JP2007009024A - Detergent composition for automatic dishwasher - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for automatic dishwashers which has excellent detergency, inhibits formation of scales, has low corrosion properties on articles to be washed, is safe and environmentally friendly, and particularly exhibits excellent performance in automatic dishwashers. <P>SOLUTION: The detergent composition for automatic dishwashers comprises a silicate as component (A), 0.0125-10,000 pts.mass, based on 100 pts.mass component (A), copolymer of an olefin monomer and an unsaturated carboxylic acid monomer and/or its salt as component (B), and 0.0125-10,000 pts.mass, based on 100 pts.mass-component (A), polymer mainly having an unsaturated carboxylic acid monomer as component (C). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a cleaning composition for an automatic dishwasher having excellent cleaning performance and being safe and environmentally friendly.

  Conventionally, in cleaning compositions for automatic dishwashers, silicates have been blended as builders for suppressing the corrosion and deterioration of tableware. As these silicates, amorphous silicates, crystalline silicates and aluminosilicates are widely used, which are important from the viewpoint of their multi-functionality (alkali source, ion exchange capacity, corrosion resistance, buffer capacity, etc.) and cost. Become a builder.

  However, the use of these silicates in automatic dishwashers causes significant scale deposition problems. For this reason, for example, Patent Document 1 contains an alkali agent (A), an organophosphorus chelating agent (B), and (C) a water-soluble polymer dispersing agent (C), and (A) / (B) weight ratio. Characterized in that (A) / (B) = 1/1 to 10/1 and (B) / (C) weight ratio is (B) / (C) = 1/1 to 10/1. A cleaning composition for a cleaning machine (Claim 1); containing an alkali agent (A), an organophosphorus chelating agent (B), a polymer water-soluble dispersant (C) and water (D). Content of alkaline agent (A) is 5 to 50% by weight, (A) / (B) weight ratio is (A) / (B) = 1/1 to 10/1, (B) / (C) weight ratio (B) / (C) = 1/1 to 10/1, Aqueous liquid detergent composition for dishwashers (Claim 2); Alkaline agent (A), organophosphorus chelate Agent (B) and (C) the polymer water-soluble dispersant (C), the content of the alkali agent (A) is 40 to 90% by weight, and the weight ratio (A) / (B) is (A ) / (B) = 1/1 to 10/1, (B) / (C) weight ratio is (B) / (C) = 1/1 to 10/1, for dishwasher The solid or powder detergent composition of claim 3 (Claim 3); the alkali agent (A) is one or more selected from alkali metal hydroxides, alkali metal silicates and alkali metal carbonates. Any one composition according to claim 1 to 3 (claim 4) is disclosed.

  Reference Document 2 contains at least one selected from a maleic acid homopolymer having an average molecular weight of 1000 to 3000 or a water-soluble salt of these polymers in a strong alkaline detergent containing an alkali agent and a sequestering agent. A detergent composition for a washing machine (Claim 1), wherein the alkali agent is at least one selected from alkali metal hydroxides, alkali metal carbonates, and alkali metal silicates. The detergent composition for a washing machine according to claim 1 (Claim 2); the sequestering agent is ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), nitrilotriacetic acid (NTA), citric acid, malic acid, gluconic acid Or at least one selected from tripolyphosphoric acid, pyrophosphoric acid, ethanediphosphonic acid or a salt thereof. Washer detergent composition of the mounting (claim 3) is disclosed.

JP, 10-226800, A Claims JP, 2002-363596, A Claims

However, with the composition as disclosed in the above patent document, the problem of scale adhesion could not be completely solved.
In addition, in recent years, neutral to weakly alkaline detergents that are environmentally friendly and safe have been developed. Magnesium and calcium contents in water such as magnesium silicate and calcium silicate found in conventional alkaline detergents and detergents There is a problem that not a scale derived from the silicic acid content in the inside but a scale due to a decrease in solubility of the silicic acid itself occurs. Such a scale cannot be solved by a composition as disclosed in the above patent document.

  Therefore, the object of the present invention is to have excellent cleaning power, suppress generation of scale, low corrosiveness to an object to be cleaned, safe and environmentally friendly, and particularly excellent in a commercial automatic dishwasher. The present invention provides a cleaning composition for an automatic dishwasher that exhibits performance.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, the present invention has been completed.
That is, this invention contains the following (A)-(C) component, the ratio of (B) component is 0.0125-10000 mass part with respect to 100 mass parts of (A) component, (C ) The component ratio is 0.0125 to 10000 parts by mass, which relates to a cleaning composition for an automatic dishwasher:
(A) silicate;
(B) a copolymer of an olefin monomer and an unsaturated carboxylic acid monomer and / or a salt thereof; (C) a polymer mainly containing an unsaturated carboxylic acid monomer and / or a salt thereof.

  Moreover, the cleaning composition for automatic dishwashers of this invention is characterized by the mass average molecular weight of (B) component being 1000-20000, and the mass average molecular weight of (C) component being 500-20000.

  Furthermore, the cleaning composition for an automatic dishwasher of the present invention includes, as optional components, 0.1 to 20% by mass of a nonionic surfactant, 0.1 to 20% by mass of enzyme, and 0.1 to 80% by mass. Hydroxycarboxylic acid, 0.1 to 90% by weight sulfate, 0.5 to 50% by weight pH adjuster, 1 to 80% by weight chelating agent, 5 to 80% by weight inorganic neutral salt and 1 to It is characterized by containing one or more components selected from the group consisting of 80% by mass of an alkali agent.

  The cleaning composition for an automatic dishwasher of the present invention is selected from the group consisting of organic solvents, cationic surfactants, bleaches, bleach activators, fragrances, dyes, dispersants, anticorrosives, and water. 1 type or 2 or more types of other arbitrary components are contained, It is characterized by the above-mentioned.

  Furthermore, the cleaning composition for an automatic dishwasher of the present invention is characterized by containing 1 to 30% by mass of polyalkylene glycol.

  Moreover, the detergent composition for automatic dishwashers of this invention has the pH of the 0.01-0.5 mass% concentration aqueous solution of the detergent composition for automatic dishwashers in the range of 6.0-11.0. It is characterized by being.

  According to the present invention, it is possible to provide a safe and environmentally friendly cleaning composition for an automatic dishwashing machine that has excellent cleaning power, suppresses the generation of scale, and is low corrosive to an object to be cleaned. In particular, there is an effect that it is possible to provide a cleaning composition for an automatic dishwasher that exhibits excellent performance in a commercial automatic dishwasher.

The cleaning composition for an automatic dishwasher of the present invention comprises the following components (A) to (C) as essential components:
First, the component (A) will be described. The component (A) of the present invention is a silicate. Examples of the silicate of component (A) include alkali metal silicates, specifically, sodium orthosilicate, sodium metasilicate, No. 1 sodium silicate, No. 2 sodium silicate, No. 3 silica. Examples include crystalline sodium silicate or amorphous sodium silicate such as sodium silicate, potassium orthosilicate, potassium metasilicate, or layered sodium silicate, and sodium metasilicate, layered sodium silicate and No. 2 sodium silicate is preferred.

  (A) The compounding quantity of a component exists in the range of 0.1-80 weight%, Preferably it exists in the range of 5-50 mass%, Most preferably, it exists in the range of 10-40 mass%. . When the content of the component (A) is less than the above amount, the detergency may be insufficient. When the amount exceeds the above amount, it is not preferable from the viewpoint of economic efficiency and a blend balance with other components. In addition, the silicate of (A) component can also use 1 type (s) or 2 or more types together.

  Next, the component (B) will be described. Component (B) of the present invention is a copolymer of an olefin monomer and an unsaturated carboxylic acid monomer and / or a salt thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, ethanolamine salts, and the like, and sodium salts and potassium salts are preferable.

  Although the olefin monomer which comprises (B) component is not specifically limited, Preferably an amylene, an isoamylene, a hexylene, a heptylene, an octene etc. can be illustrated, Among these, the effect of this invention is efficient. Isoamylene is most preferable from the viewpoint of exhibiting the above.

  The unsaturated carboxylic acid monomer constituting the component (B) is also not particularly limited, and any unsaturated carboxylic acid compound that can be polymerized with an olefin monomer may be used. Monobasic acid or dibasic acid, for example, acrylic acid, methacrylic acid, isocrotonic acid, transcrotonic acid, vinylacetic acid, 2-methylcrotonic acid, 3,3-dimethylacrylic acid, maleic acid, fumaric acid, taikon Acid, methyl fumaric acid, propylene dicarboxylic acid, glutaconic acid, methyl maleic acid and the like can be exemplified, and among these, acrylic acid, methacrylic acid, maleic acid are preferred from the viewpoint of efficiently producing the effects of the present invention. Fumaric acid and the like, with maleic acid being particularly preferred.

  In addition, the polymerization method of an olefin monomer and an unsaturated carboxylic acid monomer is not limited at all, and any conventionally known method can be adopted, and two bases as an unsaturated carboxylic acid monomer can be used. It is also possible to polymerize the acid as an acid anhydride. Here, the ratio of the olefin monomer and the unsaturated carboxylic acid monomer in the copolymer of the olefin monomer and the unsaturated carboxylic acid monomer of the component (B) and the salt thereof is not particularly limited. From the viewpoint of efficiently exhibiting the effects of the present invention, the molar ratio is preferably 1: 3 to 3: 1, more preferably 1: 2 to 2: 1, most preferably 2: 3 to 3: 2. It is.

  In addition, the weight average molecular weight of the copolymer of the olefin monomer and unsaturated carboxylic acid monomer of component (B) and the salt thereof is in the range of 1000 to 2000, preferably 5000 to 2000, from the viewpoint of silicic acid scale prevention. Within the range of 16000.

  (B) The usage-amount of a component is in the range of 0.0125-10000 mass parts with respect to 100 mass parts of (A) component, The inside of the range of 0.125-5000 mass parts is more preferable, 0.625 More preferably within the range of ˜3000 parts by mass. If it is in this range, the scale preventing ability is sufficiently exhibited, and excellent cleaning performance is obtained.

  The content of component (B) is in the range of 0.01 to 10% by mass, preferably in the range of 0.1 to 5% by mass, and most preferably in the range of 0.5 to 3% by mass. It is. If the amount is less than the above amount, the ability to prevent scale may be insufficient. If the amount exceeds the above amount, it is not preferable because of economic efficiency and foaming property. As the component (B), an olefin monomer, particularly a copolymer with an unsaturated carboxylic acid monomer and / or a salt thereof may be used alone or in combination of two or more.

  Next, the component (C) will be described. The component (C) of the present invention is a polymer mainly composed of an unsaturated carboxylic acid monomer and / or a salt thereof. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, ethanolamine salts, and the like, and sodium salts and potassium salts are preferable.

  The unsaturated carboxylic acid monomer constituting the component (C) is not particularly limited, and any unsaturated carboxylic acid compound capable of homopolymerization can be used. However, it may be a dibasic acid, for example, acrylic acid, methacrylic acid, isocrotonic acid, transcrotonic acid, vinylacetic acid, 2-methylcrotonic acid, 3,3-dimethylacrylic acid, maleic acid, fumaric acid, itaconic acid, thymelfumaric acid , Propylene dicarboxylic acid, glutaconic acid, methylmaleic acid, etc., among these, acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like are preferable from the viewpoint of efficiently exhibiting the effects of the present invention. In particular, acrylic acid and maleic acid are preferable.

  Component (C) is a polymer mainly composed of an unsaturated carboxylic acid monomer and / or a salt thereof, and is composed of a polymer consisting only of an unsaturated carboxylic acid monomer, a salt thereof, or an unsaturated carboxylic acid monomer homopolymer. A polymer or a salt thereof is preferable, but a small amount of an olefin monomer may be copolymerized as long as it is a polymer or a salt thereof mainly composed of an unsaturated carboxylic acid monomer. The molar ratio is preferably 20% or less, more preferably 10% or less.

  In addition, the mass average molecular weight of the component (C) is preferably in the range of 500 to 20000, more preferably in the range of 1500 to 8000 from the viewpoint of scale prevention ability.

  (C) The usage-amount of a component is in the range of 0.0125-10000 mass parts with respect to 100 mass parts of (A) component, the inside of the range of 0.0625-3000 mass parts is preferable, 0.125- A range of 1000 parts by mass is more preferable. If it is in this range, the scale preventing ability is sufficiently exhibited, and excellent cleaning performance is obtained.

  The content of component (C) is in the range of 0.01 to 10% by mass, preferably in the range of 0.05 to 3% by mass, and most preferably in the range of 0.1 to 1% by mass. It is. If the amount is less than the above amount, the ability to prevent scale may be insufficient, and if the amount exceeds the above amount, it is not preferable because of economical efficiency and a blend balance with other components. The polymer mainly containing an unsaturated carboxylic acid monomer (C) and / or a salt thereof may be used alone or in combination of two or more.

  Moreover, in the cleaning composition for automatic dishwashers of the present invention, the blending ratio (mass ratio) of the component (B) and the component (C) is preferably 50: 1 to 2: 1 from the viewpoint of scale prevention. : 1 to 5: 1 is more preferable.

  The cleaning composition for an automatic dishwashing machine of the present invention can be blended with any component as desired. For example, as a preferable optional blending component, a nonionic surfactant, an enzyme, a hydroxycarboxylate, a sulfate, One or more components selected from the group consisting of a pH adjuster, a chelating agent, an inorganic neutral salt, and an alkali agent can be used.

  As the nonionic surfactant, generally known nonionic surfactants can be used. For example, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyalkylene dialkyl ether, polyoxyethylene alkenyl ether, polyoxyalkylene alkyl phenyl ether, pluronic block polymer, tetronic block polymer, reverse pluronic type Block polymer, reverse tetronic block polymer, sucrose fatty acid ester, sorbitan fatty acid ester, polyethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polypropylene glycol fatty acid ester, fatty acid ester, coconut fatty acid diethanolamide (1: 1), palm fatty acid diethanol De (1: 2), lauric acid diethanolamide, oleic acid diethanolamide, fatty acid alkanolamides such as palm kernel fatty acid diethanolamide, alkyl glucosides, amine oxides, and the like. These nonionic surfactants may be used alone or in combination of two or more.

Among the nonionic surfactants, polyoxyethylene polyoxypropylene alkyl ether is particularly preferable, and the general formula (1)
PO- (EO) _m (PO) _n- R '(1)
(In the formula, R represents a linear or branched alkyl group having an average carbon number of 11 to 16, R ′ represents a hydrogen atom or a methyl group, EO represents an addition unit of ethylene oxide, and PO represents an addition unit of propylene oxide. , M is 2.0 to 11.0, n is 0.4 to 9.5, and EO / PO additional unit m / n = 0.8 to 5.0). preferable.

  When mix | blending a nonionic surfactant, 0.125-20000 mass parts is preferable with respect to 100 mass parts of (A) component, 0.625-10000 mass parts is more preferable, 1.25-5000 is used. Part by mass is most preferred. Within this range, excellent cleaning performance can be obtained.

  Moreover, the compounding quantity to the cleaning composition for automatic dishwashers of nonionic surfactant is in the range of 0.1-20 mass%, Preferably it exists in the range of 0.5-10 mass%. The most preferable range is 1.0 to 5.0% by mass. If the blending amount of the nonionic surfactant is less than the above amount, the blending effect is not exhibited, and it is not preferable. If the blending amount exceeds the above amount, it is not preferable from the viewpoint of balance of blending components and economy.

  Next, the enzyme will be described. As examples of the enzyme, known enzymes such as amylase, protease, lipase, phospholipase, cellulase and pullulanase can be used alone or as a mixture. Among these enzymes, amylase and protease are particularly preferable, and it is preferable to use both in combination, considering that the components of dish soil are starch and protein. One or two or more enzymes may be used in combination.

  When using an enzyme, the use ratio is preferably 0.125 to 20000 parts by mass, more preferably 0.625 to 10000 parts by mass, and most preferably 1.25 to 5000 parts by mass with respect to the component (A). . Within this range, enzyme activity is sufficient, rinsing properties are good, and excellent cleaning performance is obtained.

  Moreover, the compounding quantity to the detergent composition for automatic dishwashers of an enzyme exists in the range of 0.1-20 mass%, Preferably it exists in the range of 0.5-10 mass%, Most preferably It is in the range of 1.0 to 5.0% by mass. If the amount of the enzyme is less than the above amount, it is not preferable because the effect of the mixture does not appear. On the other hand, if the amount exceeds the above amount, the economical efficiency and the rinsing property are deteriorated.

  Next, the hydroxycarboxylate will be described. Examples of the hydroxycarboxylate include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, ethanolamine salts, and the like, and sodium salts and potassium salts are preferable. Preferred examples include sodium gluconate, sodium citrate, sodium tartrate, sodium malate, sodium lactate, sodium hydroxyacetate, sodium glycerate, sodium heptinate, etc., which improve the corrosiveness to metals, particularly iron. From the viewpoint, sodium citrate, sodium tartrate, sodium heptonate and sodium gluconate are preferable, and sodium gluconate is particularly preferable. Hydroxycarboxylate may be used alone or in combination of two or more.

  When mix | blending hydroxycarboxylate, 0.125-80000 mass parts is preferable with respect to 100 mass parts of (A) component, its 6.25-40000 mass part is more preferable, and its use ratio is 12.5-. Most preferred is 30000 parts by mass. If it is in this range, anticorrosion is sufficient, and excellent cleaning performance can be obtained.

  Moreover, the compounding quantity to the detergent composition for automatic dishwashers of a hydroxycarboxylate salt exists in the range of 0.1-80 mass%, Preferably it exists in the range of 5-40 mass%, Most preferably Is in the range of 10 to 30% by mass. If the amount of the hydroxycarboxylic acid salt is less than the above amount, it is not preferable because the compounding effect does not appear, and if it exceeds the above amount, it is not preferable from the viewpoint of economic efficiency and the balance with other components.

  Next, sulfate will be described. Examples of sulfates include alkali metal salts, alkaline earth metal salts, ammonium salts, and the like, for example, sodium sulfate (bow glass), potassium sulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, and anhydrides thereof. In particular, anhydrous sodium sulfate is preferred. One or two or more sulfates can be used in combination.

  When the sulfate is blended, the use ratio is preferably 0.125 to 90000 parts by mass, more preferably 6.25 to 70000 parts by mass, and 12.5 to 40000 parts by mass with respect to 100 parts by mass of the component (A). Part is most preferred. Within this range, excellent cleaning performance can be obtained.

  The compounding quantity of the sulfate to the cleaning composition for automatic dishwashers is in the range of 0.1 to 90% by mass, preferably in the range of 5 to 80% by mass, and most preferably 10 to 70%. It is in the range of mass%. When the blending amount of the sulfate is less than the above amount, the blending effect is not manifested, and this is not preferable, and when it exceeds the above amount, it is not preferable from the viewpoint of economy and blending balance with other components.

  Next, the pH adjuster will be described. The pH adjuster is used for adjusting the pH of the cleaning liquid, and particularly preferably used for neutralizing the alkali by adding and adjusting the pH. Examples of pH adjusters include inorganic acids and organic acids, and specific examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and the like. Citric acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, tartaric acid, gluconic acid, aspartic acid, formic acid, acetic acid, lactic acid and the like. Of these, fumaric acid and citric acid are particularly preferable. In addition, the pH adjuster may be used alone or in combination of two or more.

  When the pH adjuster is blended, the use ratio may be an amount that can adjust the pH, but 0.125 to 50000 parts by mass is preferable with respect to 100 parts by mass of component (A), and 0.625 to 30000. Mass parts are more preferable, and 1.25 to 10,000 parts by mass are most preferable.

  The blending amount of the pH adjuster to the detergent composition for an automatic dishwasher may be an amount capable of adjusting the pH, and is in the range of 0.1 to 50% by mass, more preferably 0.5 to 30. It is in the range of mass%, most preferably in the range of 1-10 mass%.

  Examples of the chelating agent include aminopolyacetic acid and salts thereof, various phosphates, phosphonic acid or phosphonocarboxylic acid and salts thereof, organic acid salts, polycarboxylic acids and salts thereof, amino acids and salts thereof, and the like.

  Examples of the aminopolyacetic acid and salts thereof include nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, triethylenetetraminehexaacetic acid, bis (2-hydroxyphenyl). Acetic acid) Aminopolyacetic acid such as ethylenediamine, diencoric acid, iminodiacetic acid, hydroxyethyliminodiacetic acid and salts thereof, and alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof.

  In addition, as the various phosphates, orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, hexametaphosphoric acid and alkali metal salts thereof are used. Examples of the alkali metal combined with these include sodium and potassium.

  Further, the phosphonic acid or phosphonocarboxylic acid and its salt include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane. Phosphonic acid compounds such as hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminotrimethylenephosphonic acid, or alkali metal salts thereof, Phosphonocarboxylic acids such as alkaline earth metal salts, ammonium salts or alkanolamine salts, 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid Compounds, or alkali metal salts, alkaline earth metal salts, ammonium salts or Luke Nord amine salt, and the like.

  The organic acid salt includes maleic acid, fumaric acid, diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, carboxymethyltartaric acid, and other alkali metal salts, alkaline earth metal salts, ammonium salts, or alkanols. In addition to amine salts or sulfates such as sodium sulfate and potassium sulfate, amino acids such as aspartic acid and glutamic acid, or alkali metal salts, alkaline earth metal salts, ammonium salts or alkanolamine salts thereof can be used.

  Examples of the polycarboxylic acids and salts thereof include polyacrylic acid, polyitaconic acid, polymaleic acid, acrylic acid-maleic acid copolymer, anhydride other than the essential components (B) and (C) Examples thereof include maleic acid-styrene copolymers, maleic anhydride-ethylene copolymers, maleic anhydride-vinyl acetate copolymers, maleic anhydride-acrylic acid ester copolymers, and alkali metal salts thereof.

  Among these chelating agents, ethylenediaminetetraacetic acid tetrasodium, sodium citrate, nitrilotriacetic acid (sodium) and the like are preferably used from the viewpoint of washing performance and ion sequestration performance. In addition, these chelating agents may be used independently or may be used in combination of 2 or more type.

  The proportion of the chelating agent used is preferably 1.5 to 80000 parts by mass, more preferably 6.25 to 50000 parts by mass, and further 10 to 30000 parts by mass with respect to 100 parts by mass of the component (A). preferable. Within this range, excellent ion sequestering performance and cleaning performance can be obtained.

  The compounding amount of the chelating agent in the detergent composition for an automatic dishwasher is in the range of 1 to 80% by mass, preferably in the range of 5 to 50% by mass, and most preferably 10 to 30% by mass. Is within the range. If the blending amount of the chelating agent is less than the above amount, it is not preferable because the blending effect does not appear, and if it exceeds the above amount, it is not preferable in terms of balance with other cleaning components and economical efficiency.

Next, examples of the inorganic neutral salt include sodium chloride, potassium chloride, ammonium chloride, calcium chloride, magnesium chloride and the like.
The use ratio in the case of blending the inorganic neutral salt is more preferably 6.25 to 80000 parts by mass and 10 to 50000 parts by mass, and further preferably 15 to 40000 parts by mass with respect to 100 parts by mass of the component (A). . If it is in this range, sufficient electrolytic mass can be obtained.

  The blending amount of the inorganic neutral salt in the detergent composition for an automatic dishwasher is in the range of 5 to 80% by mass, preferably in the range of 10 to 50% by mass, and most preferably 15 to It is in the range of 30% by mass. If the blending amount of the inorganic neutral salt is less than the above amount, the blending effect is not exhibited, and this is not preferable. If the blending amount exceeds the above amount, it is not preferable in terms of balance with other cleaning components and economical efficiency.

  Next, examples of the alkali agent include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, and the like. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and alkali metal hydroxides. Examples of the alkali metal carbonate include sodium carbonate and potassium carbonate, alkali metal carbonates, Examples of the alkali metal hydrogen carbonate include alkali metal hydrogen carbonates such as sodium hydrogen carbonate (sodium bicarbonate) and potassium hydrogen carbonate, and sodium carbonate and sodium hydrogen carbonate are particularly preferable from the viewpoint of safety.

  The use ratio in the case of blending the alkali agent is preferably 1.5 to 80000 parts by mass, 6.25 to 50000 parts by mass, and more preferably 10 to 30000 parts by mass with respect to 100 parts by mass of the component (A). . Within this range, excellent detergency can be obtained.

  The blending amount of the alkaline agent in the detergent composition for an automatic dishwasher is in the range of 1 to 80% by mass, preferably in the range of 5 to 60% by mass, and most preferably 15 to 50% by mass. %. If the blending amount of the inorganic neutral salt is less than the above amount, the blending effect is not exhibited, and this is not preferable. If the blending amount exceeds the above amount, it is not preferable in terms of balance with other cleaning components and economical efficiency.

  In addition, although the compound described in the said arbitrary component has the compound described in duplicate in each component, when using such a compound, it is used together as a component which has each function. Therefore, the preferred amount to be used should be considered from each viewpoint.

  Furthermore, in addition to the above components (A) to (C) and optional components, the detergent composition for an automatic dishwasher of the present invention includes an organic solvent, a cationic surfactant, a bleach, A bleaching activator, a fragrance, a pigment, a dispersing agent such as a polymer carboxylic acid, an anticorrosive, water and the like can be blended within a range not impairing the effects of the present invention.

  The cleaning composition for an automatic dishwashing machine of the present invention can be used as a solid block cleaning agent (tablet form) that is a safe and convenient cleaning form without scattering of powder and particles. In order to obtain a shape, a polyalkylene glycol that is solid at room temperature (25 ° C.) can be blended as an optional component. Examples of usable polyalkylene glycols include polyethylene glycol, preferably having a mass average molecular weight of 1000 or more, more preferably 1000 to 6000, normal temperature (25 ° C.), preferably 40 to 65 ° C. A solid is preferred.

  When mix | blending this polyalkylene glycol, 1.25-30000 mass parts is preferable with respect to 100 mass parts of (A) component, and 3.75-10000 mass parts is more preferable. If it exists in this range, it can be set as a solid block shape with favorable solubility.

  The compounding quantity of the polyalkylene glycol to the cleaning composition for automatic dishwashers is 1 to 30% by mass, preferably 3 to 10% by mass. If the blending amount of the polyalkylene glycol is less than the above amount, it is difficult to solidify into a solid block. On the other hand, if the amount exceeds the above amount, the solubility of the cleaning composition for an automatic dishwasher is deteriorated. Absent.

  The cleaning composition for an automatic dishwashing machine of the present invention may be a product in a solid state (solid block cleaning agent) in which the blending components are solidified with the above polyalkylene glycol, or may be solidified by other conventionally known methods. It may be a solid block cleaning agent. Of course, it may be a product in the form of powder as it is. Moreover, it is good also as a liquid product by melt | dissolving in arbitrary quantity of water and / or an organic solvent. When an enzyme is blended, the solid state is most preferable from the viewpoint of enzyme stability, and powder is the next most preferable.

  The detergent composition for an automatic dishwasher of the present invention having the above-described configuration is intended for use in an automatic dishwasher, but the form thereof is not particularly limited, Thus, it may be liquid or solid (powder or tablet form may be used), but in any case, it becomes an aqueous solution when washing dishes. In addition, the compounding quantity (mass%) of the various components in this specification is based on the cleaning composition for automatic dishwashers which does not contain water.

  Here, when the detergent composition for an automatic dishwasher of the present invention becomes an aqueous solution, that is, the cleaning liquid at the time of cleaning is neutral to weakly alkaline, that is, the pH is 6.0 to 11.0. Is more preferable, and 6.0 to 8.0 is more preferable. In the present invention, the “cleaning liquid at the time of cleaning” is obtained by dissolving the cleaning composition for an automatic dishwasher of the present invention in water, and is 0.01 to 0.5% by mass, more preferably 0.03 to 0.00. This refers to an aqueous solution having a concentration of 3% by mass. Moreover, it is preferable that the operating temperature at the time of washing | cleaning is 40-80 degreeC, and 50-70 degreeC is more preferable.

  The cleaning composition for an automatic dishwasher of the present invention has an excellent cleaning power, and generation of scale is also suppressed. Further, since it is used under mild conditions from neutral to weak alkali, it can be said that it is very excellent in terms of safety and environmental load.

  In addition, it is low corrosive to objects to be washed (glass, tableware, etc.) such as ceramics, glasses, wooden products, plastic products, metal (iron, copper, silver, aluminum, stainless steel, etc.) products or automatic dishwashers themselves. In particular, it is excellent that it is low corrosive to irons (iron and iron-containing alloys).

  Also, when used as a solid block cleaning agent, it does not swell or crack over time, and further, the active ingredient such as enzyme, bleaching component, chelating agent does not deactivate and the cleaning agent dissolves. The required amount of cleaning agent can be sufficiently supplied even when the supply water temperature and the supply water pressure are low.

  The cleaning composition for an automatic dishwashing machine of the present invention is used in an automatic dishwashing machine such as a domestic automatic dishwashing machine or a commercial automatic dishwashing machine. In a commercial automatic dishwasher with many restrictions on operating conditions, it shows better cleaning performance. For example, the cleaning composition for an automatic dishwasher of the present invention exhibits excellent cleaning performance even when the cleaning time is 5 minutes or less, and shorter is 1 minute or less, and the cleaning temperature is always in the range of 45 to 70 ° C. But it shows excellent cleaning performance.

  The cleaning composition for an automatic dishwasher of the present invention exhibits excellent cleaning performance against all kinds of dirt such as fat, protein, starch, etc., made of metal such as aluminum, stainless steel, silver, melamine, plastic It exhibits excellent cleaning performance for tableware made of any material such as glass, porcelain, lacquerware, ceramics, etc., and it is low corrosive and can suppress generation of scale derived from silicate.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.
First, the evaluation method used in the examples will be described. In order to confirm the effect of the detergent composition for an automatic dishwasher of the present invention, a cleaning power test, a glass whitening suppression ability test, and a scale adhesion prevention ability test were performed. Further, the pH of the cleaning solution was measured and evaluated.
(1) Detergency test <Cleaning conditions>
Washing machine used: Automatic dishwasher made by HOBART (model AM-14)
Washing temperature: 66 ° C
Cleaning time: 40 seconds Rinsing temperature: 82 ° C
Rinse time: 9 seconds Detergent concentration: 0.1%
Water used: Water with a hardness of 10 ° DH (adjusted with calcium chloride)
<Adjustment of items to be washed>
5 g of rice starch is dissolved in 20 g of hot water and gelatinized at 80 ° C. for 5 minutes. After adding 20 g of beef tallow dissolved therein, stirring well and cooling to 50 ° C., 10 g of egg yolk added and stirred uniformly is used for dirt. The composite stain was uniformly applied to a 150 mm × 150 mm melamine resin plate using a coating rod and dried at room temperature to obtain a plate for washing test.
<Detergency evaluation method>
Five cleaning test plates were placed at predetermined positions on the cleaning rack, washed / rinsed under the above-described cleaning conditions, and then dried at room temperature. The surface of this plate was fractionated on a 5 mm × 5 mm grid, the clean grids were counted, and the ratio (%) of the clean grids relative to the whole was taken as the cleaning rate, and evaluated according to the following evaluation criteria.
◎: Cleaning rate of 80% or more ○: Cleaning rate of 60% or more and less than 80% Δ: Cleaning rate of 40% or more and less than 60% ×: Cleaning rate of less than 40%

(2) Glass whitening suppression ability test <Test method>
After the crystal glass was fully racked in the cleaning rack and the washing, rinsing and interval steps were repeated 100 cycles, the degree of whitening of the crystal glass was visually determined according to the following criteria.
<Evaluation method>
◎: not whitened ○: slightly whitened △: whitened ×: markedly whitened

(3) Silica scale adhesion prevention test <Test method>
The glass was fully racked in the washing rack, and the washing, rinsing, and interval steps were repeated 200 cycles, and then the scale generation in the washing machine was visually determined based on the following criteria. <Evaluation method>
◎: No scale adhesion ○: Little scale adhesion △: Scale adhesion x: Scale adhesion was remarkable

Examples 1-9, Comparative Examples 1-6
The cleaning composition was adjusted to the formulation described in Table 1, and each test was performed. The results are shown in Table 1. Table 2 shows a comparative example.

In the table,
Copolymer (1): Isoamylene-maleic acid (1: 1) copolymer, weight average molecular weight 6000
Copolymer (2): Isoamylene-maleic acid (1: 1) copolymer, weight average molecular weight 1 5000
Polymer acid (1): acrylic acid homopolymer, weight average molecular weight 5000
Polymer acid (2): maleic acid homopolymer, weight average molecular weight 3000
Nonionic surfactant (1): R—O— (EO) _m (PO) _n —H (R is an alkyl group having 12 to 14 carbon atoms, average added mole number m is about 8, and n is about 5) Polyoxyethylene polyoxypropylene alkyl ether used The pH data is obtained when the concentration of the detergent composition aqueous solution for an automatic dishwasher is 0.1% by mass.

  The cleaning composition for an automatic dishwasher according to the present invention is used for an automatic dishwasher such as a home automatic dishwasher or a commercial automatic dishwasher, and is made of metal such as aluminum, stainless steel, silver, melamine You can wash dishes made of any material such as glass, plastic, glass, porcelain, lacquerware, and ceramics.

Claims (6)

The following (A)-(C) component is contained, The ratio of (B) component is 0.0125-10000 mass part with respect to 100 mass parts of (A) component, and the ratio of (C) component is 0. A cleaning composition for an automatic dishwasher, characterized in that it is 0125 to 10,000 parts by mass:
(A) silicate;
(B) a copolymer of an olefin monomer and an unsaturated carboxylic acid monomer and / or a salt thereof;
(C) A polymer mainly composed of an unsaturated carboxylic acid monomer and / or a salt thereof.   The cleaning composition for an automatic dishwasher according to claim 1, wherein the component (B) has a mass average molecular weight of 1,000 to 20,000, and the component (C) has a mass average molecular weight of 500 to 20,000.   As optional components, 0.1-20% by weight nonionic surfactant, 0.1-20% by weight enzyme, 0.1-80% by weight hydroxycarboxylic acid, 0.1-90% by weight sulfate, 1 type selected from the group which consists of 0.5-50 mass% pH adjuster, 1-80 mass% chelating agent, 5-80 mass% inorganic neutral salt, and 1-80 mass% alkali agent, or The cleaning composition for automatic dishwashers according to claim 1 or 2, comprising two or more components.   Furthermore, it contains one or more other optional components selected from the group consisting of organic solvents, cationic surfactants, bleaches, bleach activators, fragrances, dyes, dispersants, anticorrosives and water. The cleaning composition for an automatic dishwasher according to any one of claims 1 to 3.   The cleaning composition for an automatic dishwasher according to any one of claims 1 to 4, further comprising 1 to 30% by mass of polyalkylene glycol.   The automatic of any one of Claims 1 thru | or 5 whose pH of the 0.01-0.5 mass% concentration aqueous solution of the cleaning composition for automatic dishwashers exists in the range of 6.0-11.0. A detergent composition for dishwashers.