JP2018145384A - Molten solid detergent composition for automatic dishwashers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fused solid type detergent composition for automatic dishwasher, which can be supplied as compact products that can be efficiently produced, is excellent in the storability and free from fear of deliquescence during storage of products, is excellent in dissolution stability and is not excessively dissolved or does not cause defective dissolution, and can be supplied at a low concentration.SOLUTION: A fused solid type detergent composition for automatic dishwashers of the present invention is characterized by containing 40 mass% or larger and 50 mass% or smaller of alkali metal hydroxide as an (A) component, 25 mass% or larger and 45 mass% or smaller of aminocarboxylic acid chelate agent as a (B) component, 0.1 mass% or larger and 10 mass% or smaller of a high molecule polymer as a (C) component, and water as a (D) component, and, by mass ratio, (A)/{(A)+(D)}=0.58 or larger and 0.75 or smaller.SELECTED DRAWING: None

Description

  The present invention relates to a molten solid detergent composition for an automatic dishwasher obtained by solidifying a melt-mixed detergent composition.

  Conventionally, liquid or powder detergent compositions have been used as detergents for automatic dishwashers, but liquid type detergent compositions are bulky and have problems in transportation and storage. In addition, powder type cleaning compositions can be made more compact than liquid types, but problems such as environmental pollution and workability degradation due to powder scattering, and dissolution of compounding ingredients in powder cleaning compositions There is a problem that the composition and concentration of the cleaning liquid are not always constant due to the difference in speed and the like, and it is difficult to obtain uniform cleaning properties. In recent years, due to increasing environmental awareness, there is an increasing demand for phosphorus-free detergents that can be used at low concentrations with more concentrated active ingredients. Instead of liquid-type and powder-type detergent compositions, compaction at high concentrations Therefore, there is a need for a melted solid detergent composition for an automatic dishwasher in which the solubility of each component is uniform and stable washing performance is exhibited as compared with a powder type.

  On the other hand, the molten solid detergent composition for an automatic dishwasher contains 20 to 60% by weight of an alkali metal hydroxide salt, a sequestering agent such as an aminocarboxylate, and part of the alkali metal hydroxide salt is anhydrous. Solid detergent (patent document 1) dispersed in the state of alkali metal hydroxide salt, about 2 to 15% by weight of an alkali source at least partly of sodium or the like, and aminocarboxyl at least partly of potassium salt A solid-type detergent (Patent Document 2) containing about 20 to 40% by weight of an acid-type metal ion sequestering agent has been proposed.

Japanese Patent Laid-Open No. 2002-3895 Japanese National Patent Publication No. 6-501717

  A melted solid detergent composition for an automatic dishwasher is distributed as a cartridge-type detergent in which a composition obtained by melting and mixing each component is filled and stored in a container such as plastic and cooled and solidified. However, when the alkali metal hydroxide salt and the aminocarboxylic acid chelating agent are blended at a high concentration, the viscosity of the melted and mixed slurry is rapidly increased, and the filling efficiency of the slurry into the container is deteriorated or the container is filled. There was a problem that the slurry was previously solidified and filling was difficult. In addition, the solid detergent described in Patent Document 2 contains a potassium salt in a part of the high-concentration aminocarboxylic acid type sequestering agent, so that the product after solidification is easily deliquescent during storage. was there. In addition, in order to demonstrate stable performance at a low concentration, it is important that the composition after molding is uniform and free of components, and has a proper solubility so that it can be stably supplied. In this technique, the viscosity is low at the time of high temperature filling and the components are biased, the melting point is low and it is easy to melt, or it is too hard to be melted, so the supply stability at a low concentration is not sufficient.

  The present invention has been made in view of the above-described conventional problems, and solves the problems of conventional molten solid detergent compositions for automatic dishwashers containing alkali metal hydroxides and aminocarboxylic acid chelating agents. , Providing a molten solid detergent composition for automatic dishwashers that is compact, has no component bias, has excellent long-term storage stability, has good dissolution stability, and has excellent low-concentration detergency and scale prevention. The purpose is to do.

  In order to solve the above-mentioned problems, the present inventor has intensively studied, and as a result, an alkali metal hydroxide, an aminocarboxylic acid chelating agent and a polymer are blended at a specific ratio, and the alkali metal hydroxide and water are mixed. By setting the ratio within a specific range, the present inventors have found that the problem of the melted solid detergent composition in which the alkali metal hydroxide and the aminocarboxylic acid chelating agent are blended at a high concentration can be solved. It came to complete.

That is, the present invention
(1) Alkali metal hydroxide 40% by mass or more and 50% by mass or less as component (A), aminocarboxylic acid chelating agent 25% by mass or more and 45% by mass or less as component (B), high as component (C) Molecular polymer 0.1% by mass or more and 10% by mass or less, (D) water as component, (A) / {(A) + (D)} = 0.58 or more, 0.75 or less in mass ratio A molten solid detergent composition for an automatic dishwasher, characterized in that
(2) The molten solid detergent composition for an automatic dishwasher according to the above (1), wherein the mass ratio of the component (A) to the component (C) is (A) / (C) = 5 or more and 39 or less,
(3) The above (1) or (2), wherein the polymer of component (C) is at least one selected from an acrylic acid / sulfonic acid copolymer, an acrylic acid / maleic acid copolymer, and a salt thereof. ) Molten solid detergent composition for automatic dishwashers,
(4) A molten solid detergent composition for an automatic dishwasher according to any one of (1) to (3), further containing 5% by mass or less of a nonionic surfactant as component (E),
(5) The molten solid detergent composition for automatic dishwashers according to any one of (1) to (4), further containing 15% by mass or less of an inorganic builder as component (F),
(6) The molten solid detergent composition for an automatic dishwasher according to any one of (1) to (5) above, further comprising a chlorine bleach coated with a coating containing a benzoate as component (G) object,
(7) The molten solid detergent composition for an automatic dishwasher according to any one of the above (1) to (6) is installed in an elution hopper having a discharge port at the lower end portion, and water is supplied from a water supply nozzle. The molten solid detergent composition for automatic dishwashers in the hopper is dissolved in water, and the concentration of the molten solid detergent composition for automatic dishwashers is 0.01% by mass or more and 0.09% by mass or less. It consists of a process of heating and holding the adjusted cleaning liquid in the cleaning liquid tank of the automatic dishwasher, a process of cleaning the dishes by spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet, and a process of rinsing with the rinsing liquid after cleaning. A dishwashing method using an automatic dishwasher,
(8) In the rinsing step, the rinsing liquid is sprayed by 1 L or more and 3 L or less per 2500 cm ² of the flat area of the washing machine to rinse the dishes.
Is a summary.

  The molten solid detergent composition for automatic dishwashing machine of the present invention (hereinafter sometimes simply referred to as a molten solid detergent composition) comprises an alkali metal hydroxide and an aminocarboxylic acid chelating agent at a high concentration. In addition, when filling the slurry with each component melted into a container to produce a product, the viscosity of the slurry may increase rapidly, or solidification before filling may make filling the container difficult. Therefore, it can be efficiently manufactured and provided as a compact product. In addition, the melted solid detergent composition of the present invention has excellent storage stability, there is no risk of deliquescence during product storage, etc., and it has good dissolution stability and does not dissolve excessively or cause poor dissolution. In this way, it is possible to provide a stable supply.

  In the molten solid detergent composition of the present invention, examples of the alkali metal hydroxide used as the component (A) include potassium hydroxide, sodium hydroxide and a mixture thereof, and sodium hydroxide is preferable. As the aminocarboxylic acid chelating agent used as component (B), nitrilotriacetic acid or a salt thereof, ethylenediaminetetraacetic acid or a salt thereof, glutamic acid diacetic acid or a salt thereof, methylglycine diacetic acid or a salt thereof, diethylenetriaminepentaacetic acid or a salt thereof Examples thereof include salts, hydroxyethylethylenediamine triacetic acid or its salt, triethylenetetramine hexaacetic acid or its salt, and the like. Among these aminocarboxylic acid-based chelating agents, nitrilotriacetic acid or a salt thereof, ethylenediaminetetraacetic acid or a salt thereof, glutamic acid diacetic acid or a salt thereof, methylglycine diacetic acid or a salt thereof is particularly preferable because of a good cleaning effect. Nitrilotriacetic acid or a salt thereof, and ethylenediaminetetraacetic acid or a salt thereof are preferable because of good efficiency.

  Examples of the polymer polymer (C) include carboxylic acid polymers, sulfonic acid polymers, and salts thereof, and the polymer polymers can be used in combination of two or more. Examples of the carboxylic acid polymer include polyacrylic acid, polymethacrylic acid, acrylic acid copolymer, maleic acid copolymer, and methacrylic acid copolymer. Polyacrylic acid and acrylic acid / maleic acid A copolymer is more preferred. The weight average molecular weight of the carboxylic acid polymer is preferably 3,000 or more and 120,000 or less, and particularly preferably 10,000 or more and 90,000 or less. If the weight average molecular weight of the carboxylic acid polymer is less than 3,000, it is not preferable in terms of preventing recontamination, and if it exceeds 120,000, it is not preferable in terms of storage stability. The weight average molecular weight of polymaleic acid is preferably 300 or more and 2,000 or less, and particularly preferably 400 or more and 1,500 or less. Examples of the sulfonic acid polymer include acrylic acid / sulfonic acid monomer copolymers, and the weight average molecular weight of the sulfonic acid polymer is preferably 1,000 or more and 20,000 or less, particularly preferably 2,000 or more, 15 , 000 or less. When the weight average molecular weight of the sulfonic acid polymer is less than 1,000, it is not preferable from the viewpoint of scale prevention, and when it exceeds 20,000, it is not preferable from the viewpoint of storage stability. As the carboxylic acid polymer and sulfonic acid polymer salt used as the polymer, alkali metal salts such as sodium and potassium are preferred. The polymer polymer used as the component (C) includes an acrylic acid / sulfonic acid copolymer and an acrylic acid / maleic acid copolymer in terms of suppressing bulkiness of the molten solid detergent composition and preventing scale. Or a salt thereof, and an acrylic acid / sulfonic acid copolymer or a salt thereof is particularly preferable.

  (D) As component water, tap water, softened water, pure water, RO water, ion-exchanged water, distilled water, etc. can be used, but pure water, RO water, ion-exchanged water, distilled water are used. preferable.

  The molten solid detergent composition of the present invention comprises (A) component alkali metal hydroxide 40% by mass or more and 50% by mass or less, and (B) component aminocarboxylic acid chelating agent 25% by mass or more and 45% by mass. % Or less, (C) component polymer 0.1% by mass or more and 10% by mass or less, (A) component, (B) component, (C) component water is the remaining component (D) water However, (A) component 41 mass% or more and 45 mass% or less, (B) component 28 mass% or more, 35 mass% or less, (C) component 1 mass% or more and 5 mass% or less are preferable. When the amount of the component (A) is less than 40% by mass, the washability and scale prevention properties are reduced when used at a low concentration, and when it exceeds 50% by mass, the viscosity increases during production and it is difficult to produce. . When the amount of the component (B) is less than 25% by weight, the washability and scale prevention properties are lowered at the time of use at a low concentration, and when it exceeds 45% by weight, the viscosity increases at the time of production and it becomes difficult to produce. If the amount of the component (C) is less than 0.1% by mass, the scale-preventing property is lowered, and the viscosity at the time of production becomes insufficient, so that the component after solidification becomes non-uniform. Sometimes the viscosity increases, making it difficult to manufacture. In addition, the alkali metal hydroxide of component (A) has a value of (A) / {(A) + (D)} by mass ratio with respect to the total amount of water of component (A) and component (D). Although it mix | blends so that it may become 0.58 or more and 0.75 or less, it may mix | blend so that the value of (A) / {(A) + (D)} may be 0.60 or more and 0.72 or less. It is preferable to blend such that the value of (A) / {(A) + (D)} is 0.63 or more and 0.69 or less. Even if the blending ratio of the component (A) is in the range of 40% by mass or more and 50% by mass or less, if the value of (A) / {(A) + (D)} is less than 0.58, the solubility Deteriorated, uniformity of components and long-term storage stability deteriorated, and if it exceeds 0.75, viscosity will increase during production, making it difficult to manufacture, and long-term storage stability deteriorated To do.

  The molten solid detergent composition of the present invention preferably includes a mass ratio of the component (A) to the component (C) such that the value of (A) / (C) is 5 or more and 39 or less. More preferably, the value of A) / (C) is 8 or more and 35 or less. When the value of (A) / (C) is 5 or more and 39 or less, the composition becomes small and compact, there is no occurrence of deliquescence during long-term storage, and the scale prevention property when using low concentrations is good. It becomes a composition.

  In addition to the components (A) to (D), the molten solid detergent composition of the present invention can further contain 5% by mass or less of a nonionic surfactant as the component (E). In addition to the components (A) to (D), when 5% by mass or less of the component (E) is further blended, the detergency, the ability to prevent re-attachment of food stains to the object to be cleaned, and the foam suppression property are improved. . When the amount of the component (E) exceeds 5% by mass, it is not preferable in terms of storage stability and moldability (the molten solid detergent composition is difficult to solidify). (E) It is more preferable to mix | blend 0.1 mass% or more and 4 mass% or less, and it is still more preferable to mix | blend 1 mass% or more and 3 mass% or less. As the nonionic surfactant used as the component (E), polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether (ethylene oxide and propylene oxide may be either random or block), Polyoxyalkylene alkenyl ethers such as oxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether (ethylene oxide and propylene oxide may be either random or block), polyethylene glycol propylene oxide adduct, polypropylene glycol ethylene oxide adduct, glycerin fatty acid Ester or its ethylene oxide adduct, sorbitan fatty acid ester, polyoxyethylene Vitan fatty acid ester, alkyl polyglucoside, fatty acid monoethanolamide or its ethylene oxide adduct, fatty acid-N-methyl monoethanolamide or its ethylene oxide adduct, fatty acid diethanolamide or its ethylene oxide adduct, sucrose fatty acid ester, alkyl (poly ) Glycerol ether, polyglycerin fatty acid ester, polyethylene glycol fatty acid ester, fatty acid methyl ester ethoxylate, N-long chain alkyldimethylamine oxide and the like. Among these, a reverse pluronic block polymer is preferable because it is excellent in detergency, foam suppression, and uniformity of components. Specifically, Adeka Pluronic 25R-1 and Adeka Pluronic 25R-2 manufactured by ADEKA are preferable.

  The molten solid detergent composition of the present invention may further contain 15% by mass or less of an inorganic builder as the component (F). Inorganic builders include carbonates, sulfates, and hydrochlorides. Specifically, examples of the carbonate include sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, lithium sesquicarbonate, and combinations thereof. be able to. Among these, sodium carbonate, sodium sulfate, sodium chloride, and magnesium chloride are exemplified. When an inorganic builder is blended, there are a cleaning assisting effect and a long-term storage stability improving effect. When mix | blending an inorganic builder, 0.5 mass% or more and 10 mass% or less are more preferable. As an inorganic builder, silicate causes silicic acid scale and phosphorous phosphate causes eutrophication such as lakes and marshes. Any amount can be blended.

The molten solid detergent composition of the present invention may further contain a chlorine bleach coated with a coating containing a benzoate as component (G). Even when a chlorine-based bleaching agent coated with a coating agent containing a benzoate is added to the slurry aqueous solution during the production of the molten solid detergent composition, the effective chlorine amount does not decrease. In addition, when cleaning is performed using a molten solid type cleaning composition, since it is excellent in effective chlorine stability and fast solubility, sufficient cleaning properties, biofilm prevention properties, and bleaching properties can be exhibited. The blending amount in the melted solid detergent composition is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.1% by mass in order to obtain good detergency, biofilm prevention and bleaching properties. % To 5% by mass, particularly preferably 0.3% to 3% by mass. Within this range, good detergency, biofilm prevention and bleaching properties can be obtained.
Further, the coating amount is preferably a mass ratio of chlorine bleach to benzoate and a chlorine bleach / benzoate value of 0.001 or more and 1,000 or less, more preferably 0.01 or more, 100 Hereinafter, it is more preferably 0.1 or more and 10 or less. If the mass ratio of the chlorine bleach to the benzoate is less than 0.001, a sufficient stabilizing effect may not be expected, and if it exceeds 1,000, no further effect can be expected.
When chlorine bleach that is not coated with a coating containing benzoate is used, the chlorine component is decomposed by contact with temperature, water, or other chemicals during the production of the molten solid detergent composition of the present invention. In addition, when the molten solid detergent composition is diluted and used, the chlorine component in the portion in contact with water (hot water) is decomposed, and the biofilm prevention and bleaching properties cannot be exhibited. In addition, when a surfactant is used as a coating agent, foaming occurs in the dishwasher, resulting in a reduction in cleaning efficiency. Use of silica, calcium stearate or the like as a coating agent is not preferable because it remains in the dishwasher and inhibits washing.

  Chlorine bleaches include chloramine B (N-chlorobenzenesulfonamide sodium), dichloramine B (N, N′-dichlorobenzenesulfonamide), chloramine T (N-chloro-P-toluenesulfonamide sodium), dichloramine T ( N, N′-dichloro-P-toluenesulfonamide) and the like. Examples include chlorinated isocyanuric acids such as trichloroisocyanuric acid, dichloroisocyanuric acid, or salts thereof, hypochlorites such as calcium hypochlorite, trisodium chlorophosphate, chlorine dioxide, and the like. Among these, sodium dichloroisocyanurate and calcium hypochlorite are preferable, and sodium dichloroisocyanurate is particularly preferable. These may be used alone or in combination of two or more. The coating agent only needs to contain a benzoate, but preferably contains 50% by mass or more of benzoate, more preferably contains 80% by mass or more, and particularly preferably contains 95% by mass or more. Examples of the benzoate include sodium benzoate, potassium benzoate, calcium benzoate, and magnesium benzoate. Sodium benzoate is preferable from the viewpoint of solubility during washing. The method for coating the chlorine bleach is not particularly limited. For example, benzoate is dissolved or suspended in a solvent such as water, ethanol, methanol, ether or the like in a dry chlorine bleach. For example, a method of spraying and drying the solution, and a method of coating the dried chlorine bleach with a fine benzoate powder and spraying a binder such as water.

  In addition to the above components, the molten solid detergent composition of the present invention may further contain silicone, a chlorine agent and the like as optional components as necessary. Further, it may contain components such as a viscosity modifier, an antiseptic, a bactericide, a pH adjuster, a fragrance, and a pigment that are usually used in the technical field.

  The molten solid detergent composition of the present invention is obtained by cooling and solidifying a slurry obtained by melting and mixing each component under heating. Usually, the slurry is filled in a container such as plastic and solidified by cooling in the container. It is commercialized.

As a method for washing dishes with an automatic dishwasher using the molten solid detergent composition of the present invention, the molten solid detergent composition is dissolved in water in the washing liquid tank of the automatic dishwasher, A step of heating and holding the cleaning liquid in which the concentration of the molten solid detergent composition is adjusted to 0.01% by mass or more and 0.09% by mass or less in the cleaning liquid tank, and spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet The method of performing the process of wash | cleaning tableware and the process of rinsing with a rinsing liquid after washing | cleaning continuously is mentioned. In order to dissolve the molten solid detergent composition in water so that the concentration of the molten solid detergent composition is 0.01% by mass or more and 0.09% by mass or less, the electric power of the aqueous solution of the molten solid detergent is Since the conductivity is proportional to the concentration of the molten solid detergent, the concentration of the molten solid detergent can be controlled by measuring the electrical conductivity of the aqueous solution in the washing tank in which the molten solid detergent is dissolved. Become. Usually, the electric conductivity of the aqueous solution in the cleaning tank is measured mechanically by the concentration of the molten solid type cleaning solution, and when the electric conductivity is low, the molten solid type cleaning agent is automatically supplied. In this case, as a supply method, using an elution hopper filled with a molten solid detergent composition in a container, the required amount of the molten solid detergent composition in the hopper is dissolved with water, and passed through a supply pipe. The method of sending to a dishwasher is mentioned. The cleaning liquid prepared by diluting the melted solid detergent composition to a predetermined concentration is usually kept at 40 ° C. or higher and 70 ° C. or lower in the cleaning liquid tank. The cleaning liquid is sprayed to the tableware in the cleaning machine cabinet for 30 seconds or more and 120 seconds or less. As the rinsing liquid, tap water is usually used, but a rinsing agent may or may not be used. The rinsing liquid is preferably 1 L or more and 3 L or less per 2500 cm ² of the tableware installation flat area of the washing machine. The temperature of the rinsing liquid is preferably 40 ° C. or higher and 95 ° C. or lower, more preferably 60 ° C. or higher and 90 ° C. or lower. As the tap water of the diluted solid detergent composition rinse water, for example, tap water in Arakawa-ku, Tokyo (pH = 7.6, total alkalinity (calculated as calcium carbonate) 40.5 mg / L, German hardness 2.7 ° DH (of which calcium hardness 2.0 ° DH, magnesium hardness 0.7 ° DH), chloride ion 21.9 mg / L, sodium and its compounds 15 mg / L, nitrate nitrogen and nitrous acid State nitrogen 1.2 mg / L, fluorine and its compound 0.1 mg / L, boron and its compound 0.04 mg / L, total trihalomethane 0.016 mg / L, residual chlorine 0.4 mg / L, organic matter (total organic carbon content) ) 0.7 mg / L).

  The present invention will be described more specifically with reference to examples and comparative examples. In the following Examples and the like, “%” represents mass% unless otherwise specified, and the numerical values of the examples and comparative examples in the table represent pure mass%. The compounds used in Examples and Comparative Examples are described below.

(A) Component A-1: Sodium hydroxide Product name: Granular caustic soda, manufactured by Asahi Glass Co., Ltd. A-2: Potassium hydroxide Product name: Flake caustic potash, manufactured by Toagosei Co., Ltd.

(B) Component B-1: Sodium nitrilotriacetate Product name: Trilon A92R, BASF B-2: Ethylenediaminetetraacetate sodium salt Product name: Dissolvin NA, Akzo Nobel B-3: Glutamic acid diacetate sodium salt Product name: Dissolvin GL-47-S, Akzo Nobel B-4: Methylglycine diacetate sodium salt Product name: Trilon M Powder, BASF B-5: 3-hydroxy-2,2'-iminodisuccinic acid tetra Sodium salt Product name: HIDS, 50% pure, manufactured by Nippon Shokubai Co., Ltd.

(C) Component C-1: Acrylic acid / sulfonic acid monomer copolymer sodium 1 (weight average molecular weight is 5,000)
C-2: acrylic acid / maleic acid copolymer sodium (weight average molecular weight 70,000)
C-3: Sodium polyacrylate (weight average molecular weight is 4,000)
C-4: Acrylic acid / sulfonic acid monomer copolymer sodium 2 (weight average molecular weight 11,000)
C-5: Sodium polymaleate (weight average molecular weight is 500)

(D) Component D-1: Ion exchange water

(E) Component E-1: Reverse pluronic block polymer 1 (a block polymer in which polyoxypropylene chains are bonded to both ends of a polyoxyethylene chain) 20% oxyethylene chain content, trade name: Adeka Pluronic 25R-2 ADEKA E-2: Reverse pluronic block polymer 2 (block polymer in which polyoxyethylene chain is bonded to both ends of polyoxyethylene chain) Oxyethylene chain content: 10%, trade name: Adeka Pluronic 25R-1 ADEKA E-3: Aliphatic alcohol alkoxylate, Trade name: Pullurafak LF403, BASF

(F) Component F-1: Sodium carbonate F-2: Sodium sulfate

(G) Component Chlorine bleach coated with a coating containing a benzoate G-1: coating sodium dichloroisocyanurate 1 (coating is sodium benzoate manufactured by Ueno Food Techno Co., Ltd .: product name sodium benzoate Ueno) , More than 99.0% pure)
G-2: Coating sodium dichloroisocyanurate 2 (the coating agent is potassium benzoate manufactured by Wako Pure Chemical Industries, Ltd .: product name: potassium benzoate, pure content: 99.0% or more)
G-3: Coating calcium hypochlorite (the coating agent is sodium benzoate manufactured by Ueno Food Techno Co., Ltd .: product name sodium benzoate Ueno, pure content 99.0% or more)
G-4: Coating sodium trichloroisocyanurate (the coating agent is sodium benzoate manufactured by Ueno Food Techno Co., Ltd .: product name sodium benzoate Ueno, pure content 99.0% or more)
G-5: Coating sodium dichloroisocyanurate 3 (Coating agent is Ueno Food Techno Co., Ltd. sodium benzoate: Product name Sodium benzoate Ueno, pure content 99.0% or more, adipine manufactured by Wako Pure Chemical Industries, Ltd. Acid dipotassium: Product name Dipotassium adipate 95.0% or more mixed at a mass ratio of 2: 1)
The component (G) is air-sprayed with a coating solution (a methanol solution in which a coating agent is dissolved) together with compressed air by a spray gun while rotating a granular chlorine bleach in a rotating drum (coating pan). Spray as much as possible to spread the coating solution evenly over the entire chlorine bleach. After spraying, it was prepared by drying with hot air at 70 ° C. The effective chlorine content of the chlorine bleach coated with the resulting benzoate-containing coating is determined by sodium thiosulfate titration, and the coating amount is the mass ratio of the chlorine bleach to the benzoate. / The benzoate value was adjusted to 2.5.

Other components Other: Silicone Product name: DOW CORNING TORAY FS Antifoam 1266, manufactured by Toray Dow Corning

Examples 1-90, Comparative Examples 1-6
Slurries having the formulations shown in Tables 1 to 10 were prepared, and this was cooled and solidified to obtain molten solid-type cleaning compositions. Each test of the detergency, scale prevention property, production efficiency, melt stability, component uniformity, long-term storage stability, and bulk specific gravity of the melted solid detergent composition were measured under the following conditions. The results are shown in Tables 1-10.

* 1: Detergency test 1 (66 ° C)
<To be cleaned>
A contaminated dish obtained by uniformly coating 2 g of commercially available mayonnaise (manufactured by Kewpie) on a glass dish having a diameter of 20 cm and drying at room temperature was used as an object to be cleaned.
<Test method>
The cleaning liquid diluted to 0.04% by mass with the concentration of the molten solid cleaning composition is stored in the cleaning liquid tank of the cleaning machine and held at 66 ° C., and five contaminated dishes are installed in the cleaning rack under the following conditions. Washing and rinsing were performed. Artificial hard water prepared to have a hardness of 3 ° DH using calcium chloride was used as dilution water and rinse water of the molten solid detergent composition.
<Cleaning conditions>
Washing machine: Hoshizaki, electric automatic dishwasher JWE-680AJ
Washing temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Water volume per rinse: 2L
<Detergency evaluation>
The dish after washing and rinsing was dried at room temperature, and then the fluorescent lamp was irradiated and reflected in a dark room, and the remaining state of the soil was evaluated by visual judgment based on the following criteria.
(Double-circle): There is no difference compared with a clean dish.
○: Only light cloudiness is recognized.
X: Cloudiness and spots are recognized.
And ○ and ◎ were judged as practical.

* 2: Scale prevention test <Test method>
A cleaning solution in which 36 250 mL glasses were placed in a cleaning rack and the concentration of the molten solid cleaning composition was diluted to 0.01% by mass and 0.09% by mass from artificial hard water prepared with calcium chloride to a hardness of 10 ° DH. After washing under the following conditions, rinsing was performed, and after the washing machine was continuously operated 200 times in the interval (supply stop time) step, the amount of scale adhered in the washing machine cabinet was visually determined and evaluated according to the following criteria.
<Cleaning conditions>
Washing machine: Hoshizaki, electric automatic dishwasher JWE-680AJ
Washing temperature: 66 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Interval: 5 seconds Rinse volume: 2L
<Evaluation criteria>
A: No adhesion of scale was observed.
○: Almost no adhesion of scale was observed.
Δ: Slight adhesion of scale is observed, but there is no problem in use.
X: Significant scale adhesion was observed.
And Δ, ○, and ◎ were determined to be practical.

* 3: Manufacturing efficiency test (viscosity, filling speed)
<Test method>
After 1 kg of molten slurry was prepared in a 1 L stainless beaker, the entire amount was filled in a 1 L plastic container and evaluated according to the following criteria.
<Filling conditions>
Filling temperature: 65 ° C
<Evaluation criteria>
A: Almost all (99% or more) could be filled in less than 10 seconds.
A: Almost all (99% or more) could be filled in 10 seconds or more and less than 30 seconds.
X: Even if it took 30 seconds or more, the entire amount could not be filled (less than 99%).
And ○ and ◎ were judged as practical.

* 4: Dissolution stability test <Test method>
1 L of water was placed in a 1 L glass beaker and maintained at 60 ° C., and stirred using a rotor having a length of 40 mm and a diameter of 8 mm with a magnetic stirrer (model number RS-4DR (As One Corporation)) at a rotation speed of 600 rpm. Then, 3.2 g of a regular quadrangular pyramid-shaped molten solid detergent composition having a height of 10 mm or more and 15 mm or less was added, and the time required until it could not be visually confirmed after dissolution was measured. Evaluation based on the criteria.
A: Time required for dissolution is 90 seconds or more and less than 240 seconds.
○: Time required for dissolution is 30 seconds or more, less than 90 seconds or 240 seconds or more, less than 600 seconds,
X: Time required for dissolution is less than 30 seconds or 600 seconds or more.
And ○ and ◎ were judged as practical.

* 5: Ingredient uniformity test (uneven distribution)
<Test method>
1 kg of a melt slurry of the molten solid detergent composition is prepared, and a part (about 10 g) of the melt slurry is sampled to measure the chelating power. After that, the entire amount of the slurry is filled at 65 ° C., placed in a 1 L polyethylene bottle, left to stand at 25 ° C. for 24 hours to solidify, and then 30 g or more of the solidified material at the top and bottom of the container is collected and the chelating power is measured. did. Evaluation was made according to the following evaluation criteria using the chelating power of the molten slurry as a theoretical value.
<Measurement method of chelating power>
Weigh accurately the detergent composition in a 100 mL beaker and dilute to about 100 mL with distilled water. Add 2 mL of 1 mol / L NaOH and 10 mL of 1/100 mol / L calcium chloride dihydrate solution. Add about 0.1 g of NN indicator (1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3-naphthoic acid) and stir well. Titrate with 1/100 mol / L EDTA solution, and the point at which the color changed from reddish purple to blue is the end point. The chelating power is calculated by the following formula (1). The chelating power is calculated by titration when a blank without titration of the detergent is titrated and the following formula with the detergent added.
(Equation 1)
Chelating power (CaCO ₃ mg / g) = [(a) − (b)] × 100.09 / (s) (1)
(A): Titration volume when no sample is added (mL)
(F): Titration volume when adding sample (mL)
(S): Sampling amount <Evaluation criteria> Compared with theoretical values A: Misalignment between upper and lower chelating powers is less than 5%.
○: The difference in chelating power between the upper part and the lower part is 5% or more and less than 15%.
X: The deviation of the chelating power between the upper and lower parts is 15% or more.
And ○ and ◎ were judged as practical.

* 6: Long-term storage stability (deliquescent)
The molten slurry of the molten solid detergent composition is placed in a 1 L polyethylene bottle, allowed to stand at 25 ° C. for 24 hours to solidify, and then heated at a temperature of 40 using a thermo-hygrostat (HIFLEX FX214C, manufactured by Enomoto Kasei Co., Ltd.). It was placed in an atmosphere of 70 ° C. and humidity of 70% and stored in that state for one month. And the external appearance was observed visually and evaluated by the following evaluation criteria.
<Evaluation criteria>
A: No deliquescent surface was observed after 1 month.
○: After 1 month, almost no surface deliquescence was observed.
×: After one month, surface deliquescence was noticeable.
And ○ and ◎ were judged as practical.

* 7: Bulk specific gravity test <Test method>
A molten solid detergent composition having a mass of 500 g was prepared in a 1 L stainless beaker by vigorously stirring at 300 rpm using a three-one motor. The slurry-like molten solid detergent composition was filled in a container at a temperature of 65 ° C., the specific gravity was measured from the mass and volume at that time, and evaluated according to the following criteria.
A: Specific gravity is 1.5 or more.
○: Specific gravity is 1.3 or more and less than 1.5.
X: Specific gravity is less than 1.3.
And ○ and ◎ were judged as practical.

* 8: Detergency test 2 (40 ° C)
<To be cleaned>
A contaminated dish obtained by uniformly coating 2 g of commercially available mayonnaise (manufactured by Kewpie) on a glass dish having a diameter of 20 cm and drying at room temperature was used as an object to be cleaned.
<Test method>
The cleaning liquid diluted to 0.04% by mass with the concentration of the molten solid cleaning composition is stored in the cleaning liquid tank of the cleaning machine and held at 40 ° C., and five contaminated dishes are installed in the cleaning rack. Washing and rinsing were performed. Artificial hard water prepared to have a hardness of 3 ° DH using calcium chloride was used as dilution water and rinse water of the molten solid detergent composition.
<Cleaning conditions>
Washing machine: Hoshizaki, electric automatic dishwasher JWE-680AJ
Washing temperature: 40 ° C
Cleaning time: 41 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Water volume per rinse: 2L
<Detergency evaluation>
The dish after washing and rinsing was dried at room temperature, and then the fluorescent lamp was irradiated and reflected in a dark room, and the remaining state of the soil was evaluated by visual judgment based on the following criteria.
(Double-circle): There is no difference compared with a clean dish.
○: Only light cloudiness is recognized.
(Triangle | delta): Only cloudiness is recognized.
X: Cloudiness and spots are recognized.
And Δ, ○, and ◎ were determined to be practical.

* 9 Biofilm prevention test <Test method>
Prepare 5% by weight of each melted solid detergent composition by making 5g of each molten solid detergent composition into 100g using sterilized Mueller Hinton medium (Nihon Becton Dickinson Co., Ltd.). did. This conc solution was further diluted with a sterilized Mueller Hinton medium so that the concentration of the molten solid detergent composition was 0.07% by mass, and each was prepared on a 24-well microplate (Asahi Techno Glass Co., Ltd.). Weighed 2 mL.
Using a LB medium (manufactured by Nippon Becton Dickinson Co., Ltd.) for each of Pseudomonas aeruginosa NBRC13275 and Klebsiella pneumoniae ATCC13883, the bacterial solution which had been pre-cultured for 18 hours at 37 ° C. Used to inoculate 100 μL of the test solution in the microplate. After culturing at 37 ° C. for 48 hours, the culture solution was discarded, and each well was washed 5 times with 2 mL of sterilized purified water. The biofilm adhered to the microplate wall was stained with 0.1% by mass crystal violet solution, rinsed with sterilized water, and the formation state of the biofilm was visually observed.
A: The biofilm covers less than 20% of the plate wall surface.
○: A state in which the biofilm covers 20% or more and less than 40% of the plate wall surface.
Δ: A state in which the biofilm covers 40% or more and less than 60% of the plate wall surface.
X: A state in which the biofilm covers 60% or more and 100% or less of the plate wall surface.
And Δ, ○, and ◎ were determined to be practical.

* 10 Bleachability test <Cleaning conditions>
Washing machine used: Hoshizaki, electric automatic dishwasher JWE-680AJ
Washing temperature: 66 ° C
Cleaning time: 40 seconds Rinsing temperature: 82 ° C
Rinsing time: 9 seconds Cleaning liquid: 0.07% by weight of molten solid detergent composition Diluted water and water used for dilution and rinsing: Hard water with a German hardness of 3 ° DH in terms of calcium carbonate Water volume per rinse: 2L
<Adjustment of the object to be cleaned>
A white porcelain dish (12 cm in diameter) was immersed in black tea at 80 ° C. for 5 minutes, and then heated at 100 ° C. for 30 minutes, and the browned contaminated dish was used as an object to be washed for bleaching test.
<Test method>
Ten contamination dishes prepared by the above method were placed in a washing rack of a dishwasher, washed under the above washing conditions, rinsed, and dried at room temperature. The remaining state of tea astringent was evaluated by visual judgment based on the following criteria.
A: Tea astringency has been removed.
○: Tea astringency is almost removed.
Δ: Tea astringency is removed, but the remaining tea astringency is observed.
X: Tea astringency is not removed.
And Δ, ○, and ◎ were determined to be practical.

* 11 Metal corrosion prevention test <Test method>
The test piece [stainless steel (SUS430), gray cast iron (FC200)] is used after previously washed with a neutral detergent, treated with acetone and dried. Each molten solid detergent composition is diluted to 0.07% by mass with 75 mg / L [German hardness 4.2 ° DH] hard water in terms of calcium carbonate, and 60 mL is put into a 70 mL capacity glass bottle with a lid. The test piece was immersed therein and stored in a thermostat at 70 ° C. for 5 days. The test piece after storage was taken out, rinsed with ion-exchanged water and dried, the appearance of the surface of the test piece was visually observed, and the corrosivity was determined according to the following criteria.
<Metallic corrosion prevention evaluation criteria>
A: There is no corrosion.
○: Almost no corrosion.
Δ: Corrosion is slightly observed, but there is no problem in use.
X: Corroded severely.
And Δ, ○, and ◎ were determined to be practical.

* 12 Odor test <cleaning conditions>
Washing machine: Hoshizaki, electric automatic dishwasher JWE-680AJ
Washing temperature: 66 ° C
Cleaning time: 40 seconds Rinsing temperature: 82 ° C
Rinse time: 6 seconds Water volume per rinse: 2L
Cleaning liquid: 0.1% by weight dilution of molten solid detergent composition Water used for diluting and rinsing molten solid detergent composition: Hard water with a German hardness of 3 ° DH in terms of calcium carbonate
A contaminated dish obtained by uniformly applying 2 g of mayonnaise (manufactured by Kewpie) on a glass dish having a diameter of 20 cm and drying at room temperature was used as an object to be cleaned.
<Test method>
The object to be cleaned is set in the cleaning machine, cleaned and rinsed, the door of the cleaning machine is opened, and the odor in the atmosphere in the cleaning machine is evaluated in five levels by five panelists (5: no odor, 4: almost No odor, 3: slightly odor, 2: odor, 1: strong odor), and evaluation was made according to the following criteria from the average score of all panelists.
<Evaluation criteria>
○: The average score is 3.5 or more and 5 or less.
Δ: The average score is 2.5 or more and less than 3.5.
X: The average score is 1 or more and less than 2.5.
And Δ and ○ were determined to be practical.

That is, the present invention
(1) 40% by mass or more and 50% by mass or less of alkali metal hydroxide as component (A)
(B) 25% by mass or more and 45% by mass or less of aminocarboxylic acid-based chelating agent as a component,
(C) 0.1% by mass or more and 10% by mass or less of a polymer as a component,
(D) Water as a component,
The mass ratio of the component (A) to the component (C), the value of (A) / (C) is 8 or more and 35 or less, and the mass ratio is (A) / {(A) + (D) } Is 0.60 or more and 0.69 or less, a molten solid detergent composition for an automatic dishwasher,
(2) The molten solid detergent composition for an automatic dishwasher according to the above (1), wherein the high molecular polymer of the component (C) is an acrylic acid / sulfonic acid copolymer or a salt thereof,
(3) The molten solid detergent composition for an automatic dishwasher according to (1) or (2), further containing 5% by mass or less of a nonionic surfactant as component (E) ,
(4) The molten solid detergent composition for an automatic dishwasher according to any one of (1) to (3), further containing 15% by mass or less of an inorganic builder as the component (F) ,
(5) The molten solid detergent composition for an automatic dishwasher according to any one of (1) to (4), further comprising a chlorine bleach coated with a coating containing a benzoate as component (G) object,
(6) The chlorine bleach coated with the coating containing the benzoate of component (G), the mass ratio of chlorine bleach to benzoate, and the value of chlorine bleach / benzoate is 0. A molten solid detergent composition for an automatic dishwasher according to the above (5), which is 0.001 or more and 1,000 or less ,
(7) The molten solid detergent composition for an automatic dishwasher according to any one of the above (1) to (6) is installed in an elution hopper having a discharge port at the lower end portion, and water is supplied from a water supply nozzle. The molten solid detergent composition for automatic dishwashers in the hopper is dissolved in water, and the concentration of the molten solid detergent composition for automatic dishwashers is 0.01% by mass or more and 0.09% by mass or less. It consists of a process of heating and holding the adjusted cleaning liquid in the cleaning liquid tank of the automatic dishwasher, a process of cleaning the dishes by spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet, and a process of rinsing with the rinsing liquid after cleaning. A dishwashing method using an automatic dishwasher,
(8) In the rinsing step, the rinsing liquid is sprayed at 1 L or more and 3 L or less per 2500 cm ² of the washing machine in a flat area to rinse the dishes.
Is a summary.

* 5: Ingredient uniformity test (uneven distribution)
<Test method>
1 kg of a melt slurry of the molten solid detergent composition is prepared, and a part (about 10 g) of the melt slurry is sampled to measure the chelating power. After that, the entire amount of the slurry is filled at 65 ° C., placed in a 1 L polyethylene bottle, left to stand at 25 ° C. for 24 hours to solidify, and then 30 g or more of the solidified material at the top and bottom of the container is collected and the chelating power is measured. did. Evaluation was made according to the following evaluation criteria using the chelating power of the molten slurry as a theoretical value.
<Measurement method of chelating power>
Weigh accurately the detergent composition in a 100 mL beaker and dilute to about 100 mL with distilled water. Add 2 mL of 1 mol / L NaOH and 10 mL of 1/100 mol / L calcium chloride dihydrate solution. Add about 0.1 g of NN indicator (1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3-naphthoic acid) and stir well. Titrate with 1/100 mol / L EDTA solution, and the point at which the color changed from reddish purple to blue is the end point. The chelating power is calculated by the following formula (1). The chelating power is calculated by titration when a blank without titration of the detergent is titrated and the following formula with the detergent added.
(Equation 1)
Chelating power (CaCO ₃ mg / g) = {(a) − (b)} × 100.09 / (s) (1)
(A): Titration volume when no sample is added (mL)
( B ): Titration volume when adding sample (mL)
(S): Sampling amount <Evaluation criteria> Compared with theoretical values A: Misalignment between upper and lower chelating powers is less than 5%.
○: The difference in chelating power between the upper part and the lower part is 5% or more and less than 15%.
X: The deviation of the chelating power between the upper and lower parts is 15% or more.
And ○ and ◎ were judged as practical.

Claims (8)

(A) 40 mass% or more of alkali metal hydroxide as a component, 50 mass% or less,
(B) 25% by mass or more and 45% by mass or less of aminocarboxylic acid-based chelating agent as a component,
(C) 0.1% by mass or more and 10% by mass or less of a polymer as a component,
(D) Water as a component,
And a mass ratio of (A) / {(A) + (D)} = 0.58 or more and 0.75 or less, a molten solid detergent composition for an automatic dishwasher. The molten solid detergent composition for an automatic dishwasher according to claim 1, wherein the mass ratio of the component (A) to the component (C) is (A) / (C) = 5 or more and 39 or less. The automatic dishwashing according to claim 1 or 2, wherein the high molecular polymer of component (C) is at least one selected from acrylic acid / sulfonic acid copolymers, acrylic acid / maleic acid copolymers, and salts thereof. A melt-type cleaning composition for machines. The molten solid detergent composition for an automatic dishwasher according to any one of claims 1 to 3, further comprising 5% by mass or less of a nonionic surfactant as component (E). Furthermore, the molten solid-type cleaning composition for automatic dishwashers in any one of Claims 1-4 which contains 15 mass% or less inorganic builder as (F) component. Furthermore, the molten solid-type cleaning composition for automatic dishwashers in any one of Claims 1-5 containing the chlorine-type bleaching agent coat | covered with the coating agent containing a benzoate as (G) component. The molten solid detergent composition for an automatic dishwasher according to any one of claims 1 to 6 is installed in an elution hopper having a discharge port at a lower end portion, and water is supplied from a water supply nozzle to A cleaning liquid prepared by dissolving a molten solid detergent composition for an automatic dishwasher in water and adjusting the concentration of the molten solid detergent composition for an automatic dishwasher to 0.01 mass% or more and 0.09 mass% or less. It consists of a process of heating and holding in the cleaning liquid tank of an automatic dishwashing machine, a process of cleaning the dishes by spraying the cleaning liquid in the cleaning liquid tank into the cleaning machine cabinet, and a process of rinsing with a rinsing liquid after cleaning. How to wash dishes with an automatic dishwasher. 8. The method for washing dishes by an automatic dishwasher according to claim 7, wherein in the rinsing step, the rinsing liquid is sprayed by 1 L or more and 3 L or less per 2500 cm ² of a flat area of the washing machine to rinse the dishes.