JP2005154716A - Detergent composition for automatic dishwashers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for automatic dishwashers, in which the liquidity of a determined aqueous diluted solution is neutral, which has good environmental safety and working safety, which achieves excellent detergent performance and storage stability that are equivalent to those of alkaline detergents, and which also has good finishing property after rinsing. <P>SOLUTION: The detergent composition for automatic dishwashers contains (a) a 3 to 40 mass% nonionic surfactant, (b) a 0.2 to 10 mass% polymeric chelating agent, (c) a specific acescent or alkalescent 50 to 96.8 mass% water-soluble electrolyte, and a 0.1 to 7 mass% enzyme for detergents. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cleaning composition for an automatic dishwasher suitable for cleaning hard surfaces such as tableware, glass, ceramics, metals, plastics, etc., and is excellent in environmental safety and work safety, and is neutral while being alkaline. The present invention relates to a cleaning composition for an automatic dishwasher having excellent cleaning performance and storage stability comparable to the cleaning agent.

  Conventionally, automatic dishwashers have been widely used in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like in order to efficiently wash used dishes. Further, not only tableware 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.

  In liquid detergents used in these automatic washing machines, alkali hydroxide metal salts such as sodium hydroxide and potassium hydroxide are usually 10 to 50% by mass (below) for the purpose of removing strong oil stains. (Abbreviated as “%”).

  For example, Japanese Patent Laid-Open No. 2-55800 (see Patent Document 1) discloses a detergent in which a cleaning agent as a main component and a surfactant as an auxiliary cleaning component are separated and a supply device for the detergent Is disclosed. This product is weakly alkaline and is safer than conventional ones, but because the detergent is separated into two or more types, each component is not consumed at an equal rate and remains irregular. When trouble occurs in the operation of the dedicated detergent supply device, there is a problem that the mixing ratio of each component is disturbed and a uniform washing cannot be obtained.

  JP-A-6-33100 (see Patent Document 2) discloses a washing machine for an automatic dishwasher comprising a low-foaming nonionic surfactant, a washing builder, and a specific aliphatic carboxylic acid as essential components. Agents are disclosed. This has the advantage of being homogeneous and stable as a whole despite having a relatively large amount of low-foaming nonionic surfactant, but is stable at low temperatures up to -6 ° C. However, it does not have stability in a wide temperature environment.

  Further, JP-A-10-17900 (see Patent Document 3) discloses a dishwasher comprising a low-foaming nonionic surfactant, an organic solvent that is at least one of a polyhydric alcohol and a glycol ether, and water. A cleaning and drying toughening agent composition is disclosed. This is used in combination with an alkaline cleaning agent, which is the main cleaning agent, during cleaning operations, and by using it together, it is possible to obtain cleaning performance, suppression of spot generation, and degree of foam suppression. However, as in the prior art, it is premised on cleaning with an alkaline cleaning agent, and does not provide a safer cleaning agent. Moreover, since two kinds of drugs are used in combination, there is a problem that handling is complicated.

JP-A-2-55800 JP-A-6-33100 Japanese Patent Laid-Open No. 10-17900

  A detergent containing more than 5% of the above alkali metal hydroxide salt becomes a “non-medicinal deleterious substance” and requires special knowledge and handling from the viewpoint of safety. In addition, the above alkali metal hydroxide salt may erode the surface of glass tableware or cause blackening of aluminum tableware / cooking utensils, or it may cause strong irritation when scattered and adhered to the skin. Have the problem of giving. In consideration of safety during handling and storage, the container is housed in a thick and sturdy plastic container, which causes a problem of high cost.

  In recent years, instead of the alkali metal hydroxide salt, use of milder alkali agents and blending of various surfactants having high cleaning performance against oil stains have been required. Most of the above surfactants are foamy and are not suitable for nozzle-jet mechanical cleaning via a pump, or are easily decomposed by alkali or the like of the cleaning composition. On the other hand, a detergent composition using a surfactant that does not easily cause foaming or decomposition tends to cause separation / precipitation of the detergent composition itself, so that a homogeneous liquid detergent composition at the time of use can be obtained. There is a problem that it is difficult to get.

  Therefore, it is excellent in work safety and environmental safety, eliminating the complication of using two or more kinds of drugs in combination, and cleaning with a new composition that has the same or better cleaning performance and storage stability than a single agent. Development of an agent composition is strongly desired. Further, there is a demand for a neutral automatic dishwashing detergent having excellent cleaning performance against not only oil and fat stains but also starch stains and protein stains.

  The present invention has been made in view of such circumstances, and contains a nonionic surfactant, a polymer chelating agent and a specific weakly acidic to weakly alkaline water-soluble electrolytic substance, and 0.2% dilution thereof. A detergent composition having an aqueous solution pH (JIS-Z-8802: 1984 “pH measurement method”) in the range of 5.8 to 8.6 at 25 ° C. and excellent in environmental safety and work safety. In addition, an object of the present invention is to provide a cleaning composition for an automatic dishwasher that can be used as a single agent and has excellent cleaning performance and storage stability comparable to an alkaline cleaning agent.

In order to achieve the above object, the present invention includes the following components (a) to (c), and the pH of a 0.2% diluted aqueous solution (JIS-Z-8802: 1984 “pH measurement method”). ) Is set at 5.8 to 8.6 at 25 ° C. The first gist is a detergent composition for an automatic dishwasher.
(A) 3-40 mass% of surfactant.
(B) Polymer chelating agent 0.2-10 mass%.
(C) Selected from an organic acid consisting of sulfate, bicarbonate, citric acid, gluconic acid, malic acid, succinic acid, fumaric acid, tartaric acid, lactic acid, maleic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, or a water-soluble salt thereof. 50 to 96.8% by mass of at least one weakly acidic to weakly alkaline water-soluble electrolytic substance.

  In addition, the detergent composition for an automatic dishwasher, in which the surfactant of the component (a) is at least one of a nonionic surfactant and / or an anionic surfactant, has the second gist, ) Component non-ionic surfactant is polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide propylene oxide addition , Ethylene oxide propylene oxide adduct of glycerin, glycerin fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, sorbitan fatty acid ester and propylene glycol fatty acid ester The automatic dishwashing detergent composition is at least one selected et the third aspect.

  The polymer chelating agent of the component (b) is an acrylic acid polymer and a salt thereof, a maleic acid polymer and a salt thereof, an acrylic acid-maleic acid copolymer and a salt thereof, poly-α-hydroxyacrylic acid and It is at least one selected from salts thereof, acrylic acid-maleic acid-polyethylene glycol copolymers and salts thereof, olefin-maleic acid copolymers and salts thereof, acrylic acid-sulfonic acid copolymers and salts thereof The cleaning composition for an automatic dishwasher is a fourth gist.

In addition, in the weakly acidic to weakly alkaline water-soluble electrolytic substance of the component (c), at least a part of the water-soluble salt of the organic acid is a sodium salt, potassium salt, ammonium salt, magnesium salt, amine salt, ethanolamine salt. According to a fifth aspect of the present invention, there is provided a detergent composition for an automatic dishwasher, wherein the sulfate, which is a weakly acidic or weakly alkaline water-soluble electrolytic substance of component (c), is sodium sulfate, potassium sulfate, ammonium sulfate, and magnesium sulfate. A sixth gist of the cleaning composition for an automatic dishwasher, which is at least one selected from the above. Furthermore, among the above-mentioned component (c), which is a weakly acidic to weakly alkaline water-soluble electrolytic substance, the above automatic dishwashing containing at least magnesium sulfate in an amount of 3 to 30% by mass in terms of anhydride (MgSO ₄ ) The machine detergent composition is a seventh aspect. And the washing | cleaning agent composition for automatic dishwashers in which the bicarbonate which is the weak acidic thru | or weak alkaline water-soluble electrolytic substance of the said (c) component contains 5-96.8 mass% in the whole washing | cleaning agent composition. This is the eighth gist. Furthermore, let the 9th summary be the detergent composition for automatic dishwashers containing 0.1-7 mass% of enzyme for detergents of (d) component.

  A tenth aspect of a method for cleaning an object to be cleaned, wherein the cleaning composition for an automatic dishwasher is used in an automatic dishwasher as a 0.05 to 0.4% by weight diluted aqueous solution. To do.

  The cleaning composition for an automatic dishwasher of the present invention has a pH of a predetermined dilute aqueous solution (JIS-Z-8802: 1984 “pH measurement method”) at 25 ° C. and 5.8 to 8.6, and is environmentally safe. In addition to being excellent in safety and work safety, it achieves excellent cleaning performance and storage stability comparable to alkaline cleaners, and also has excellent finish after rinsing.

  And while the conventional cleaning composition is an alkaline cleaning composition mainly composed of an alkaline agent, the present invention has a surfactant, a polymer chelating agent, and a specific weakly acidic composition. Because it is a neutral detergent composition based on a weak alkaline water-soluble electrolytic substance, even if it may adhere to the skin, its irritation is much lower than before It has become. Therefore, the cleaning composition for an automatic dishwasher according to the present invention is used for automatic dishwashers, not only for the main washing of the automatic dishwashing machine but also for its preliminary washing (immersion), It can also be effectively used in cleaning applications.

  In addition, since it is a neutral cleaning agent, not only the surface of glass tableware, aluminum tableware, and cooking utensils, but also objects to be cleaned that have gold, silver or patterns on the surface of tableware. Has no adverse effect and has excellent finish after rinsing.

Further, it is possible to accommodate in a thin plastic container or a bag such as a pouch without being restricted by the conventional method.
Furthermore, in the conventional alkaline cleaning agent, it was necessary to neutralize the cleaning waste liquid with acid according to the wastewater treatment facility, etc., but in the cleaning composition for an automatic dishwasher of the present invention, Such a neutralization operation is not necessary.

  Therefore, the cleaning composition for an automatic dishwasher of the present invention is not limited to tableware / cooking utensils and the like, as well as for cleaning hard surfaces such as glass, ceramics, porcelain, metal, plastics, various manufacturing factories and processing factories. It can also be used as an automatic washing machine for washing instruments, containers, etc., plastic containers used for distribution, etc. Besides, it can be widely used for washing hard surfaces such as tiles and floors in food factories and food processing factories, washing containers such as glass bottles and beer bottles for beverages, and washing metal surfaces. Especially, it is suitable for using for the automatic dishwasher in a hotel, a restaurant, a school, a hospital, a restaurant, a catering company, a company cafeteria, etc.

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

  First, the cleaning composition for an automatic dishwashing machine of the present invention includes (a) a surfactant, (b) a polymer chelating agent, and (c) a sulfate, bicarbonate, citric acid, At least one weakly acidic to weakly alkaline water-soluble water selected from organic acids consisting of gluconic acid, malic acid, succinic acid, fumaric acid, tartaric acid, lactic acid, maleic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, or water-soluble salts thereof It is characterized by containing an electrolytic substance and an enzyme for detergent.

  Examples of the surfactant as the component (a) include nonionic surfactants and / or anionic surfactants. Here, as the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide propylene oxide adduct, glycerin Examples thereof include ethylene oxide propylene oxide adducts, glycerin fatty acid esters, sucrose fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and propylene glycol fatty acid esters.

  Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkane sulfonate salt, α-olefin sulfonate salt and the like. Specifically, examples of the alkyl benzene sulfonate include sodium alkyl benzene sulfonate, alkyl benzene sulfonate triethanolamine, and alkyl benzene sulfonate diethanolamine. Examples of the alkyl sulfate sulfonate include sodium lauryl sulfate, lauryl sulfate triethanolamine, Examples include ammonium lauryl sulfate, potassium lauryl sulfate, lithium lauryl sulfate, and barium lauryl sulfate, and examples of alkyl ether sulfate include sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate. Triethanolamine, ammonium polyoxyethylene alkyl ether sulfate And the like.

  The nonionic surfactant and the anionic surfactant are blended for the purpose of improving detergency, oil re-adhesion preventing property to the object to be washed, and foam suppression. Two or more species may be used in combination.

  These nonionic surfactants will be described in more detail. As polyoxyethylene alkyl ether, 2 to 20 mol of ethylene oxide (polyoxyethylene; EO) is added to a straight or branched alcohol having 6 to 24 carbon atoms. Polyoxyethylene alkyl ethers added, and poly-polyethylenes having 2 to 12 moles of EO added to linear or branched alcohols having 8 to 18 carbon atoms and an HLB in the range of 8 to 15 and 8 to 15 carbon atoms. Examples thereof include oxyethylene alkyl ether.

  Moreover, as polyoxyethylene polyoxypropylene alkyl ether, 1 to 40 mol of EO and 1 to 50 mol of propylene oxide (polyoxypropylene; PO) are added to a linear or branched alcohol having 6 to 24 carbon atoms. Polyoxyethylene polyoxypropylene alkyl ether, 1 to 20 mol of EO and 1 to 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 0.5 to 5, polyoxyethylene polyoxypropylene alkyl ether in the range of 5 to 5 and EO 1 to 15 mol and PO 1 to 50 mol are added to a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.00. And polyoxyethylene polyoxypropylene alkyl ethers in the range of 05 to 1.

  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 0.25 to 4.0. The pluronic block polymer has an average molecular weight of 500 to 10. A pluronic block polymer having an ethylene oxide content of 5% to 80% of the total average molecular weight, an average molecular weight of 500 to 10,000, and an EO / PO weight ratio of 0. And pluronic block polymers in the range of .05 to 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 an ethylene oxide propylene oxide adduct of a polyhydric alcohol, there can be mentioned one obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane.

  Moreover, as an ethylene oxide propylene oxide addition product of glycerol, what added 3-45 mol of EO and 15-120 mol of PO to glycerol is mention | raise | lifted.

  Examples of monoglycerol fatty acid esters include glycerol monocaproate, glycerol monocaprylate, glycerol monocaprate, glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, and glycerol monostearate. Examples thereof include esters, glycerol monobehenate, glycerol monooleate, glycerol monoelaidate, glycerol monoricinoleate, and glycerol monocondensed ricinoleate.

  Examples of sucrose fatty acid esters include caproic acid sucrose ester, caprylic acid sucrose ester, capric acid sucrose ester, lauric acid sucrose ester, myristic acid sucrose ester, palmitic acid sucrose ester, and stearic acid sucrose ester. Sugar ester, behenic acid sucrose ester, oleic acid sucrose ester, elaidic acid sucrose ester, ricinoleic acid sucrose ester, condensed ricinoleic acid sucrose ester, etc.

  The polyglycerin fatty acid ester is a partial ester of a fatty acid having 6 to 22 carbon atoms and a polyglycerin having an average degree of polymerization of glycerin of 2 to 10, and specifically, diglycerin, triglycerin, tetra Glycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, etc., caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidin An ester with a saturated or unsaturated fatty acid such as acid, ricinoleic acid, linoleic acid, or linolenic acid, or a mixture thereof.

  For example, diglycerol monocaprylate, triglycerol monocaprylate, tetraglycerol monocaprylate, pentaglycerol monocaprylate, hexaglycerol monocaprylate, heptaglycerol monocaprylate, octaglycerol monocaprylate, nonaglycerol monocaprylate, Decaglycerol monocaprylate, tetraglycerol monolaurate, tetraglycerol monostearate, tetraglycerol monooleate, hexaglycerol monolaurate, hexaglycerol monostearate, hexaglycerol tristearate, hexaglycerol monooleate, deca Examples include glycerin monolaurate and decaglycerin monooleate.

  The polyoxyethylene fatty acid ester is a partial ester of a fatty acid having 6 to 22 carbon atoms and a polyoxyethylene having an average degree of polymerization of ethylene oxide of 2 to 10, and specifically has an average degree of polymerization. 2-10 polyoxyethylene and saturation of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, elaidic acid, ricinoleic acid, linoleic acid, linolenic acid, etc. Or an ester with an unsaturated fatty acid or mixture thereof.

Examples of sorbitan fatty acid esters include caproic acid sorbitan ester, caprylic acid sorbitan ester, capric acid sorbitan ester, lauric acid sorbitan ester, myristic acid sorbitan ester, palmitic acid sorbitan ester, stearic acid sorbitan ester, behenic acid sorbitan ester, oleic acid Examples include sorbitan ester, elaidic acid sorbitan ester, ricinoleic acid sorbitan ester, condensed ricinoleic acid sorbitan ester and / or 10 to 100 mol adducts thereof of ethylene oxide.

  Examples of the propylene glycol fatty acid ester include propylene glycol caproic acid ester, propylene glycol caprylic acid ester, propylene glycol capric acid ester, propylene glycol lauric acid ester, propylene glycol myristic acid ester, propylene glycol palmitic acid ester, propylene glycol stearic acid ester. Examples include acid esters, propylene glycol behenic acid esters, propylene glycol oleic acid esters, propylene glycol elaidic acid esters, propylene glycol ricinoleic acid esters, and propylene glycol condensed ricinoleic acid esters.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate ester salt, alkyl ether sulfate ester salt, alkane sulfonate salt, α-olefin sulfonate salt and the like. Examples of the alkyl benzene sulfonate include sodium alkyl benzene sulfonate, triethanol amine alkyl benzene sulfonate, diethanol amine alkyl benzene sulfonate, and the like. Examples of alkyl sulfate salts include sodium lauryl sulfate, lauryl sulfate triethanolamine, ammonium lauryl sulfate, potassium lauryl sulfate, lithium lauryl sulfate, and barium lauryl sulfate. Is preferred. Examples of the alkyl ether sulfate salt include polyoxyethylene alkyl ether sulfate sodium, polyoxyethylene alkyl ether sulfate triethanolamine, and polyoxyethylene alkyl ether sulfate ammonium. As the above anionic surfactants, alkyl sulfate salts, alkyl ether sulfate salts, alkane sulfones are particularly preferred from the viewpoints of washing performance in hard water, washing performance in combination with nonionic surfactants, and low foaming properties. Acid salts are preferably used.
These anionic surfactants may be used alone or in combination of two or more in combination with nonionic surfactants.

  The blending amount of the surfactant as the component (a) is 3 to 40% by mass (hereinafter referred to as%) with respect to the entire detergent composition for automatic dishwashing machine (hereinafter abbreviated as detergent composition). (Abbreviated). That is, when the blending amount is less than 3%, the desired cleaning performance is poor, and the cleaning agent is not compact and is disadvantageous in terms of cost. On the other hand, if it exceeds 40%, the balance as a whole becomes worse, and a synergistic effect with other components cannot be obtained any more. In particular, setting in the range of 5 to 15% is preferable in terms of cleaning performance and cost.

  The cleaning composition of the present invention comprises at least one of the nonionic surfactant and the anionic surfactant.

  Of the nonionic surfactants, the following combinations are particularly preferred from the viewpoint of cleaning performance, foam suppression, and prevention of oil reattachment to an object to be washed.

(1) A polyoxyethylene alkyl ether obtained by adding 2 to 12 moles of EO to a linear or branched alcohol having 8 to 18 carbon atoms and having an HLB in the range of 8 to 15, and a linear chain having 6 to 18 carbon atoms. Alternatively, 1 to 20 moles of EO and 1 to 20 moles of PO are added to the branched alcohol, and the polyoxyethylene polyoxypropylene alkyl ether having a weight ratio of EO / PO in the range of 0.5 to 5 is added to trimethylolpropane. Three kinds of combinations consisting of an ethylene oxide propylene oxide adduct of polyhydric alcohol added with 3 to 45 mol of EO and 15 to 120 mol of PO.

(2) A polyoxyethylene alkyl ether obtained by adding 2 to 12 moles of EO to a linear or branched alcohol having 8 to 18 carbon atoms in the HLB range of 8 to 15 and a linear chain having 6 to 18 carbon atoms. Alternatively, polyoxyethylene polyoxypropylene alkyl ether having 1 to 20 moles of EO and 1 to 20 moles of PO added to a branched alcohol and having a weight ratio of EO / PO in the range of 0.5 to 5; Polyoxyethylene polyoxypropylene alkyl ether in which 1 to 15 moles of EO and 1 to 50 moles of PO are added to 18 linear or branched alcohols, and the weight ratio of EO / PO is in the range of 0.05 to 1, A polyhydric alcohol ethylene oxide propylene oxide adduct obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane; Ranaru four kinds of combinations.

(3) A polyoxyethylene alkyl ether obtained by adding 2 to 12 moles of EO to a linear or branched alcohol having 8 to 18 carbon atoms in the HLB range of 8 to 15 and a linear chain having 6 to 18 carbon atoms. Alternatively, 1 to 20 moles of EO and 1 to 20 moles of PO are added to the branched alcohol, and the weight ratio of EO / PO is in the range of 0.5 to 5 and EO is added to glycerin. Three combinations consisting of ethylene oxide propylene oxide adduct of glycerin added with 3 to 45 mol and PO 15 to 120 mol.

(4) A polyoxyethylene alkyl ether obtained by adding 2 to 12 moles of EO to a linear or branched alcohol having 8 to 18 carbon atoms and having an HLB in the range of 8 to 15, and a linear chain having 6 to 18 carbon atoms. Alternatively, polyoxyethylene polyoxypropylene alkyl ether having 1 to 20 moles of EO and 1 to 20 moles of PO added to a branched alcohol and having a weight ratio of EO / PO in the range of 0.5 to 5; Polyoxyethylene polyoxypropylene alkyl ether in which 1 to 15 moles of EO and 1 to 50 moles of PO are added to 18 linear or branched alcohols, and the weight ratio of EO / PO is in the range of 0.05 to 1, 4 types of combinations consisting of glycerin added with 3 to 45 mol of EO and 15 to 120 mol of PO with glycerin ethylene oxide propylene oxide adduct Together.

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

(6) Polyoxyethylene poly having a weight ratio of EO / PO in the range of 2 to 5 by adding 1 to 20 mol of EO and 1 to 20 mol of PO to a linear or branched alcohol having 6 to 18 carbon atoms. 1-20 mol of EO and 1-20 mol of PO are added to oxypropylene alkyl ether and a linear or branched alcohol having 6-18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. Three kinds of combinations comprising polyoxyethylene polyoxypropylene alkyl ether and ethylene oxide propylene oxide adduct of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerin.

(7) Polyoxyethylene poly having a weight ratio of EO / PO in the range of 2 to 5 by adding 1 to 20 moles of EO and 1 to 20 moles of PO to a linear or branched alcohol having 6 to 18 carbon atoms. 1-20 mol of EO and 1-20 mol of PO are added to oxypropylene alkyl ether and linear or branched alcohol having 6-18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. 1 to 15 mol of EO and 1 to 50 mol of PO are added to a polyoxyethylene polyoxypropylene alkyl ether and a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.05 to A polyoxyethylene polyoxypropylene alkyl ether in the range of 0.5, and a polyvalent alkyl obtained by adding 3-45 mol of EO and 15-120 mol of PO to trimethylolpropane. Four combinations of ethylene oxide-propylene oxide adducts of Lumpur.

(8) Polyoxyethylene poly having a weight ratio of EO / PO in the range of 2 to 5 by adding 1 to 20 moles of EO and 1 to 20 moles of PO to a linear or branched alcohol having 6 to 18 carbon atoms. 1-20 mol of EO and 1-20 mol of PO are added to oxypropylene alkyl ether and linear or branched alcohol having 6-18 carbon atoms, and the weight ratio of EO / PO is in the range of 0.5-2. 1 to 15 mol of EO and 1 to 50 mol of PO are added to a polyoxyethylene polyoxypropylene alkyl ether and a linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.05 to Polyoxyethylene polyoxypropylene alkyl ether in the range of 0.5 and glycerin ethylene obtained by adding EO to 3-45 mol and PO15-120 mol to glycerin Four combinations of the key side propylene oxide adduct.

(9) Polyoxy in which 1 to 20 mol of EO and 1 to 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 to 2 1 to 15 mol of EO and 1 to 50 mol of PO are added to ethylene polyoxypropylene alkyl ether and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.05 to 0.5. Of polyoxyethylene polyoxypropylene alkyl ether in the range of 3 and 3 and an ethylene oxide propylene oxide adduct of polyhydric alcohol obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane .

(10) 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 0.5 to 2 1 to 15 mol of EO and 1 to 50 mol of PO are added to ethylene polyoxypropylene alkyl ether and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.05 to 0.5. Three combinations comprising polyoxyethylene polyoxypropylene alkyl ether in the range of glycerol and ethylene oxide propylene oxide adduct of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerin.

(11) Polyoxy in which 1 to 20 mol of EO and 1 to 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 to 2 Two combinations comprising ethylene polyoxypropylene alkyl ether and an ethylene oxide propylene oxide adduct of polyhydric alcohol obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane.

(12) A polyoxy compound 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 an EO / PO weight ratio in the range of 0.5 to 2 An ethylene polyoxypropylene alkyl ether 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, or an average molecular weight of 500 to 10, A reverse pluronic block polymer having a weight ratio of EO / PO in the range of 0.05 to 0.5 and a trimethylolpropane added with 3 to 45 moles of EO and 15 to 120 moles of PO. Three kinds of combinations consisting of an adduct of dihydric alcohol with ethylene oxide and propylene oxide.

(13) Polyoxy in which 1 to 20 mol of EO and 1 to 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 to 2 Ethylene polyoxypropylene alkyl ether 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, or an average molecular weight of 500 to 10, A reverse pluronic block polymer having a weight ratio of EO / PO in the range of 0.5 to 1 and a polyhydric alcohol in which 3 to 45 mol of EO and 15 to 120 mol of PO are added to trimethylolpropane 3 types of combinations of ethylene oxide and propylene oxide adducts.

(14) 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 a weight ratio of EO / PO in the range of 0.5 to 2 Ethylene polyoxypropylene alkyl ether, polymethyl alcohol ethylene oxide propylene oxide adduct obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane, and 3 to 45 mol of EO to glycerin and PO15 to Three kinds of combinations consisting of glycerin and ethylene oxide / propylene oxide adduct added with 120 mol.

(15) 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 a weight ratio of EO / PO in the range of 0.5 to 2 Ethylene polyoxypropylene alkyl ether, polymethyl alcohol ethylene oxide propylene oxide adduct obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane, sorbitan fatty acid ester, polyglycerin fatty acid ester, glycerin fatty acid Three kinds of combinations consisting of at least one selected from esters.

(16) 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 a weight ratio of EO / PO in the range of 0.5 to 2 1 to 15 mol of EO and 1 to 50 mol of PO are added to ethylene polyoxypropylene alkyl ether and linear or branched alcohol having 6 to 18 carbon atoms, and the weight ratio of EO / PO is 0.05 to 0.5. Two combinations of polyoxyethylene polyoxypropylene alkyl ethers in the range of

  In particular, the combination of the above (9), (10), (12), (14), (15) and (16) is particularly suitable from the viewpoint of foam suppression.

Among these, in the cleaning composition of the present invention, when the nonionic surfactant and the anionic surfactant are used in combination, the mixing ratio of the nonionic surfactant and the anionic surfactant is 99: by weight. A range of 1 to 9: 1 is preferable from the viewpoint of synergistic effect of the cleaning performance.
Further, in the cleaning composition of the present invention, when an anionic surfactant is blended, it is preferable to add an antifoaming agent from the viewpoint of foam suppression.

  The detergent composition of the present invention includes 2,4,7,9-tetramethyl-5-decyne-4,7-diol and polyoxyethylene acetylene as part of the surfactant (a). Renic glycol ether, or a derivative or isomer thereof may be used. The number of moles of polyoxyethylene added in polyoxyethylene acetylenic glycol ether is preferably 1 to 4, and from the viewpoint of balance with other components and improvement of foam suppression, polyoxyethylene (1. 3) Acetylenic glycol ether [the number of moles added in ()] is preferably used.

  In addition, as the polymer chelating agent as the component (b), acrylic acid polymer and salt thereof, maleic acid polymer and salt thereof, acrylic acid-maleic acid copolymer and salt thereof, poly-α-hydroxyacrylic Examples thereof include acids and salts thereof, acrylic acid-maleic acid-polyethylene glycol copolymers and salts thereof, olefin-maleic acid copolymers and salts thereof, and acrylic acid-sulfonic acid copolymers and salts thereof. Examples of these salts include sodium salts, potassium salts, ammonium salts, and ethanolamine salts. Of these, sodium salts and potassium salts are preferable. In particular, preferably from the viewpoint of sequestering ability, anti-redeposition property and cleaning performance, sodium polymaleate, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium poly-α-hydroxyacrylate An acrylic acid-maleic acid-polyethylene glycol copolymer, a sodium salt of an olefin-maleic acid copolymer, and a sodium salt of an acrylic acid-sulfonic acid copolymer are preferably used.

  These polymer chelating agents as component (b) are blended for the purpose of improving sequestering ability, threshold effect, water-insoluble substance dispersion performance, anti-redeposition property and cleaning performance. Or you may use it in combination of 2 or more types.

  The salt of the maleic acid polymer, acrylic acid polymer, and copolymer of maleic acid and acrylic acid can also be selected from commercially available products. For example, if sodium polymaleate, It can be appropriately prepared by adding sodium hydroxide (neutralization reaction). Therefore, when sodium hydroxide and potassium hydroxide are added, a mixture of sodium polymaleate and potassium polymaleate can be obtained at an arbitrary ratio.

  The average molecular weight of the maleic acid polymer, acrylic acid polymer and salts thereof is preferably 600 to 15,000, particularly preferably 1,000 to 15,000. The average molecular weight of the copolymer of maleic acid and acrylic acid and the salt thereof is preferably 1,000 to 100,000, particularly preferably 3,000 to 80,000. . The polymer and copolymer salts may be all neutralized salts or partially neutralized salts.

  The blending amount of the polymer chelating agent as the component (b) is set within a range of 0.2 to 10% with respect to the entire cleaning composition. That is, if the blending amount is less than 0.2%, the desired effect of preventing recontamination and the cleaning performance are poor, and if it exceeds 10%, the balance as a whole deteriorates and the storage stability decreases, and other components This is because no further synergistic effects can be obtained. In particular, setting in the range of 0.5 to 7% is possible in terms of sequestering ability, threshold effect, water-insoluble substance dispersion performance, recontamination prevention effect and cleaning performance in balance with other components. Is preferred.

Moreover, as said (c) component, the organic acid which consists of sulfate, bicarbonate, a citric acid, gluconic acid, malic acid, succinic acid, fumaric acid, tartaric acid, lactic acid, maleic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid Alternatively, at least one weakly acidic to weakly alkaline water-soluble electrolytic substance selected from water-soluble salts thereof can be used.
Specifically, sulfates such as sodium sulfate and potassium sulfate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, citric acid, gluconic acid, malic acid, succinic acid, fumaric acid, tartaric acid, lactic acid, maleic acid, ethylenediamine Examples of organic acids such as acetic acid and nitrilotriacetic acid, and water-soluble salts thereof include sodium salts, potassium salts, ammonium salts, magnesium salts, amine salts, and ethanolamine salts. These water-soluble salts may be anhydrous or hydrated salts.

  These weakly acidic to weakly alkaline water-soluble electrolytic substances may be used alone or in combination of two or more. Among these, a combination of a sulfate and a water-soluble salt of an organic acid, a combination of a sulfate and a bicarbonate, and a water-soluble salt of an organic acid is preferable from the viewpoint of a synergistic effect of cleaning performance.

  In particular, from the viewpoint of cleaning performance and solubility of the cleaning composition, in the weakly acidic to weakly alkaline water-soluble electrolyte (c), at least a part of the water-soluble salt of the organic acid is a sodium salt, It is preferable to select potassium salt, ammonium salt, magnesium salt, amine salt or ethanolamine salt.

  The blending amount of the weakly acidic to weakly alkaline water-soluble electrolytic substance as the component (c) is set in the range of 50 to 96.8% with respect to the entire cleaning composition. That is, when the blending amount is less than 50%, it is difficult to obtain sufficient cleaning performance from the balance with other components. On the other hand, when the blending amount exceeds 96.8%, the overall balance is deteriorated and the synergistic effect with other components is achieved. This is because no more can be obtained.

When a sulfate is selected as the weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c), the cleaning performance should be at least one selected from sodium sulfate, potassium sulfate, ammonium sulfate and magnesium sulfate. In particular, from the viewpoint of washing performance against protein stains, it is preferable to contain at least 3 to 30% of magnesium sulfate in terms of anhydride (MgSO ₄ ) in the entire cleaning composition. That is, when the blending amount is less than 3%, the cleaning performance against protein soil is poor, while when it exceeds 30%, the solubility and storage stability due to the consolidation of the cleaning composition are deteriorated, and further cleaning performance is reduced. This is because the above improvement cannot be obtained. Magnesium sulfate can be used by obtaining commercially available anhydrides or hydrates such as trihydrate, pentahydrate and heptahydrate.

  In addition, when a bicarbonate is selected as the weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c), it is 5 to 96 in the whole detergent composition from the viewpoint of washing performance against protein soil and emulsification stability. It is preferable to contain 8%. That is, when the blending amount is less than 5%, the cleaning performance is poor, while when it exceeds 96.8%, the balance as a whole is deteriorated, and further improvement of the cleaning performance and emulsion stability is not recognized. This is because a synergistic effect with other components cannot be obtained.

  Examples of the detergent enzyme as the component (d) include amylase, protease, lipase, cellulase, glucanase, and the like. Among them, amylase, protease, and lipase are preferably used from the viewpoint of washing performance and cost.

  These detergent enzymes may be used alone or in combination of two or more. And the compounding quantity of the said enzyme for detergents is set to the range of 0.1 to 7% in the whole cleaning composition. That is, when the blending amount is less than 0.1%, the improvement in cleaning performance is poor due to the balance with other components. On the other hand, when the blending amount exceeds 7%, a synergistic effect with other components cannot be obtained any more, and the cost is low. This is also disadvantageous. In addition, when the enzyme for detergent which is said (d) component is mix | blended, the compounding quantity of the weak acidic thru | or weak alkaline water-soluble electrolytic substance of the said (c) component is 100% of the whole cleaning composition as a balance. Thus, it is added in the range of 50 to 96.7%.

  The cleaning composition for an automatic dishwasher of the present invention includes, as optional components, a pH adjuster, a dye, a fragrance, a metal corrosion inhibitor, a bactericide, a deodorant, an antistatic agent, an antifoaming agent, and a solvent. Etc. can be used.

  Moreover, as embodiment of the cleaning composition for automatic dishwashers of this invention, it can manufacture suitably in powder form, a granular form, and a slurry form.

  And the detergent composition for automatic dishwashers of this invention is 0.05-0.4 according to the amount of food stain | pollution | contamination, such as starch stain | pollution | contamination, protein stain | pollution | contamination, and oil stains, and the stain | pollution | contamination which adhered to the to-be-washed object. Used in automatic dishwashers as a dilute aqueous solution of mass%.

  The liquid detergent composition for an automatic dishwasher according to the present invention is obtained using the above essential components and optional components, and includes a specific surfactant, a polymer chelating agent, a specific weakly acidic to weak component as a cleaning component. Since it contains an alkaline water-soluble electrolytic substance and a detergent enzyme, the pH of the 0.2% diluted aqueous solution (JIS-Z-8802: 1984 “pH measurement method”) is 25 ° C. It is set to 5.8 to 8.6, and has excellent environmental safety and work safety, and has achieved excellent cleaning performance and storage stability comparable to alkaline cleaners. Moreover, it has excellent finish after rinsing.

  Since the conventional cleaning composition is an alkaline cleaning composition mainly composed of an alkaline agent, it is a neutral cleaning composition mainly composed of a surfactant or the like. Even if it adheres to the skin, its irritation is much lower than conventional and easy to handle. Moreover, it is possible to accommodate in a thin plastic container or a bag such as a pouch without being limited to being accommodated in a conventional thick plastic container.

  Furthermore, in the conventional alkaline cleaning agent, it was necessary to neutralize the cleaning waste liquid with acid according to the wastewater treatment facility, etc., but in the cleaning composition for an automatic dishwasher of the present invention, Such neutralization work is not required. In addition, since it is a neutral detergent mainly composed of specific nonionic surfactants, it is not only the surface of glass tableware, aluminum tableware and cooking utensils, but also the surface of the tableware is gold or silver wire. It does not have an adverse effect on objects to be cleaned and has a pattern, and is excellent in finish after rinsing.

  Therefore, the cleaning composition for automatic dishwashers of the present invention is suitable for cleaning hard surfaces such as glass, ceramics, metals, plastics and the like. Moreover, it can be used not only for tableware but also as an automatic washing machine for washing instruments and containers in various manufacturing factories, processing factories, and plastic containers used for distribution. In addition, it can also be preferably used for cleaning hard surfaces such as tiles and floors in food factories and food processing factories, cleaning containers such as glass bottles and beer bottles for beverages, and cleaning metal surfaces. In particular, it is suitable for use in automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias and the like. In addition, it can be used effectively also in the washing | cleaning uses, such as the tableware by the conventional hand washing.

  Next, examples will be described together with comparative examples. The present invention is not limited to these.

  While preparing the detergent composition for automatic dishwashers of the composition shown in Examples 1 to 93 and Comparative Examples 1 to 8 in Table 1 to Table 21 below, measuring the pH, foam suppression, washing performance, Five items of influence on glass and ability to suppress scale formation were evaluated. In addition, the component and its pure part (%) which were used in Table 1-2 of the postscript are as follows, and the numerical value in a table | surface is shown as it is. The number of moles of ethylene oxide added to the surfactant is indicated by “P”, and the number of moles of propylene oxide added is indicated by “q”. Furthermore, the results of the above five items are also shown in Tables 1 to 21 below.

[Component A]
Nonionic surfactant 1;
Polyoxyethylene (P = 9) branched alkyl (C12-C14) ether HLB = 13 Cloud point = 55 ° C.
Product name: Neugen ET-135 (Daiichi Kogyo Seiyaku Co., Ltd.)

Nonionic surfactant 2;
Polyoxyethylene (P = 8) linear alkyl (C9-C11) ether HLB = 13.9 Cloud point = 80 ° C.
Product name: Neodoll 91-8T (manufactured by Shell Japan)

Nonionic surfactant 3;
Polyoxyethylene (P = 15) Polyoxypropylene (q = 4) Linear alkyl (C = 12-14) ether EO / PO weight ratio = 2.84 Cloud point = 73 ° C.
Product name: Neugen LP-180 (Daiichi Kogyo Seiyaku Co., Ltd.)

Nonionic surfactant 4;
Polyoxyethylene (P = 3) linear alkyl (C12, C13) ether HLB = 9.0
Product name: Neugen ET-97 (Daiichi Kogyo Seiyaku Co., Ltd.)

Nonionic surfactant 5;
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.67 Average molecular weight: 3,300
Product name: Epan 740 (Daiichi Kogyo Seiyaku Co., Ltd.)

Nonionic surfactant 6;
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
EO / PO weight ratio = 0.67 Average molecular weight: 2,800
Product name: Pluronic RPE 1740 (BASF)

Nonionic surfactant 7;
Polyoxyethylene (P = 9.2) Polyoxypropylene (q = 7.5) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 0.93 Cloud point = 44 ° C.
Product name: NTD-02 (Daiichi Kogyo Seiyaku Co., Ltd.)

Nonionic surfactant 8;
Polyoxyethylene (P = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14, 15) ether EO / PO weight ratio = 1.26
Prototype

Nonionic surfactant 9;
Polyoxyethylene (P = 8) Polyoxypropylene (q = 6) Linear alkyl (C = 12, 13) ether EO / PO weight ratio = 1.01 Cloud point = 31 ° C.
Product name: Pepol AS-054C (manufactured by Toho Chemical Industry Co., Ltd.)

Nonionic surfactant 10;
Polyoxyethylene (P = 4) polyoxypropylene (q = 38) linear alkyl (C16-C18) ether represented by the following general formula (1) EO / PO weight ratio = 0.08
Product Name: Adecanol LG-299 (Asahi Denka Kogyo Co., Ltd.)

Nonionic surfactant 11;
Polyoxyethylene polyoxypropylene block polymer (pluronic block polymer)
EO / PO weight ratio = 0.11 Average molecular weight = 2,000 Cloud point 24 ° C.
Product name: Pluronic PE6100 (manufactured by BASF)

Nonionic surfactant 12;
Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer)
Average molecular weight = 2,800 EO / PO weight ratio = 0.11
Product name: Pluronic RPE2510 (manufactured by BASF)

Nonionic surfactant 13;
Trimethylolpropane EO, PO adduct represented by the following chemical formula (2) Average molecular weight = 4,500 EO / PO weight ratio = 0.21
Prototype

Nonionic surfactant 14;
Glycerin EO, PO adduct represented by the following chemical formula (3)

Nonionic surfactant 15;
2,4,7,9-Tetramethyl-5-decyne-4,7-diol Product name: Surfynol 104 (manufactured by Nissin Chemical Industry Co., Ltd.)

Nonionic surfactant 16;
Polyoxyethylene (P = 1.3) acetylenic glycol ether Product name: Surfynol 420 (manufactured by Nissin Chemical Industry Co., Ltd.)

Nonionic surfactant 17;
Sorbitan fatty acid ester Product name: Poem C250 (Riken Vitamin Co., Ltd.)

Nonionic surfactant 18;
Polyglycerin fatty acid ester Product name: Sunsoft A-121E (manufactured by Taiyo Chemical Co., Ltd.)

Nonionic surfactant 19;
Glycerin fatty acid ester Product name: TP-1 (manufactured by Taiyo Chemical Co., Ltd.)

Anionic surfactant 1;
Sodium lauryl sulfate Product name: Monogen Y-100 (Daiichi Kogyo Seiyaku Co., Ltd.)

Anionic surfactant 2;
Sodium alkylbenzene sulfonate (Kao Corporation)

Anionic surfactant 3;
Sodium polyoxyethylene lauryl sulfate (pure content: 25%)
Product name: LES-73 (Daiichi Kogyo Seiyaku Co., Ltd.)

Anionic surfactant 4;
Sodium alkane sulfonate (sodium sulfonate of C14-17 secondary alcohol / pure content: 30%)
Product name: SAS30 (manufactured by Clariant Japan)

[B component]
Polymer chelating agent 1;
Sodium polymaleate average molecular weight = 1,800
Prototype

Polymer chelating agent 2;
Sodium polyacrylate average molecular weight = 15,000
Product name: Socaran PA-40P (BASF)

Polymer chelating agent 3;
Acrylic acid-maleic acid copolymer Average molecular weight = 70,000
Product name: Socaran CP-45G (BASF)

Polymer chelating agent 4;
Sodium poly-α-hydroxyacrylate average molecular weight = 12,000 (pure content 30%)
Product name: Pale Black 1200 (Nippon Peroxide)

Polymer chelating agent 5;
Acrylic acid-maleic acid-polyethylene glycol copolymer Average molecular weight = 8,000 (pure 50%)
Product name: PX1E-LK100 (manufactured by Nippon Shokubai Co., Ltd.)

Polymer chelating agent 6;
Sodium salt of olefin-maleic acid copolymer Average molecular weight = 12,000 (25% pure)
Product name: Socaran CP9 (BASF)

Polymer chelating agent 7;
Sodium salt of acrylic acid-sulfonic acid copolymer (acrylic acid, 2-hydroxy-3-allyloxypropanesulfonic acid sodium salt, pure 50%)
Product name: Aquaric GL246 (manufactured by Nippon Shokubai Co., Ltd.)

[Component c]
Sodium sulfate Product name: Neutral anhydrous sodium sulfate (Shikoku Kasei Co., Ltd.)

Potassium sulfate Product name: Potassium sulfate (Otsuka Chemical Co., Ltd.)

Magnesium sulfate anhydrous salt Product name: Magnesium sulfate MG0K (manufactured by Ako Kasei Co., Ltd.)

Magnesium sulfate trihydrate Product name: Magnesium sulfate MG3K (manufactured by Ako Kasei Co., Ltd.)

Magnesium sulfate pentahydrate Product name: Magnesium sulfate MG5K (manufactured by Ako Kasei)

Magnesium sulfate heptahydrate Product name: Purified magnesium sulfate (Ako Kasei Co., Ltd.)

Ammonium sulfate Product name: Ammonium sulfate (manufactured by Nissan Chemical Industries)

Sodium bicarbonate Product name: Sodium bicarbonate (Tokuyama)

Sodium citrate Product name: Trisodium citrate (manufactured by Iwata Chemical Industries)

Citric acid Product name: Purified citric acid (manufactured by Fuso Chemical Industries)

Sodium gluconate Product name: Sodium gluconate (Fujisawa Pharmaceutical Co., Ltd.)

Monosodium succinate Product name: Monosodium succinate (manufactured by Fuso Chemical Industries)

Sodium malate Product name: Sodium malate (manufactured by Fuso Chemical Industries)

Ethylenediaminetetraacetic acid trisodium product name: Kirest 2CS (manufactured by Chubu Kirest Co., Ltd.)

Nitrilotriacetic acid disodium product name: Nitrilotriacetate disodium (manufactured by Nacalai Tesque, reagent)

[D component]
amylase:
Product name: Termamyl 60TNT (Novozyme)

Protease 1:
Product name: Everase 8.0T (Novozyme)

Protease 2:
Product name: Alcalase 3.0T (Novozyme)

Lipase:
Product name: Lipolase (Novozyme)

The test method and evaluation method for each item are as shown below.
[PH measurement]
Measurement method 0.20% dilution prepared with ion-exchanged water of the cleaning composition prepared in accordance with JIS Z-8802: 1984 using a pH meter (pH METER F-12, manufactured by HORIBA, Ltd.) The pH value of the liquid at 25 ° C. was measured.
A: 5.6 or more and 8.6 or less X: Less than 5.6 or more than 8.6

[Foam suppression]
Test method: The prepared detergent composition is diluted to 0.20% with tap water, 50 ml is poured into a colorimetric tube with a capacity of 100 ml, stoppered, and kept at 45 ° C. for 1 hour. Was kept at 45 ° C. The height of the foam immediately after the colorimetric tube was shaken 30 times up and down at a rate of 3 reciprocations per second was determined and determined according to the following criteria.
Evaluation criteria A: Bubble height is less than 6 mm B: Bubble height is 6 mm or more and less than 11 mm Δ: Bubble height is 11 mm or more and less than 16 mm ×: Bubble height is 16 mm or more

[Cleaning performance]
Test Method The prepared cleaning composition was put into a commercial automatic dishwasher (DW-DR61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. And the ceramic dish which is the following to-be-cleaned object was wash | cleaned as 10 sheets 1 set, and the washing | cleaning performance was evaluated by the evaluation criteria of a postscript. Three types of dirt, beef tallow dirt, curry dirt, and egg yolk dirt, were prepared, and each of the dirts was evaluated for cleaning.
* Operating conditions Cleaning temperature: 45 ° C
Rinsing temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 30 seconds, rinsing: 8 seconds)
Tap water hardness: (as CaCO ₃ ) 70-80 ppm
Beef tallow dirt: Refined beef tallow was used.
Curry stain: A commercially available retort curry (trade name: Bon Curry: manufactured by Otsuka Foods Co., Ltd.) was used.
Egg stain: Egg yolk of chicken egg was used.
Object to be cleaned: A ceramic dish having a diameter of 10 cm was attached to the standard soil so as to be 4 g / sheet and dried at room temperature for 1 hour. Only the egg soil was washed after being immersed at 40 ° C. for 30 minutes immediately before washing.
・ Evaluation criteria ◎: Dirt removal of 90% or more ○: Dilution of 70% or more and less than 90% △: Dilution of 50% or more and less than 70% ×: Dilution of less than 50%

[Influence on glass surface]
Test Method A commercially available 8 ounce tumbler glass (manufactured by HOYA) was immersed in the prepared cleaning composition under the following conditions. And the state of the tumbler glass after immersion was observed visually, and the following evaluation criteria evaluated.
* Soaking conditions Detergent concentration: 0.20%
Immersion temperature: 60 ° C
Immersion time: 2 weeks / Evaluation criteria A: No discoloration or corrosion is observed on the surface of the tumbler glass.
○: The tumbler glass surface is slightly discolored.
Δ: Large discoloration on the surface of the tumbler glass.
X: Corrosion on the surface of the tumbler glass is large.

[Scale generation suppression performance]
Test method: Using artificial hard water (total hardness: 250 mg / L), the detergent composition was diluted to 0.20%, 50 ml was poured into a colorimetric tube with a capacity of 100 ml, and kept at 60 ° C. for 4 hours. The amount of scale produced was visually determined according to the following criteria.
Evaluation criteria A: No scale was generated.
○: There was almost no scale generation.
Δ: Scale was generated.
X: Scale adhesion was remarkable.

Claims (10)

The following components (a) to (c) are contained, and the pH of the 0.2% diluted aqueous solution (JIS-Z-8802: 1984 “pH measurement method”) is 25 ° C. and 5.8 to 8. A cleaning composition for an automatic dishwasher, characterized in that it is set to 6.
(A) 3-40 mass% of surfactant.
(B) Polymer chelating agent 0.2-10 mass%.
(C) Selected from an organic acid consisting of sulfate, bicarbonate, citric acid, gluconic acid, malic acid, succinic acid, fumaric acid, tartaric acid, lactic acid, maleic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, or a water-soluble salt thereof. 50 to 96.8% by mass of at least one weakly acidic to weakly alkaline water-soluble electrolytic substance.   The detergent composition for an automatic dishwasher according to claim 1, wherein the surfactant of the component (a) is at least one of a nonionic surfactant and / or an anionic surfactant.   The nonionic surfactant which is the surfactant of the component (a) is polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, polyhydric alcohol ethylene oxide Propylene oxide adduct, glycerin ethylene oxide propylene oxide adduct, glycerin fatty acid ester, sucrose fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, and propylene glycol fatty acid ester The cleaning composition for automatic dishwashers according to claim 1 or 2.   The polymer chelating agent of the component (b) is an acrylic acid polymer and a salt thereof, a maleic acid polymer and a salt thereof, an acrylic acid-maleic acid copolymer and a salt thereof, poly-α-hydroxyacrylic acid and a salt thereof An acrylic acid-maleic acid-polyethylene glycol copolymer and a salt thereof; an olefin-maleic acid copolymer and a salt thereof; and an acrylic acid-sulfonic acid copolymer and a salt thereof. The cleaning composition for automatic dishwashers as described in any one of 1-3.   In the weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c), at least a part of the water-soluble salt of the organic acid is a sodium salt, potassium salt, ammonium salt, magnesium salt, amine salt, ethanolamine salt. The cleaning composition for automatic dishwashers as described in any one of Claims 1-4 characterized by these.   The sulfate which is a weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c) is at least one selected from sodium sulfate, potassium sulfate, ammonium sulfate and magnesium sulfate. The cleaning composition for automatic dishwashers as described in any one of these. The sulfate which is a weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c) contains at least 3 to 30% by mass of magnesium sulfate in terms of anhydride (MgSO ₄ ). The cleaning composition for automatic dishwashers as described in any one of 6.   The bicarbonate which is a weakly acidic or weakly alkaline water-soluble electrolytic substance of the component (c) is contained in an amount of 5 to 96.8% by mass in the whole cleaning composition. The cleaning composition for automatic dishwashers as described in any one of these.   Furthermore, (d) 0.1-7 mass% of enzymes for detergents are contained, The cleaning composition for automatic dishwashers as described in any one of Claims 1-8 characterized by the above-mentioned.   The cleaning composition for an automatic dishwasher according to any one of claims 1 to 9 is used in an automatic dishwasher as a 0.05 to 0.4 mass% diluted aqueous solution. How to wash things.