trisodium citrate were added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min) and mixed for 1 minute. Next, an aqueous solution of the polymer compound (a) was added and mixed for 5 minutes. Next, a surface modifier (half the amount to be added to the cleaning composition) was added and further mixed for 1 minute to obtain particles (A). In addition, the addition amount of each component was made into the quantity calculated from the mixture ratio shown in Table 1 corresponding to 30 kg of cleaning composition.

<Production method of cleaning composition>
Examples and Comparative Examples: After producing the particles (A), particles (B), particles (C), and particles (F) were further added and mixed for 1 minute. Next, polypropylene glycol was added and mixed for 3 minutes, a surface modifier (half the amount added to the cleaning composition) was added, and further mixed for 1 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.

<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: 3.5 ° DH or 8.0 ° DH water Detergent composition addition: 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 0.9 g or 1.8 g per plate on a magnetic dish having a diameter of 11 cm.

<Finished glass cup evaluation method>
The number of water spots formed on the washed glass cup was counted over a fluorescent lamp, and the average number of nine was determined. The results are shown in Table 1.

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

(note)
1) A copolymer polymerized at a molar ratio of N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6 (weight average molecular weight 20,000, 25% by weight aqueous solution)
2) Trilon M Granlat (BASF methyl glycine diacetic acid 3Na), average particle size 400 μm
3) Tokuseal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210-270 mL / 100 g), primary particle size of about 20 nm
4) Sodium percarbonate whose surface is coated with sodium metaborate. Average particle size 700μm
5) Duramil 60T (Novo Nordisk Bioindustry Co., Ltd.), average particle size 600 μm
6) Sabinase 18.0T (Novo Nordisk Bio Industry Co., Ltd.), average particle size 600 μm
7) Socaran CP45 (BASF Corporation), average particle size 400 μm
8) Weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)

Claims (2)

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 30/70. A detergent composition for an automatic dishwasher comprising a polymer compound (a) of ~ 90/10, and methylglycine diacetic acid or a salt thereof (b). The cleaning composition for an automatic dishwasher according to claim 1, comprising particles (A) containing the polymer compound (a) and methylglycine diacetic acid or a salt thereof (b).