JP2010144087A - Method for producing solid detergent for automatic dishwasher, and solid detergent for automatic dishwasher obtained by the same - Google Patents

Abstract

The present invention provides a method for producing a high-quality solid dishwashing agent for an automatic dishwasher at low cost without incurring energy costs, and a solid detergent for an automatic dishwasher obtained thereby.
Under non-heating, non-cooling, and non-pressurization, the following components (A) to (E) are mixed and stirred and mixed, and then the following component (F) is mixed and stirred and mixed. Solidify the mold.
(A) Alkali agent 5-30 mass%.
(B) Water 15-60 mass%.
(C) Nonionic surfactant 0.01-5 mass%.
(D) 5-50 mass% of water-soluble chelating agents.
(E) Polymer electrolyte polymer 0.1-10 mass%.
(F) 10-50 mass% of anhydrous alkali metal hydroxide salts.
[Selection figure] None

Description

  The present invention is suitable for cleaning hard surfaces such as metal, glass, ceramics, and plastics, and more particularly, a method for producing a solid cleaning agent for an automatic dishwasher suitable for use in an automatic dishwasher and the like, and automatic dishwashing obtained thereby. The present invention relates to a machine-use solid cleaning agent.

  2. Description of the Related Art Conventionally, automatic dishwashers have been widely used in hotels, restaurants, catering companies, hospitals, company cafeterias and the like in order to efficiently wash used dishes and cooking utensils. Further, not only foods but also various manufacturing factories, processing factories, etc., automatic washing machines are used for washing instruments, containers, plastic containers used for distribution, and the like.

  Conventionally, these automatic cleaning machines are generally of a type using a powder cleaning agent, but recently, it has been proposed to use a solid cleaning agent and is commercially available in part. According to this method, there is an advantage that a high concentration cleaning agent can be supplied in a sanitary manner at a uniform concentration. Further, since a compact paper container can be used, handling is easy, storage space is small, and the container is easy to process. These advantages are expected to increase demand for solid detergents.

  However, such a solid cleaning agent is generally obtained by heating and melting a cleaning composition containing a high concentration cleaning agent and cooling and solidifying it. There exists a problem that an agent component may thermally decompose and the problem that the energy cost for a heating starts. Therefore, it is an important subject to efficiently solidify the cleaning composition by not heating and melting or by lowering the heating temperature as much as possible.

  In order to meet such a problem, several solid cleaning agents that can be produced at relatively low heating temperatures and methods for producing the same have been proposed. For example, “including at least one first solid component made of an alkaline hydrating chemical containing an alkali metal hydroxide and a second solid component made of a sequestering agent, A solid solid cast hydrated detergent composition containing at least 30% by weight, in which each component is uniformly blended, a solid cast detergent-containing product obtained by combining it with a specific shape mold, and "Manufacturing method and method of using the same" are disclosed (see Patent Document 1).

  Also, “(a) In a particular mixing system, a solid hydratable alkaline material comprising an alkali metal hydroxide and an alkaline aqueous medium is less than 100 μm effective to form a solid alkaline matrix by hydration. Uniform and highly alkaline, characterized in that it is produced by a method comprising a mixing step of mixing in a fine state until a particle size is achieved, and (b) a discharging step of solidifying the alkaline matrix into a solid composition. A "solid cleaning composition" is disclosed (see Patent Document 2).

Furthermore, “a solid cleaning agent characterized in that a part of the alkali metal hydroxide salt is dispersed and contained in the form of an undissolved anhydrous alkali metal hydroxide salt, an alkali metal hydroxide salt and a sequestering agent. Forming an aqueous slurry solution containing the main component, and then adding an anhydrous alkali metal hydroxide salt to the aqueous slurry solution to form an aqueous slurry solution in which at least a portion of the added anhydrous alkali metal hydroxide salt is dispersed in an undissolved state; "A method for producing a solid detergent in which a slurry aqueous solution is filled into a mold and solidified" is disclosed (see Patent Document 3).
Japanese Patent Publication No.59-4480 Japanese Patent No. 3920325 Japanese Patent Laid-Open No. 2002-3895

  However, the solid detergent of Patent Document 1 has a problem that it is hard and poor in solubility. Moreover, the manufacturing method of the said patent document 2 has the subject that a manufacturing process becomes complicated with a transfer from a manufacturing facility to a manufacturing facility, etc., and a long time is required for manufacturing time. Furthermore, although the said literature 3 solidifies the predetermined slurry aqueous solution and obtains a solid cleaning agent, it is necessary to mix the said slurry aqueous solution on the comparatively high heating conditions of 65 to 75 degreeC. There is a problem that the energy cost is still high. In addition, the slurry aqueous solution is not uniform, and there is a problem that the hardness is uneven and as a result, uniform cleaning performance and the like cannot be obtained.

  The present invention has been made in view of such circumstances, and is a method for producing a high-quality solid detergent for an automatic dishwasher that is inexpensive and has an appropriate hardness and uniform solubility without incurring energy costs. An object of the present invention is to provide a solid detergent for an automatic dishwasher obtained thereby.

In order to achieve the above object, the present invention is a method for producing a solid detergent used in an automatic dishwasher, wherein the following components (A) to (E) are contained in the following proportions relative to the whole solid detergent: And the step of obtaining a slurry aqueous solution X by stirring and mixing under non-heating, non-cooling and non-pressurization, and the following (F) component in the slurry aqueous solution X and the solid detergent By mixing with the following ratio with respect to the whole, and stirring and mixing under non-heating, non-cooling and non-pressurization, a slurry aqueous solution Y in which at least a part of the component (F) is dispersed in an undissolved state is obtained. A first gist is a method for producing a solid detergent for an automatic dishwasher comprising a step and a step of filling the slurry-like aqueous solution Y into a mold and solidifying it.
(A) Alkaline agent (excluding anhydrous silicate and carbonate) 5-30% by mass.
(B) Water 15-60 mass%.
(C) Nonionic surfactant 0.01-5 mass%.
(D) 5-50 mass% of water-soluble chelating agents.
(E) Polymer electrolyte polymer 0.1-10 mass%.
(F) 10-50 mass% of anhydrous alkali metal hydroxide salts.

  In addition, the present invention provides, in particular, a method for producing a solid detergent for an automatic dishwasher in which anhydrous silicate is blended as component (G) in the step of obtaining the slurry aqueous solution X. In the step of obtaining the slurry aqueous solution X, the third summary is a method for producing a solid detergent for an automatic dishwasher in which a carbonate is blended as the component (H).

  And among these, especially in the process of obtaining the said slurry-like aqueous solution Y, in this invention, the manufacturing method of the solid detergent for automatic dishwashers which mix | blended the silicone type antifoamer as (I) component This is the fourth gist.

Furthermore, the present invention is a solid detergent for an automatic dishwasher obtained by any one of the first to fourth production methods, wherein the following components (A) to (F) are contained in the whole solid detergent: The solid content in the entire solid detergent is set to 40 to 75% by mass, and the solid detergent has a hardness of 25 mm and a needle with a diameter of 3 mm at a puncture speed. The solid detergent for automatic dishwashers set to a range where the maximum load is 2 to 10 kg when pierced at a speed of 50 ± 0.5 mm / min until the depth reaches 10 mm from the surface of the solid detergent. It is set as the summary of 5.
(A) Alkaline agent (excluding anhydrous silicate and carbonate) 5-30% by mass.
(B) Water 15-60 mass%.
(C) Nonionic surfactant 0.01-5 mass%.
(D) 5-50 mass% of water-soluble chelating agents.
(E) Polymer electrolyte polymer 0.1-10 mass%.
(F) 10-50 mass% of anhydrous alkali metal hydroxide salts.

  In particular, the present invention includes, in particular, the alkali agent of the component (A), an aqueous solution of sodium hydroxide having a concentration of 25 to 50% by mass, an aqueous solution of potassium hydroxide having a concentration of 25 to 50% by mass, and 30 to 50% by mass. A solid detergent for an automatic dishwasher, which is derived from at least one selected from the group consisting of an aqueous solution of potassium silicate having a concentration of 30% and an aqueous solution of sodium silicate having a concentration of 30 to 50% by mass, is a sixth aspect.

  Furthermore, among these, the water-soluble chelating agent of the component (D) is sodium gluconate, sodium citrate, ethylenediaminetetraacetic acid tetrasodium, nitrilotriacetic acid trisodium, glutamic acid-N, N. A solid detergent for an automatic dishwasher which is at least one selected from the group consisting of tetrasodium diacetate, sodium tripolyphosphate, sodium orthophosphate and 1-hydroxyethylidene-1,1-diphosphonic acid And the polymer electrolyte polymer of the component (E) is polyacrylic acid, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, poly-α-hydroxypolyacrylic acid sodium salt, acrylic acid-2 The group consisting of sodium hydroxy-3-allyloxypropanesulfonate An automatic dishwasher solid detergent is at least one selected et a seventh gist of the.

  In the present invention, the “slurry aqueous solution” refers to a liquid material that is slurried when the base liquid is an aqueous solution and contains a component that does not partially dissolve therein.

  The method for producing a solid detergent for an automatic dishwasher according to the present invention comprises adding an anhydrous alkali metal hydroxide salt to a specific slurry aqueous solution X under non-heating, non-cooling and non-pressurization, After being dispersed in a dissolved state, it is filled in a mold and solidified. According to this production method, the material composition can be solidified without any operations such as heating, cooling, and pressurization, so that the energy cost is low and it is economical. Moreover, even though the obtained solid detergent has sufficient hardness (hardness), moderate solubility is promoted by the presence of the anhydrous alkali metal hydroxide salt dispersed in the undissolved state. Therefore, there is no unevenness in the dissolution rate and the dissolution amount, and a homogeneous detergent diluent can be provided.

  And the solid detergent for automatic dishwashers of the present invention obtained by the above-mentioned manufacturing method not only has excellent uniform solubility as described above, but also excellent cleaning for dishes, cooking utensils, etc. In particular, it has excellent cleaning performance for removing attached oily and dirt soils and protein soils. In addition, it is excellent in scale generation suppressing ability, anti-redeposition performance, and finished performance after cleaning. Furthermore, it is excellent in storage stability, and even when stored for a long period of time, there is no discoloration or conversion into a slurry, and stable quality can be maintained.

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

  The solid cleaning agent for automatic dishwashers of the present invention (hereinafter abbreviated as “the present cleaning agent”) includes (A) alkaline agent (excluding anhydrous silicate and carbonate), (B) water, (C) non An ionic surfactant, (D) a water-soluble chelating agent, (E) a polymer electrolyte polymer, and (F) an anhydrous alkali metal hydroxide salt are essential components.

As the alkali agent (excluding anhydrous silicate and carbonate) of the component (A), a sodium hydroxide aqueous solution having a concentration of 25 to 50% by mass, a potassium hydroxide aqueous solution having a concentration of 25 to 50% by mass, and 30 to 50% by mass. % Aqueous potassium silicate solution, 30-50 mass% aqueous sodium silicate solution, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 sodium silicate, potassium silicate, etc. And 48 mass% sodium hydroxide aqueous solution, 48 mass% concentration potassium hydroxide aqueous solution, No. 3 sodium silicate, molar ratio of SiO ₂ and K ₂ O (SiO ₂ : K ₂ O) It is preferable to use potassium silicate having a ratio of 1: 1 to 1: 3.5.

  The alkali agent of the component (A) is blended in the range of 5 to 30% by mass with respect to the entire cleaning agent. If it is less than 5% by mass, it has poor detergency against proteins and starch stains, and if it exceeds 30% by mass, the overall balance becomes worse, storage stability is reduced, and No further synergies can be obtained.

  The water of the component (B) used in the present invention includes water contained in the form of crystal water and aqueous solution derived from each component other than the component (B), and water added from the outside without being derived from each component. The sum of Examples of the “water added from the outside” include pure water, ion-exchanged water, soft water, distilled water, and tap water. These may be used alone or in combination of two or more. Of these, tap water and ion-exchanged water are preferably used from the viewpoint of economy and storage stability.

  The water of the said (B) component is mix | blended in 15-60 mass% with respect to this cleaning agent whole. If it is less than 15% by mass, not only the viscosity of the slurry aqueous solutions X and Y is too high and the production efficiency is lowered, but also a desired solid molded product cannot be obtained in some cases. On the other hand, when it exceeds 60% by mass, it is difficult to solidify, and even if solidified, practical hardness (hardness) cannot be obtained, which is unsuitable.

  Examples of the (C) nonionic surfactant used in the present invention include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, and polyhydric alcohol ethylene oxide propylene. Oxide adducts, ethylene oxide propylene oxide adducts of glycerin, glycerin fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, etc. Or may be used in combination of two or more.

  Among these, at least one of polyoxyalkylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide propylene oxide adduct, and glycerin ethylene oxide propylene oxide adduct is preferable.

  When these nonionic surfactants are described in more detail, as polyoxyethylene polyoxypropylene alkyl ether, 1 to 40 mol of ethylene oxide (EO) is added to a linear or branched alcohol having 6 to 24 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether added with 1 to 50 mol of propylene oxide (PO), 1 to 20 mol of EO and 1 to 20 mol of PO in a linear or branched alcohol having 6 to 18 carbon atoms And polyoxyethylene polyoxypropylene alkyl ether having a weight ratio of EO / PO in the range of 0.5 to 5, 1 to 15 mol of EO in a linear or branched alcohol having 6 to 18 carbon atoms Polyoxyethylene in which 1 to 50 mol of PO is added and the weight ratio of EO / PO is in the range of 0.05 to 1 Polyoxypropylene alkyl ether and the like.

  The pluronic block polymer has an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 4.0. The pluronic block polymer has an average molecular weight of 500 to 10. A pluronic block polymer having an EO content in the range of 5% to 80% of the total average molecular weight, an average molecular weight in the range of 500 to 10,000, and an EO / PO weight ratio of 0.00. Examples include pluronic block polymers in the range of 05-1.

  The reverse pluronic block polymer includes a reverse pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 1.

  Furthermore, as the EO / PO adduct of polyhydric alcohol, trimethylolpropane added with 3-45 mol of EO and 15-120 mol of PO can be mentioned. As the EO / PO adduct of glycerin, Examples include glycerin added with 3 to 45 mol of EO and 15 to 120 mol of PO.

  The above nonionic surfactants are formulated for the purpose of improving detergency, prevention of re-attachment of food stains to the object to be cleaned, and foam suppression, and each can be used alone or in combination of two or more. May be used. In particular, the combination as described below is preferable in terms of improving the cleaning performance, the ability to prevent reattachment of oil to the object to be cleaned, and the foam suppression.

  (1) Polyoxy having 1 to 20 mol of EO and 1 to 20 mol of PO added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO being in the range of 2 to 5 1-20 mol of EO and 1-20 mol of PO are added to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is EO of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2, polyhydric alcohol obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane -Three kinds of combinations consisting of PO adduct (b).

  (2) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a straight or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO is in the range of 2 to 5. 1-20 mol of EO and 1-20 mol of PO are added to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is EO / PO adduct of glycerin in which polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and 3-45 mol of EO and 15-120 mol of PO are added to glycerin (C) 3 types of combinations.

  (3) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 2 to 5. EO / PO weight ratio by adding 1 to 20 mol of EO and 1 to 20 mol of PO to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms Of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and linear or branched alcohol having 6 to 18 carbon atoms and 1 to 15 mol of EO and 1 to 50 of PO. And polyoxyethylene polyoxypropylene alkyl ether (a-3) having a weight ratio of EO / PO in the range of 0.05 to 0.5, 3 to 45 mol of EO in trimethylolpropane, and PO. Four combinations consisting 15 to 120 EO · PO adduct of a polyhydric alcohol obtained by adding a molar and (b).

  (4) Polyoxy having 1 to 20 moles of EO and 1 to 20 moles of PO added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO being in the range of 2 to 5 EO / PO weight ratio by adding 1 to 20 mol of EO and 1 to 20 mol of PO to ethylene polyoxypropylene alkyl ether (a-1) and linear or branched alcohol having 6 to 18 carbon atoms Of polyoxyethylene polyoxypropylene alkyl ether (a-2) in the range of 0.5 to 2 and linear or branched alcohol having 6 to 18 carbon atoms and 1 to 15 mol of EO and 1 to 50 of PO. And polyoxyethylene polyoxypropylene alkyl ether (a-3) having a weight ratio of EO / PO in the range of 0.05 to 0.5, 3 to 45 mol of EO and glycerin and PO 15 to 120 Four combinations consisting EO · PO adduct of glycerin was added and Le and (c).

  (5) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. A polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5, trimethylolpropane having 3 to 45 mol of EO and 15 to 120 mol of PO. Three kinds of combinations consisting of an EO / PO adduct (b) of a monohydric alcohol.

  (6) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5, and glycerol EO obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerol -3 types of combinations consisting of PO adduct (c).

  (7) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. Polyoxyethylene polyoxypropylene alkyl ether (a-2), EO / PO adduct of polyhydric alcohol (b) or glycerin obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane Two kinds of combinations consisting of EO and PO adducts (c) of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to the above.

  (8) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. A polyoxyethylene polyoxypropylene alkyl ether (a-2) and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 0.5 ( d-1) or a reverse pluronic block polymer (e-1) having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.05 to 0.5, and trimethylolpropane EO / PO adduct (b) of polyhydric alcohol obtained by adding 3 to 45 moles of EO and 15 to 120 moles of PO or 3 to 45 moles of EO and 15 to 12 parts of glycerin Three combinations consisting EO · PO adduct of glycerin was added and molar and (c).

  (9) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. A polyoxyethylene polyoxypropylene alkyl ether (a-2) and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.5 to 4.0 ( d-2) or a reverse pluronic block polymer (e-2) having an average molecular weight in the range of 500 to 10,000 and an EO / PO weight ratio in the range of 0.5 to 1.0, and trimethylolpropane EO / PO adduct (b) of polyhydric alcohol obtained by adding 3 to 45 moles of EO and 15 to 120 moles of PO, or 3 to 45 moles of EO and 15 to 120 moles of PO in glycerin. Three combinations consisting preparative EO · PO adduct of glycerin was added and (c).

  (10) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. Polyoxyethylene polyoxypropylene alkyl ether (a-2), EO · PO adduct (b) of polyhydric alcohol obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane, Three combinations consisting of EO and PO adduct (c) of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerin.

  (11) 1-20 mol of EO and 1-20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. The weight of EO / PO by adding 1 to 15 mol of EO and 1 to 50 mol of PO to polyoxyethylene polyoxypropylene alkyl ether (a-2) and a linear or branched alcohol having 6 to 18 carbon atoms. Two combinations comprising polyoxyethylene polyoxypropylene alkyl ether (a-3) having a ratio in the range of 0.05 to 0.5.

  In particular, the combination of any of the above (5), (6), (7), (8), (10) and (11) is particularly suitable from the viewpoint of cleaning performance and foam suppression.

  The blending amount of the nonionic surfactant as the component (C) is set in a range of 0.01 to 5% by mass with respect to the entire cleaning agent. That is, when the blending amount is less than 0.01% by mass, the desired cleaning performance is poor. On the other hand, when it exceeds 5% by mass, the stability of the cleaning agent system is deteriorated from the overall balance, and a synergistic effect with other components is achieved. This is because no more can be obtained. In particular, setting in the range of 0.1 to 3% by mass is preferable in terms of cleaning performance, stability of the cleaning agent system, and cost.

  Examples of the water-soluble chelating agent (D) used in the present invention include sodium orthophosphate, sodium polyphosphate, sodium pyrophosphate, sodium metaphosphate, sodium hexametaphosphate, potassium orthophosphate, potassium polyphosphate, potassium pyrophosphate, and metaphosphoric acid. Phosphate such as potassium and potassium hexametaphosphate, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium iminodiacetate, sodium ethylenediaminepentaacetate, sodium glycol etherdiaminetetraacetate, sodium hydroxyethyliminodiacetate, sodium triethylenetetraminehexaacetate , Sodium dienecorate, potassium ethylenediaminetetraacetate, potassium nitrilotriacetate, potassium iminodiacetate, potassium ethylenediaminepentaacetate Aminocarboxylates such as glycol ether diamine potassium tetraacetate, potassium hydroxyethyliminodiacetate, potassium triethylenetetramine hexaacetate, potassium diencorate, sodium citrate, sodium malate, sodium tartrate, sodium succinate, sodium gluconate, Organic acid salts such as sodium fumarate, potassium citrate, potassium malate, potassium tartrate, potassium succinate, potassium gluconate, potassium fumarate, glutamic acid-N, N′-tetraacetic acid tetrasodium salt, ethane-1,1- Sodium diphosphonate, sodium ethane-1,1,2-triphosphonate, sodium ethane-1-hydroxy-1,1-diphosphonate, potassium ethane-1,1-diphosphonate, ethane-1,1,2-triphosphonic acid Cali Phosphonates such as potassium ethane-1-hydroxy-1,1-diphosphonate, sodium ethanehydroxy-1,1,2-triphosphonate, sodium ethane-1,2-dicarboxy-1,2-diphosphonate Hydroxyphosphonates such as sodium methanehydroxyphosphonate, potassium ethanehydroxy-1,1,2-triphosphonate, potassium ethane-1,2-dicarboxy-1,2-diphosphonate, potassium methanehydroxyphosphonate, -Sodium phosphonobutane-1,2-dicarboxylate, sodium 1-phosphonobutane-2,3,4-tricarboxylate, sodium α-methylphosphonosuccinate, potassium 2-phosphonobutane-1,2-dicarboxylate, 1-phosphonobutane- Potassium 2,3,4-tricarboxylate, α-me Phosphonocarboxylic acids such as potassium Ruhosuhonokohaku acid.

  Of these, sodium gluconate, sodium citrate, ethylenediaminetetraacetic acid tetrasodium, nitrilotriacetic acid trisodium, glutamic acid-N, N′-tetraacetic acid tetrasodium, sodium tripolyphosphate, ortholine Sodium acid, 1-hydroxyethylidene-1,1-diphosphonate is used. These may be used alone or in combination of two or more.

  (D) The water-soluble chelating agent of component is mix | blended in 5-50 mass% with respect to this cleaning agent whole. If it is less than 5% by mass, the cleaning property against oil stains becomes poor and the ability to suppress scale formation decreases, and if it exceeds 50% by mass, the balance as a whole deteriorates and the desired performance is reduced. Decreasing and not preferable.

  Examples of the polymer electrolyte polymer of the component (E) used in the present invention include polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid. , Polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride-diisobutylene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, maleic anhydride-ethylene copolymer, maleic anhydride Acid-ethylene cross-linked copolymer, maleic anhydride-vinyl acetate copolymer, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride Acid-isoprene copolymer, maleic anhydride and Poly-β-ketocarboxylic acid derived from carbon oxide, itaconic acid-ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid -Methylene copolymer, itaconic acid-fumaric acid copolymer, ethylene glycol-ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer and the like. Moreover, these salts can be used similarly. Among them, from the viewpoint of cleanability and availability, polyacrylic acid, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium poly-α-hydroxypolyacrylate, acrylic acid— It is preferred to use sodium 2-hydroxy-3-allyloxypropane sulfonate. These may be used alone or in combination of two or more.

  The average molecular weight of the polymer electrolyte polymer depends on the type, but for example, when sodium polyacrylate is used, the average molecular weight is 1,000 to 70,000, particularly the average molecular weight is 6,000 to 30,000. It is preferable to use those. Further, when an acrylic acid-maleic acid copolymer is used, it is preferable to use one having an average molecular weight of 40,000 to 100,000, particularly an average molecular weight of 50,000 to 75,000.

  The polymer electrolyte polymer of the component (E) is blended in the range of 0.1 to 10% by mass with respect to the entire cleaning agent. If it is less than 0.1% by mass, the desired effect of preventing recontamination and cleaning properties are poor, and if it exceeds 10% by mass, the balance as a whole becomes worse and storage stability decreases. A synergistic effect with other components cannot be obtained any more, which is not preferable.

  Examples of the anhydrous alkali metal hydroxide salt of component (F) used in the present invention include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Potassium oxide is preferably used.

  The anhydrous alkali metal hydroxide salt of the component (F) is blended in the range of 10 to 50% by mass with respect to the entire cleaning agent. If it is less than 10% by mass, not only the detergency is deteriorated but also a desired solid molded article cannot be obtained, and if it exceeds 50% by mass, a synergistic effect with other components is further obtained. It is not economical.

  And in this invention, as anhydrous silicate of (G) component which is an arbitrary component which can be used with the said essential (A)-(F) component, anhydrous sodium metasilicate, anhydrous potassium metasilicate, etc. Among them, anhydrous sodium metasilicate and anhydrous potassium metasilicate are preferably used from the viewpoint of easy availability.

  When using the anhydrous silicate of said (G) component, it is preferable to mix | blend in 0-50 mass% with respect to this cleaning agent whole. If it exceeds 50% by mass, the balance as a whole becomes worse and the productivity is lowered, which is not preferable.

  Similarly, the carbonate of the component (H), which is an optional component, includes sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate, sodium carbonate decahydrate, among others. Sodium carbonate and sodium bicarbonate are preferably used from the viewpoint of economy.

  When using the carbonate of the said (H) component, it is preferable to mix | blend in 0-30 mass% with respect to this cleaning agent whole. If it exceeds 30% by mass, the balance as a whole is deteriorated, the productivity is lowered, and a synergistic effect with other components cannot be obtained any more, which is not preferable.

  Similarly, the silicone-based antifoaming agent of component (I), which is an optional component, includes self-emulsifying silicone-based antifoaming agents, emulsion-type silicone-based antifoaming agents, oil-type silicone-based antifoaming agents, etc. A self-emulsifying silicone antifoaming agent is preferably used.

  The silicone-based antifoaming agent (I) is preferably blended in the range of 0 to 5% by mass with respect to the entire cleaning agent. If it exceeds 5% by mass, the balance as a whole is deteriorated, the productivity is lowered, and the storage stability is also deteriorated.

  In this cleaning agent, as optional components other than the components (G) to (H), a solvent such as glycerin, propylene glycol, ethyl alcohol, isopropyl alcohol, a builder such as a chelating agent other than the component (D), pH A regulator, a solubilizer, a viscosity modifier, an enzyme, an enzyme stabilizer, a fluorescent agent, a dye, a fragrance, a metal corrosion inhibitor, a softener, an electrostatic inhibitor, and the like can be blended.

  And pH (JIS Z-8802: 1984 "pH measuring method") of the 0.1 mass% aqueous solution formed by diluting this cleaning agent with water is set in the range of 8.0 to 12.5. Is practically preferable.

  Next, the production method of the present invention, that is, a method for obtaining the present cleaning agent using the essential components (A) to (F) and the like will be described.

  The production method of the present invention is greatly characterized in that it is under non-heating, non-cooling and non-pressurization in a series of steps for obtaining the present cleaning agent from the material composition. That is, first, under non-heating, non-cooling and non-pressurization, (A) alkaline agent, (B) water, (C) nonionic surfactant, (D) water-soluble chelating agent, (E) polymer electrolyte heavy The coalescence is mixed with stirring to form a slurry aqueous solution X. At this time, it is preferable to add the polymer electrolyte polymer of the component (E) last. This is because it is easy to impart an appropriate viscosity to the slurry-like aqueous solution X close to supersaturation.

  Next, under the same non-heating, non-cooling and non-pressurization, (F) anhydrous alkali metal hydroxide is added to the slurry aqueous solution X, and the mixture is stirred and mixed. The addition of the anhydrous alkali metal hydroxide (F) increases the viscosity of the slurry aqueous solution X and becomes supersaturated, so that at least a part of the anhydrous alkali metal hydroxide is uniformly dissolved. A dispersed slurry aqueous solution Y is obtained.

  Then, the obtained slurry-like aqueous solution Y is filled in a mold of any size (for example, a container loaded in a cleaning agent dissolving apparatus) and solidified. Thereby, a solid present cleaning agent can be obtained.

  The present cleaning agent thus obtained is uniformly used in an undissolved state while having a hardness as a solid cleaning agent when used in a cleaning agent dissolving apparatus for an automatic dishwasher. Dispersed anhydrous alkali metal hydroxide salt promotes moderate solubility, so that a homogeneous detergent dilution solution can be obtained without causing uneven dissolution rate and amount of dissolution, as well as homogeneous cleaning performance for dishes, cooking utensils, etc. It has the advantage that finish can be maintained.

  The temperature of the slurry aqueous solution X and the slurry aqueous solution Y is generally in the range of 15 ° C. to 50 ° C., although the temperature rises due to its own reaction heat. That is, as described above, there is an advantage that energy costs can be reduced without requiring operations such as heating, cooling, and pressurization in a series of manufacturing steps.

  Furthermore, the above stirring and mixing process can be performed using a single mixing kettle, and does not involve transfer from the manufacturing equipment to the manufacturing equipment. There are advantages such as being complicated and not requiring much time for manufacturing time.

  This cleaning agent has a hardness (solid hardness) in the range of 2 to 10 kg at the maximum load when piercing a needle with a diameter of 3 mm at 25 ° C. at a puncture speed of 50 ± 0.5 mm / min and reaching 10 mm from the surface. It has a hardness that is easy to handle.

  In addition, the measuring method of the said hardness is evaluated by the method shown below.

[Hardness measurement method]
Rheometer (manufactured by Sun Kagaku Co., Ltd., model: CR-200) is placed on a sample cradle with a molded solid detergent (cylindrical, height 70 mm, diameter 60 mm) so that the circular cross-section becomes the top and bottom surfaces. After mounting, the sample holder is applied to the center of the upper surface of the sample by applying the tip of a penetration adapter (a rod with a diameter of 3 mm, the tip of which is a cone with a height of 5 mm and pointed). Is pushed up at a constant speed (50 ± 0.5 mm / min), pierced until the tip of the adapter reaches a certain depth (10 mm), and the load (kg) at that time can be obtained.

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

[Examples 1 to 87, Comparative Examples 1 to 31]
A solid detergent for an automatic dishwasher (hereinafter referred to as a test detergent) having the composition described in Tables 1 to 26 below is prepared, and its manufacturability, hardness, solubility, storage stability, and scale generation inhibiting ability The following test methods were used to evaluate the eight test items of cleaning performance, anti-reattachment performance, and finish after cleaning. And the result was combined with Table 1-Table 26 of the postscript, and was shown. The components used in each of the test detergents are as follows, and the numerical values in the table are the contents of the respective components (mass%, pure content conversion).

[Component A] Alkaline agent / Alkaline agent 1
Sodium hydroxide (pure 48%)
Product name: 48% caustic soda, manufactured by Shin-Etsu Chemical Co., Ltd., alkaline agent 2
Potassium hydroxide (48% pure)
Product name: Caustic potash 48%, Toagosei Co., Ltd., Alkaline 3
Sodium silicate (pure content 39%, molar ratio SiO ₂ : Na ₂ O = 3: 1)
Product Name: JIS No. 3 sodium silicate, manufactured by Guangei Chemical Co., Ltd., alkali agent 4
Potassium silicate (pure content 40%, molar ratio SiO ₂ : K ₂ O = 3: 1)
Product name: Potassium Silicate, manufactured by Nippon Chemical Industry Co., Ltd.

[Component C] Nonionic surfactant / surfactant 1
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 3,300
Product name: Epan 740, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., surfactant 2
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.67, average molecular weight: 2,800
Product name: Pluronic RPE 1740, manufactured by BASF, surfactant 3
Polyoxyethylene (P = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14, 15) ether EO / PO weight ratio = 1.26
Prototype / Surfactant 4
Polyoxyethylene (P = 8) Polyoxypropylene (q = 6) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 1.01
Product name: Pepol AS-054C, manufactured by Toho Chemical Industries, Ltd., surfactant 5
Polyoxyethylene (m = 4) Polyoxypropylene (q = 38) Linear alkyl (C16-C18) ether EO / PO weight ratio = 0.08
Product name: Adecatol LG-299, manufactured by Asahi Denka Kogyo Co., Ltd., surfactant 6
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,000
Product name: Pluronic PE6100, manufactured by BASF, surfactant 7
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.11, average molecular weight = 2,800
Product name: Pluronic RPE2510, manufactured by BASF, surfactant 8
Trimethylolpropane EO, PO adduct EO / PO weight ratio = 0.21, average molecular weight = 4,500
Prototype / Surfactant 9
Glycerin EO, PO adduct prototype

[Component D] Water-soluble chelating agent / water-soluble chelating agent 1
Sodium gluconate Product name: Sodium gluconate, manufactured by Fuso Chemical Industry Co., Ltd., water-soluble chelating agent 2
Sodium citrate Product name: Trisodium citrate, manufactured by Iwata Chemical Industry Co., Ltd., water-soluble chelating agent 3
Ethylenediaminetetraacetic acid tetrasodium Trade name: Trilon B, manufactured by BASF, water-soluble chelating agent 4
Nitrilotriacetic acid trisodium Product name: Trilon A92R, manufactured by BASF, water-soluble chelating agent 5
Glutamic acid-N, N′-diacetate tetrasodium product name: Dissolvin GL-PD, manufactured by Akzo Nobel, water-soluble chelating agent 6
Sodium tripolyphosphate Product name: Wandet B, manufactured by Nippon Chemical Industry Co., Ltd., water-soluble chelating agent 7
Sodium orthophosphate Product name: Sodium tertiary phosphate, manufactured by Nippon Chemical Industry Co., Ltd., water-soluble chelating agent 8
1-hydroxyethylidene-1,1-diphosphonic acid Product name: Diquest 2016D, manufactured by Solusia

[E component] polymer electrolyte polymer / polymer electrolyte polymer 1
Polyacrylic acid (48% pure, average molecular weight 4,500)
Product name: Primary LMW-45, manufactured by ROHM & HAAS, polyelectrolyte polymer 2
Sodium polyacrylate (44% pure, average molecular weight 3,500)
Product name: Aqualic DL40S, manufactured by Nippon Shokubai Co., Ltd., polyelectrolyte polymer 3
Sodium polyacrylate (45% pure, average molecular weight 8,000)
Product name: Sokalan 30CL, manufactured by BASF, polyelectrolyte polymer 4
Sodium salt of acrylic acid-maleic acid copolymer (pure content 35%, average molecular weight 40,000)
Product name: Acusol 505N, manufactured by ROHM & HAAS, polyelectrolyte polymer 5
Sodium poly-α-hydroxypolyacrylate (pure content 30%, average molecular weight 10,000 to 14,000)
Product name: Pale Plaque 1200, manufactured by Nippon Peroxide Co., Ltd./Polyelectrolyte polymer 6
2-hydroxy-3-allyloxypropanesulfonic acid sodium acrylate (pure content 50%, average molecular weight 3,000)
Product name: Aqualic GL246, manufactured by Nippon Shokubai Co., Ltd.

[Component F] Anhydrous alkali hydroxide metal salt / Anhydrous alkali hydroxide 1
Anhydrous sodium hydroxide Product name: Tosoh Pearl, manufactured by Tosoh Corporation ・ Anhydrous alkali hydroxide 2
Anhydrous potassium hydroxide Brand name: Potassium hydroxide special grades

[Component G] Anhydrous silicate / anhydrous silicate Anhydrous sodium metasilicate Product name: Anhydrous sodium metasilicate, manufactured by Nippon Chemical Industry Co., Ltd.

[H component] Carbonate / Metal carbonate 1
sodium carbonate
Product name: Light soda ash, Tokuyama Soda Co., Ltd. Metal carbonate 2
sodium hydrogen carbonate
Product name: Sodium bicarbonate, manufactured by Tokuyama Soda Co., Ltd.

[Component I] Silicone-based antifoaming agent / silicone-based antifoaming agent Silicone Product name: KS-530, manufactured by Shin-Etsu Chemical Co., Ltd.

(1) Manufacturability [Test method]
In all the steps of mixing, stirring, and filling, it was determined according to the following evaluation criteria whether or not the test cleaning agent could be produced without delay.
〔Evaluation criteria〕
○: Filling was possible and solidification was possible ×: Filling was impossible or solidification was not possible, and ○ was determined to be practical.

(2) Hardness [Test method]
A test cleaning agent (columnar shape, height 70 mm, diameter 60 mm) was attached to a sample base of a rheometer (manufactured by Sun Kagaku Co., Ltd., model: CR-200) so that the circular cross-section becomes the upper and lower surfaces. After that, the tip of the adapter for penetration (a 3 mm diameter rod, the tip of which is a 5 mm high cone and pointed) is applied to the center of the upper surface of the sample, and the sample holder is fixed. It was measured by pushing up at a speed (50 ± 0.5 mm / min), piercing until the tip of the adapter reached a certain depth (10 mm), and determining the load (kg) at that time. In addition, it can be determined that those having a maximum load in the range of 2 to 10 kg are generally practical, but those having a maximum load of less than 2 kg or exceeding 10 kg may be determined to have no practicality. it can.

(3) Solubility [Test method]
On top of a magnetic stirrer (manufactured by Yamato Scientific Co., Ltd., model: MG600), a water bath set at 50 ° C. (manufactured by Tokyo Science Instruments Co., Ltd., model: SB-35) is placed and placed in the water bath. 1 L of hot water and a 1 L beaker containing a stir bar were placed and hot water was rotated at a rotation speed of 500 rpm. Then, the time from charging to complete dissolution was measured and judged according to the following evaluation criteria.
〔Evaluation criteria〕
A: Dissolution time is less than 60 seconds O: Dissolution time is 60 seconds or more and less than 120 seconds Δ: Dissolution time is 120 seconds or more and less than 180 seconds X: Dissolution time is 180 seconds or more
And ◎ and ○ were judged to be practical.

(4) Storage stability [Test method]
The test cleaning agent poured into a 250 ml polypropylene container and solidified was placed in a 37 ° C. constant temperature bath (manufactured by Yamato Kagaku Co., model: IN800) for one month. And the external appearance was observed visually and it determined in accordance with the following evaluation criteria.
〔Evaluation criteria〕
○: After 1 month, no discoloration or conversion to slurry was observed. ×: After 1 month, discoloration / conversion to slurry was observed, and ○ was determined to be practical.

(5) Scale generation suppression ability [test method]
A colorimetric tube with a capacity of 100 ml containing 50 ml of a detergent diluent diluted to 0.05% by mass using artificial hard water (total hardness: 150 mg / L) was placed in a constant temperature bath (manufactured by Yamato Kagaku Co., Ltd., Model: After being placed in IS82) for 24 hours, the generation state of the scale in the colorimetric tube was visually observed and judged according to the following evaluation criteria.
〔Evaluation criteria〕
◎: No scale was generated. ○: Little scale was generated. △: Scale was generated. ×: Scale adhesion was remarkable.

(6) Detergency [Test method]
The test cleaning agent was put into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and washed under the following operating conditions. And the earthenware dish which is the following to-be-washed | cleaned object was wash | cleaned as a set of 10, and the removal degree of dirt was determined visually according to the following evaluation criteria. In addition, beef tallow, curry, and egg yolk were prepared as dirt, and cleaning evaluation was performed on each dirt.
* Operating condition Detergent concentration: 0.1% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70-80 ppm (as CaCO ₃ )
Beef tallow dirt: Refined beef tallow was used.
Curry dirt: A commercially available retort curry (bon curry) was used.
Egg yolk stain: Only egg yolk was used, especially with good mixing.
Object to be cleaned: A ceramic dish having a diameter of 10 cm was adhered to the soil so as to be 4 g / sheet and dried at room temperature for 1 hour.
〔Evaluation criteria〕
◎ ... 90% or more soil removal ○ ... 70 or more, less than 90% soil removal △ ... 50 or more, less than 70% soil removal × ... 50% or less soil removal

(7) Anti-reattachment performance [test method]
30 g of salad oil colored with the test detergent and oil red (Sudan IV, manufactured by Wako Pure Chemical Industries, Ltd.) is put into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.), and a clean melamine dish is prepared. Washing was performed under the following operating conditions. And the adhesion degree (re-adhesion degree) of the colored salad oil to the clean melamine dish after the rinse rinse was visually observed and judged according to the following evaluation criteria.
* Operating condition Detergent concentration: 0.1% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70-80 ppm (as CaCO ₃ )
〔Evaluation criteria〕
◎… There was no dirt on the cleaning dish. ○… There was almost no dirt on the cleaning dish. △… Smudged on the cleaning dish.

(8) Finishability after washing [Test method]
The test cleaning agent was put into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and washed under the following operating conditions. And the glass cup which is a to-be-washed object shown below was wash | cleaned as 1 set, and the finished performance after washing | cleaning was evaluated according to the following evaluation criteria.
* Operating condition Detergent concentration: 0.1% by mass
Washing temperature: 60 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing 15 seconds)
Of use water hardness (as CaCO ₃₎ 70~80ppm
Object to be washed: Milk was poured into an 8 ounce glass cup (manufactured by Sasaki Glass Co., Ltd.) and left for 5 minutes. Next, after discarding the milk, it was air-dried for 30 minutes without rinsing with water.
〔Evaluation criteria〕
◎: No water spots are observed ○: 1-2 water spots are observed △: 3-5 water spots are observed X: 6 or more water spots are observed

  From the above results, it can be seen that the test detergents of Examples 1 to 87 show good performance in all test items. On the other hand, it turns out that the test cleaning agent of Comparative Examples 1-31 lacks practicality in any test item.

Claims (8)

It is a manufacturing method of the solid detergent used for an automatic dishwasher, Comprising: The following (A)-(E) component is mix | blended so that it may become the following ratio with respect to the said solid detergent whole, non-heating, non-cooling, and The step of obtaining a slurry aqueous solution X by stirring and mixing under non-pressurization, and the slurry aqueous solution X, the following component (F) is blended so as to have the following ratio with respect to the whole solid detergent, A step of obtaining a slurry aqueous solution Y in which at least a part of the component (F) is dispersed in an undissolved state by stirring and mixing under non-heating, non-cooling, and non-pressurization, and filling the slurry aqueous solution Y into a mold A process for producing a solid detergent for an automatic dishwasher, comprising a step of solidifying and solidifying.
(A) Alkaline agent (excluding anhydrous silicate and carbonate) 5-30% by mass.
(B) Water 15-60 mass%.
(C) Nonionic surfactant 0.01-5 mass%.
(D) 5-50 mass% of water-soluble chelating agents.
(E) Polymer electrolyte polymer 0.1-10 mass%.
(F) 10-50 mass% of anhydrous alkali metal hydroxide salts.   The manufacturing method of the solid cleaning agent for automatic dishwashers of Claim 1 which mix | blended anhydrous silicate as (G) component in the process of obtaining the said slurry-like aqueous solution X.   The method for producing a solid detergent for an automatic dishwasher according to claim 1 or 2, wherein in the step of obtaining the slurry aqueous solution X, a carbonate is blended as the component (H).   In the process of obtaining the said slurry-like aqueous solution Y, the manufacturing method of the solid detergent for automatic dishwashers as described in any one of Claims 1-3 which was made to mix | blend a silicone type antifoamer as (I) component. It is a solid washing | cleaning agent for automatic dishwashers obtained by the manufacturing method as described in any one of the said Claims 1-4, Comprising: The following (A)-(F) component is with respect to the said solid washing | cleaning agent whole. In addition to being contained in the following ratio, the solid content in the entire solid detergent is set to 40 to 75 mass%, and the hardness of the solid detergent is a needle with a 3 mm diameter needle at 25 ° C. Solid for an automatic dishwasher characterized in that the maximum load when pierced at a speed of ± 0.5 mm / min until reaching a depth of 10 mm from the surface of the solid detergent is 2 to 10 kg. Washing soap.
(A) Alkaline agent (excluding anhydrous silicate and carbonate) 5-30% by mass.
(B) Water 15-60 mass%.
(C) Nonionic surfactant 0.01-5 mass%.
(D) 5-50 mass% of water-soluble chelating agents.
(E) Polymer electrolyte polymer 0.1-10 mass%.
(F) 10-50 mass% of anhydrous alkali metal hydroxide salts.   The alkali agent of the component (A) is a sodium hydroxide aqueous solution having a concentration of 25 to 50% by mass, a potassium hydroxide aqueous solution having a concentration of 25 to 50% by mass, a potassium silicate aqueous solution having a concentration of 30 to 50% by mass and 30 to 50% by mass. The solid detergent for automatic dishwashers according to claim 5, which is derived from at least one selected from the group consisting of a sodium silicate aqueous solution having a concentration of%.   The water-soluble chelating agent of the above component (D) is sodium gluconate, sodium citrate, ethylenediaminetetraacetic acid tetrasodium, nitrilotriacetic acid trisodium, glutamic acid-N, N'-diacetate tetrasodium, sodium tripolyphosphate, orthophosphoric acid The solid detergent for automatic dishwashers according to claim 5 or 6, which is at least one selected from the group consisting of sodium and 1-hydroxyethylidene-1,1-diphosphonic acid.   The polymer electrolyte polymer of the above component (E) is polyacrylic acid, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium poly-α-hydroxypolyacrylate, acrylic acid-2-hydroxy The solid detergent for automatic dishwashers according to any one of claims 5 to 7, which is at least one selected from the group consisting of sodium -3-allyloxypropane sulfonate.