JP2012214537A - Washing agent composition for automatic dish washer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a washing agent composition for automatic dish washers, which is excellent in a stain readhesion-preventing property, and can solve the problem of smell, after the washing is finished with an automatic dish washer.SOLUTION: The washing agent composition for the automatic dish washers includes (a) an ester of a 8-22C fatty acid and a polyhydric alcohol, (b) a copolymer of a 3-6C unsaturated carboxylic acid or its anhydride and a 2-12C olefin, and (c) a specific acrylic acid-maleic acid copolymer or its salt, wherein the mass ratio of (a)/[(b)+(c)] is 0.080-1.0; and the total content of (a), (b) and (c) is 0.8-11 mass%.

Description

  The present invention relates to a cleaning composition for an automatic dishwasher.

  The technique of the detergent composition for automatic dishwashers containing the ester type surfactant of a polyhydric alcohol and a fatty acid is disclosed in Patent Document 1. In addition, this publication describes that an olefin-maleic acid copolymer is used in combination. Patent Document 2 and Patent Document 3 disclose a technique for a dishwasher detergent containing an olefin-maleic acid copolymer.

JP 2005-154716 A Japanese translation of PCT publication No. 2004-518018 Special table 2008-513557 gazette

  In recent years, automatic dishwashers have rapidly spread, and washing machines that reduce the amount of washing water used from the viewpoint of energy saving and resource saving and increase the amount of tableware to be washed at one time have become mainstream. is occupying. However, when washing dishes with a large amount of dirt in such a washing machine, although the dirt can be removed at the end of washing, the odor derived from food remains remarkably, and an unpleasant odor remains in the washing machine cabinet. The problem of odor has become more prominent. Therefore, there is a strong demand to solve the problem of odor after washing at the time of washing dishes using an automatic dishwasher. In addition, in dishwashing using an automatic dishwasher, it is also desirable to have excellent anti-reattachment properties that prevent dirt, particularly oily dirt, from reattaching to tableware.

  Therefore, the subject of this invention is providing the cleaning composition for automatic dishwashers which is excellent in the anti-reattachment property of dirt, and can solve the problem of the smell after completion | finish of washing | cleaning using an automatic dishwasher.

  The present invention includes (a) an ester of a fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol (hereinafter referred to as (a) component), (b) an unsaturated carboxylic acid having 3 to 6 carbon atoms or an anhydride thereof and carbon. Copolymer with olefins of 2 to 12 (hereinafter referred to as component (b)), (c) Acrylic acid / maleic acid molar ratio of 0.6 to 9, and weight average molecular weight of 1,000 to 100,000 Acrylic acid-maleic acid copolymer or salt thereof (hereinafter referred to as component (c)), and the mass ratio of (a) / [(b) + (c)] is 0.080 to 1.0. The present invention also relates to a cleaning composition for an automatic dishwasher, wherein the total content of (a), (b), and (c) is 0.8 to 11% by mass.

  In the present invention, the detergent composition for an automatic dishwasher means a detergent composition used in an automatic dishwasher, and the composition of the present invention is a washing for washing dishes by an automatic dishwasher. Agent composition.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for automatic dishwashers which is excellent in the reattachment prevention property of dirt, such as oil stains, and solves the problem of the smell after completion | finish of washing | cleaning using an automatic dishwasher is provided.

<(A) component>
The cleaning composition for an automatic dishwasher of the present invention contains a fatty acid having 8 to 22 carbon atoms and an ester of a polyhydric alcohol as the component (a). The component (a) is preferably a polyhydric alcohol, particularly an ester of a polyhydric alcohol having 3 to 6 hydroxy groups in the molecule and a fatty acid having 8 to 22 carbon atoms. Examples of the polyhydric alcohol include glycerin, pentaerythritol, sucrose, sorbitol, sorbide, sorbitan, and polyglycerin having an average added mole number of 2 to 10. Moreover, as a C8-C22 fatty acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lauric acid, palm oil composition fatty acid, and beef tallow fatty acid are specifically mentioned. Can be mentioned.

  Since the polyhydric alcohol has a plurality of hydroxy groups, the ester compound with the fatty acid is a mixture of a plurality of compounds having different degrees of esterification such as a monoester, a diester and a triester. In the present invention, a mixture containing a large amount of a monoester is suitable. Specifically, the fatty acid is 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol per mol of the hydroxy group of the alcohol. Preference is given to mixtures obtained by esterification in molar proportions.

  Specific compounds include mono- or di-fatty acid esters or tri-fatty acid esters of glycerin and mixtures thereof, mono- or di-fatty acid esters or tri-fatty acid esters or tetra-fatty acid esters of pentaerythritol and mixtures thereof, sucrose Mono-fatty acid ester or di-fatty acid ester or tri-fatty acid ester of a polyhydric alcohol selected from sorbitol, sorbide and sorbitan, and mixtures thereof. Particularly, sorbitan and fatty acid ester are effective in reducing odor after completion of washing. To preferred.

  In the present invention, when using an ester of sorbitan and a fatty acid, a sorbitan fatty acid ester having 8 to 22 carbon atoms in the fatty acid is most preferable. Such a compound is obtained by an esterification reaction of sorbitol and / or sorbitan and a fatty acid, and as the raw material sorbitol, a commercially available product obtained by high-pressure hydrogen reduction of glucose can be used. Further, sorbitan obtained by dehydration cyclization of sorbitol may be used. From the influence on quality such as color deterioration and odor, it is preferable to use sorbitol, for example, 70% sorbitol, which is commercially available. The starting fatty acid for the esterification reaction is a saturated or unsaturated linear fatty acid having 8 to 22, preferably 12 to 20, more preferably 14 to 18, more preferably 16 to 18 carbon atoms, or a main component thereof. The mixed fatty acid can be preferably used. In the present invention, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, palm oil composition fatty acid, beef tallow fatty acid, stearic acid, oleic acid, linoleic acid, palm oil from the viewpoint of the effect of reducing odor after completion of washing Composition fatty acids and beef tallow fatty acids are preferred, oleic acid, linoleic acid, palm oil composition fatty acids and beef tallow fatty acids are more preferred, and oleic acid is particularly preferred.

  Sorbitol and sorbitan have a plurality of hydroxy groups. For this reason, monoesters, diesters, triesters, and the like are mixed in a compound esterified with a fatty acid. Furthermore, when starting from sorbitol, a ring is formed during the esterification reaction to form 1,4-sorbitan fatty acid ester and 1,5-sorbitan fatty acid ester. Besides these, sorbide fatty acid ester And sorbitol fatty acid esters are also produced, and thus are obtained as a mixture of various compounds. Therefore, sorbitan fatty acid esters traded for industrial use often refer to the above mixture. Therefore, the sorbitan fatty acid ester as the component (a) of the present invention may be a mixture containing various ester compounds formed using sorbitol as a starting material in addition to a single compound of sorbitan fatty acid ester.

  The sorbitan fatty acid ester as the component (a) of the present invention preferably has a fatty acid / sorbitol molar ratio of 0.10 to 2.0, more preferably 0.50 to 1.5. Preferably, 0.90 to 1.1 are more preferable.

  The detergent composition for an automatic dishwasher of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 2% by mass of the component (a) from the viewpoint of odor reduction effect after completion of cleaning. More preferably, the content is 0.3 to 1% by mass.

<(B) component>
The component (b) of the present invention is a copolymer of an unsaturated carboxylic acid having 3 to 6 carbon atoms or an anhydride thereof and an olefin having 2 to 12 carbon atoms. Examples of the unsaturated carboxylic acid having 3 to 6 carbon atoms or anhydride thereof include maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, crotonic acid and citraconic acid. Further, as the olefin having 2 to 12 carbon atoms, ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene are preferable. Among these, a copolymer of maleic acid and / or maleic anhydride and diisobutylene is particularly preferable.

  In addition, the copolymerization ratio of the component (b) is a molar ratio of an unsaturated carboxylic acid having 3 to 6 carbon atoms or an anhydride thereof / an olefin having 2 to 12 carbon atoms, 0.1 to 10, and further 0.2 to 5 and more preferably 0.3 to 3. In addition, the proportion of the unsaturated carboxylic acid having 3 to 6 carbon atoms or its anhydride and the olefin having 2 to 12 carbon atoms in the constituent monomer of component (b) is 90 to 100 mol%, and further 95 to 100 mol. %, Even more preferably 98 to 100 mol%, and the component (b) is substantially a copolymer comprising an unsaturated carboxylic acid having 3 to 6 carbon atoms or an anhydride thereof and an olefin having 2 to 12 carbon atoms, or a salt thereof. Is preferred.

  The component (b) preferably has a weight average molecular weight of 5,000 to 50,000, more preferably 5,000 to 30,000. The weight average molecular weight of component (b) is determined by gel permeation chromatography using a mixed solution of acetonitrile and 0.1 M sodium chloride aqueous solution (mixing ratio of acetonitrile and sodium chloride aqueous solution is 30:70 by volume) as a developing solvent. Polyethylene glycol can be determined as a standard substance.

  The detergent composition for an automatic dishwasher according to the present invention is preferably 0.05 to 10% by mass, more preferably 0.5 to 5% by mass of the component (b) from the viewpoint of the odor reduction effect after completion of cleaning. More preferably, the content is 1 to 2% by mass.

<(C) component>
The component (c) of the present invention is a specific acrylic acid-maleic acid copolymer or a salt thereof, and has a monomer constituent unit derived from acrylic acid and a monomer constituent unit of maleic acid. The monomer structural unit derived from maleic acid may be derived from maleic anhydride. As the component (c), acrylic acid-maleic acid copolymer or a salt thereof is used because it is excellent in oil stain detergency and re-contamination prevention property. As the salt, a sodium salt, potassium salt, alkanolamine salt, or ammonium salt can be used. The salt of the copolymer may be either one using a salt-type compound as a monomer, neutralized after copolymerization, or a combination of both. Component (c) is preferably a salt of the copolymer.

  Component (c) has an acrylic acid / maleic acid molar ratio of 0.6 to 9, preferably 1 to 4, and more preferably 1.5 to 4. In addition, the molar ratio of acrylic acid / maleic acid in the component (c) can be determined by detecting a pyrolyzate of the copolymer by pyrolysis gas chromatography (PGC). The proportion of acrylic acid and maleic acid in the constituent monomer of component (c) is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, and still more preferably 98 to 100 mol%. The component is preferably a copolymer of acrylic acid and maleic acid or a salt thereof.

  The component (c) has a weight average molecular weight of 1,000 to 100,000, 10,000 to 90,000, and more preferably 50,000 to 80,000. It is preferable because of its excellent point. The weight average molecular weight of the component (c) is a mixture of phosphoric acid-containing water and acetonitrile (the phosphoric acid content is 0.1% by mass, and the mixing ratio of water and acetonitrile is 90:10 by volume). Can be obtained as a standard substance by gel permeation chromatography.

  The detergent composition for an automatic dishwasher of the present invention is preferably 0.05 to 10% by mass, more preferably 0.5 to 5% by mass of the component (c), from the viewpoint of the effect of reducing odor after completion of cleaning. More preferably, the content is 0.5 to 2% by mass.

<Cleaning composition for automatic dishwasher>
In the cleaning composition for an automatic dishwashing machine of the present invention, the mass ratio of (a) / [(b) + (c)] is 0 from the viewpoints of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. 0.080 to 1.0, preferably 0.11 to 1.0, and more preferably 0.20 to 0.30.

  Moreover, in the detergent composition for automatic dishwashers of this invention, from a viewpoint of the reattachment prevention property of a stain | pollution | contamination, and the smell reduction effect after completion | finish of washing | cleaning, (a) component, (b) component, and (c) component Total content is 0.8-11 mass%, Preferably it is 1-10 mass%, More preferably, it is 2-6 mass%, More preferably, it is 2-4 mass%.

  By combining (a) component, (b) component and (c) component of the present invention in such a content and mass ratio, the total content of (a) component, (b) component and (c) component is If it is in the above range, not only exhibits excellent cleaning power against oil stains, but also prevents re-attachment of removed oil stains and reduces the odor in the cabinet after washing is completed. A liquid detergent composition can be obtained.

  In the cleaning composition for an automatic dishwashing machine of the present invention, the mass ratio of (a) / (c) is preferably 0.00 from the viewpoint of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. It is 20-2.6, More preferably, it is 0.25-2.5, More preferably, it is 0.45-0.55.

  In the detergent composition for an automatic dishwasher of the present invention, the pH at 25 ° C. of a 1% by weight aqueous solution is 3 to 12, preferably 4 to 10, in addition to the components (a), (b) and (c). More preferably, 5 to 10 solid water-soluble organic compounds [excluding (b), (c) and the later-described (e) component, hereinafter referred to as component (d1)] and water-soluble inorganic salts [hereinafter referred to as (d2) A compound selected from the [component]] (hereinafter referred to as the component (d)). Moreover, alkali agents, such as an alkali metal carbonate, an inorganic peroxide, an enzyme, etc. can be contained.

  The component (d1) is a water-soluble organic acid having a molecular weight of 40 to 400, preferably 90 to 360, more preferably 100 to 300, particularly two or more in the molecule, from the viewpoint of the effect of reducing odor after completion of washing. Is preferably a polyvalent carboxylic acid having 2 to 6 carboxylic acid groups or a salt thereof. Specifically, a carboxylic acid selected from formic acid, acetic acid, gluconic acid, malic acid, tartaric acid, lactic acid, citric acid, succinic acid, maleic acid and fumaric acid and salts thereof are preferred, and citric acid is particularly preferred. The salt is preferably a sodium salt or a potassium salt.

  As the component (d2), sulfates, chlorides, and phosphates are preferable from the viewpoint of the effect of reducing odor after completion of washing, and salts that can have crystal water are particularly preferable. Specifically, sodium sulfate, potassium sulfate, and sodium tripolyphosphate are preferable.

  The cleaning composition for an automatic dishwasher of the present invention preferably contains 20 to 80% by mass, further 30 to 60% by mass, and further 40 to 50% by mass of the component (d).

The cleaning composition for an automatic dishwasher of the present invention is a polyalkylene glycol represented by the following formula (e1) as the component (e) [hereinafter referred to as (e1)] It is preferable to contain a compound selected from the group consisting of a compound of the following formula (e2) (hereinafter referred to as the component (e2)).
H—O— (R ¹ O) _n —H (e1)
[Wherein, R ¹ represents an ethylene group or a propylene group. n shows the average addition mole number of an ethyleneoxy group or a propyleneoxy group, n is 10-1000, Preferably it is the number of 20-100. ]
R ² -O - _{^{[(R 3 O) l / (}} R 4 O) m ] -H (e2)
[Wherein, R ² is a hydrogen atom or a hydrocarbon group having 8 to 22 carbon atoms, preferably a hydrogen atom, R ³ is an ethylene group, and R ⁴ is a propylene group. Here, the symbol / indicates that the ethyleneoxy group and the propyleneoxy group may be a block or may be bonded at random. l and m represent the average number of moles of ethyleneoxy group and propyleneoxy group, l is a number of 5 to 100, preferably 5 to 50, and m is a number of 5 to 100, preferably 5 to 50. Is the number of ]

In the formula (e1), n is from 10 to 1000, preferably from 20 to 100, and more preferably from 30 to 70, from the viewpoint of the effect of reducing odor after washing. In formula (e1), R ¹ is preferably a propylene group from the viewpoint of the effect of reducing odor after the completion of washing.

In formula (e2), R ² is preferably a hydrogen atom from the viewpoint of the effect of reducing odor after completion of washing. Preferable components (e2) include pluronic block polymers and reverse pluronic block polymers.

  From the viewpoint of the effect of reducing odor after washing, the component (e) is preferably the component (e1), and particularly preferably polypropylene glycol.

  The cleaning composition for an automatic dishwashing machine of the present invention preferably contains 0.01 to 5% by mass, further 0.1 to 4% by mass, and further 0.4 to 3% by mass of the component (e). .

  In the detergent composition for an automatic dishwasher of the present invention, the component (a) is 0.1 to 20% by mass, preferably 0.2 to 4% by mass, more preferably 0.6 to 2% by mass in the particles. It is preferable to contain contained particles [hereinafter referred to as particles (I)]. This mass% is in the particles (I).

  The particles (I) preferably contain a component (d). The content of the component (d) in the particles (I) is preferably 10 to 99% by mass, more preferably 50 to 97% by mass, and most preferably 70 to 95% by mass.

  In the particle (I) of the present invention, the component (d1) and the component (d2) may be used together, and the mass ratio of the component (d1) / (d2) is preferably 0.11 to 9.0, More preferred is 0.43 to 4.0, and particularly preferred is 0.60 to 1.0.

  In the present invention, after mixing the component (a) with the component (d1) and / or the component (d2), the mixture (hereinafter referred to as the mixture (X)) and an inorganic powder are used for the purpose of improving particle properties. It is preferable to mix [hereinafter referred to as powder (Y)]. The powder (Y) preferably has a primary particle diameter of 5 nm to 200 μm, more preferably 20 nm to 100 μm, and particularly preferably 20 nm to 50 μm. Specifically, amorphous silicate, crystalline silicate, aluminosilicate, silica and One or more selected from alumina is preferable, crystalline silicate and silica are more preferable, and silica is still more preferable. In the present invention, the mass ratio (X) / (Y) of the mixture (X) and the powder (Y) is preferably 9.0 to 1000, more preferably 11 to 200, and particularly preferably 15 to 100. .

  When silica is used as the powder (Y), amorphous silica is preferable. Specifically, Aerosil (manufactured by Nippon Aerosil Co., Ltd.), Tocsil, Fine Seal, Leorosil (manufactured by Tokuyama Co., Ltd.), Silo Pure (Fuji Silysia Co., Ltd.) or the like is preferably used.

  In the present invention, a known mixer such as Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), high speed mixer (manufactured by Fukae Kogyo Co., Ltd.), Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.), or the like can be used for the mixing step. In particular, it is preferable to use a Nauter mixer that does not require much shearing force during stirring.

  In the particles (I) of the present invention, the component (a) is 0.1 to 20% by mass, preferably 0.2 to 5% by mass, more preferably 0.8 to 2% by mass, and the component (d) is converted to anhydrous. 10 to 99% by mass, preferably 50 to 99% by mass, particularly preferably 85 to 95% by mass, and powder (Y) 0.1 to 10% by mass, preferably 1 to 7% by mass, particularly preferably 3 In the particles (I), the content of water is preferably 0.05 to 15% by mass, more preferably 0.1 to 12% by mass, and particularly preferably 0.1 to 6% by mass. 3 to 10% by mass.

  Particle (I) can contain component (b) and / or component (c), but component (b) is blended with particle (I), and component (c) is blended with particle (I). First, it is preferable to mix in the composition as particles different from the particles (I). Therefore, the particles (I) preferably contain the component (b). A plurality of particles (I) having different compositions may be used.

  The average particle diameter of the particles (I) is preferably 50 to 1000 μm, more preferably 100 to 800 μm, and particularly preferably 100 to 600 μm.

  The particle (I) may be a particle having the component (a) attached to the particle surface of the component (d), and the particles (Y) attached to the surface are more fluid. Ideal for richness. Depending on the type and concentration of the component (d1) and component (d2), the component (a) may be added and then aggregated to form aggregated particles including the component (a). Furthermore, the surface of the aggregated particles may be covered with powder (Y).

  The particles (I) are used so that the content of the component (a) in the composition is in the above range. Of all the components (a) in the composition, 80% by mass or more, more preferably 90% by mass or more, and particularly substantially 100% by mass are preferably present in the particles (I).

  Moreover, it is preferable to mix | blend alkali agents, such as an alkali carbonate metal salt, from a viewpoint of oil-stain detergency. In this case, from the viewpoint of the storage stability of the cleaning composition of the present invention, it is preferable to blend as particles different from the particles (I), that is, particles (II).

  Moreover, it is preferable to mix | blend an enzyme and / or a bleaching agent from a viewpoint of oil-stain washing | cleaning property. About an enzyme, a bleaching agent, etc., it is suitable to mix | blend as particle | grains different from particle | grains (I) from a viewpoint of stability and handleability of an enzyme or a bleaching agent itself.

  Moreover, it is preferable to mix | blend a silicate or an aluminosilicate separately from the powder (Y) of particle | grains (I) from a viewpoint of oil dirt cleaning property. In this case, it is preferable to blend as separate particles from the viewpoint of handleability.

  The cleaning composition for an automatic dishwasher of the present invention preferably contains particles other than the particles (I). Specifically, particles other than the particles (I) include particles (II) containing an alkali metal carbonate and / or alkali metal hydroxide, particles containing an aluminosilicate and / or silicate (III ), One or more particles selected from particles (IV) containing inorganic peroxides and particles (V) containing enzymes, preferably all of particles (II) to (V) It is preferable to do. Moreover, you may contain arbitrary particles other than these particles.

  The component contained in the particles (II) is an alkali metal carbonate and / or an alkali metal hydroxide from the viewpoint of oil detergency, preferably sodium carbonate, potassium carbonate, sodium hydroxide, or potassium hydroxide. Sodium carbonate and potassium carbonate are more preferable, and sodium carbonate is particularly preferable. The particles (II) may be substantially composed of an alkali metal carbonate and / or an alkali metal hydroxide. Here, that the particle is substantially composed of a component means that the content of the component in the particle is 90% by mass or more.

  The average particle diameter of the particles (II) is preferably 50 to 600 μm, more preferably 100 to 500 μm, and it is preferable to use sodium carbonate having an average particle diameter in this range. The content of the particles (II) in the composition is preferably 1 to 80% by mass, more preferably 5 to 50% by mass, and particularly preferably 10 to 30% by mass. Preferably, the particles (II) are used so that the content of alkali metal carbonate and / or alkali metal in the composition is 10 to 30% by mass, and further 15 to 25% by mass.

  The particles (III) are particles containing aluminosilicate and / or silicate. The particles (III) may be substantially composed of aluminosilicate and / or silicate.

The particles (III) are particles used for the purpose of improving the cleaning effect, and are used for purposes that are clearly different from the powder (Y) of the particles (I). Silicates are amorphous sodium silicates such as No. 1-3 sodium silicate, JP-A-7-89712, JP-A-60-227895 and Phys. Chem. Glasses. 7, p127-p138 (1966), Z Kristallogr., 129, p396-p404 (1969), as well as the commercial name "Prefeed" (δ-Na ₂ Si ₂ O ₅ ) from Tokuyama Siltech Co., Ltd. Preferred is crystalline sodium silicate. As the aluminosilicate, amorphous aluminosilicate is preferable, and Japanese Patent Application Laid-Open No. 62-191417, page 2, lower right column, line 19 to page 5, upper left column, line 17 (particularly the initial temperature is 15 to 60 ° C. is preferred), amorphous aluminosilicate described in JP-A-62-191419, page 2, lower right column, line 20 to page 5, upper left column, line 11; Examples thereof include amorphous aluminosilicates described in JP-A-132794, JP-A-7-10526, JP-A-6-227811, and JP-A-8-119622.

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

  The content of the particles (III) in the composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass. Preferably, the particles (III) are used so that the content of aluminosilicate and / or silicate in the composition is 1 to 20% by mass, and further 3 to 10% by mass.

  The particles (IV) are particles containing an inorganic peroxide. The inorganic peroxide is specifically a percarbonate (hereinafter sometimes referred to as PC), preferably sodium percarbonate, perborate, more preferably sodium perborate. Moreover, when employ | adopting a percarbonate, it is suitable to use the coated percarbonate from the point of storage stability. The particles (IV) may be substantially composed of an inorganic peroxide (including a coated one).

  The coated percarbonate is preferably one coated with a water-soluble polymer or inorganic salt. As specific examples, sodium percarbonate coated by a known method can be used. For example, Japanese Patent Publication No. 47-32200 (PC coated with paraffin), Japanese Patent Publication No. 53-15717 (PC US Pat. No. 4,131,562 (PC coated with sodium perborate and alcohol ethylene oxide adduct), US Pat. No. 4120812 (PC coated with sodium perborate with polyethylene glycol), German patent No. 2712139 (PC coated with silicate), German Patent No. 2800916 (PC coated with boric acid), European Patent No. 30759 (PC coated with wax), JP-A-58-217599 (PC coated with boric acid) Coated with salt), JP-A-59-196399 (PC coated with borate), JP-A-4-31498 (PC coated with boric acid and silicate separately), etc. What was obtained by the method can be used.

Among these, (i) sodium borate, preferably sodium metaborate, percarbonate coated with sodium orthoborate in a proportion of 0.1 to 30% by mass with respect to the percarbonate, (ii) orthoboric acid Percarbonate coated with 0.3 to 20% by mass, preferably 0.5 to 10% by mass, particularly preferably 1 to 8% by mass of boric acid selected from metaboric acid and tetraboric acid with respect to the percarbonate And (iii) and (ii) further sodium metasilicate, sodium orthosilicate, water glass No. 1, No. 2, sodium salt, potassium metasilicate, ortho orthosilicate, preferably water glass No. 1, No. 2, No. 3 sodium carbonate converted to SiO ₂ with respect to the percarbonate, 0.1 to 10% by mass, 0.2 to 7% by mass, particularly preferably 0.3 to 5% by mass. Salts are preferred. In particular, the percarbonate of (i) is preferable from the viewpoint of storage stability. As the percarbonate, sodium percarbonate is preferred.

  The coated percarbonate can be produced in the usual way. For example, it is possible to use a method in which a solution or powder containing the above-mentioned coating agent is mixed and adsorbed on a wet or dry percarbonate and dried.

  The average particle size of the coated percarbonate is preferably 100 to 2000 μm, more preferably 250 to 1000 μm, from the viewpoint of the bleaching washing effect.

  The average particle diameter of the particles (IV) is preferably 100 to 2000 μm, more preferably 250 to 1000 μm, from the viewpoint of the bleaching washing effect.

  The content of the particles (IV) in the composition is preferably 0.5 to 99% by mass, more preferably 5 to 70% by mass, still more preferably 10 to 50% by mass, and particularly preferably 20 to 40% by mass. %. Preferably, the particles (IV) are used so that the content of the inorganic peroxide in the composition is 10 to 50% by mass, and further 20 to 40% by mass.

  In the present invention, it is preferable to contain particles (V) containing an enzyme, and examples of the enzyme include cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase. Is preferred.

  Examples of proteases include commercially available enzymes such as Alcalase, Sabinase, Everase, Cannase, Esperase (Novo Nordisk Bioindustry), Ovozyme, Perfect, Properase, and Perfect OX (Genencor International).

  Examples of the amylase include commercially available enzymes such as Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry), Plaster ST, and Plaster OxAm (Genencor International).

  In the present invention, it is preferable to use protease and amylase together, and the mass ratio of amylase / protease as the amount of enzyme protein is preferably 0.010 to 16, more preferably 0.020 to 9.0, and particularly preferably 0.25. ~ 4.0.

  In the present invention, these enzymes are preferably contained as granulated particles. The amount of enzyme protein in the granulated product is 90 to 100% by mass, preferably 95 to 99% by mass in the particles (V). Moreover, the average particle diameter of particle | grains (V) is 50-1000 micrometers, Preferably it is 150-800 micrometers.

  The content of the particles (V), preferably the particles (V) in which the amount of enzyme protein is in the above range, is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass. Especially preferably, it is 0.2-5 mass%.

  In the cleaning composition for an automatic dishwashing machine of the present invention, it is preferable to add a bleach activator as the component (f) from the viewpoint of further improving the cleaning power. Preferred are compounds having one or more N- or O-acyl groups and / or optionally substituted benzoyl groups, eg substitutions consisting of anhydrides, esters, imides, acylated imidazoles or oximes A compound having a group. Examples include tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), tetraacetylglycoluril (TAGU), tetraacetylhexylenediamine (TAHD), N-acylimides such as N-nonanoyl succinimide (NOSI), Acylated phenol sulfonates such as n-nonanoyl- or isononanoyloxybenzene sulfonate (n- or iso-NOBS), lauroyloxybenzene sulfonate (LOBS), octanoyloxybenzoic acid (salt), decanoyloxybenzoic acid (salt) ) Pentaacetylglucose (PAG), 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine (DADHT) or N-carboxyl anthranilic anhydride ( SA) can be mentioned.

  In this invention, it is preferable to mix | blend polyacylated alkylenediamine from the point of the odor reduction effect after completion | finish of washing | cleaning. Examples of the polyacylated alkylenediamine include tetraacetylethylenediamine (TAED), tetraacetylmethylenediamine (TAMD), and tetraacetylglycoluril (TAGU), and tetraacetylethylenediamine (TAED) and tetraacetylmethylenediamine (TAMD) are preferable. In particular, tetraacetylethylenediamine (TAED) is effective.

  In the detergent composition for an automatic dishwasher of the present invention, the component (f) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, and still more preferably 0.5 to 2% by mass. contains. The component (f) is preferably blended in the composition separately from the particles (I) to (V) as the particles (VI) containing the component (f), and the particles (VI) are substantially In addition, particles composed of the component (f) are preferable. The particles (VI) are preferably used so that the content of the component (f) in the composition falls within the above range.

  In addition, as preferred components that can be blended in the detergent composition for an automatic dishwasher of the present invention, pigments, fragrances, antifoaming agents, polyacrylic acid and salts thereof, amphoteric copolymers (for example, acrylic acid-modified copolymers and And salts thereof, N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide copolymer, etc.).

  The amphoteric copolymer, which is a preferred component that can be blended in the detergent composition for an automatic dishwasher of the present invention, contains a monomer constituent unit having a cationic group (hereinafter referred to as monomer constituent unit (g1)) and an anionic group. And a polymer compound (g) [hereinafter referred to as component (g)] containing a monomer structural unit [hereinafter referred to as monomer structural unit (g2)].

  As the monomer structural unit (g1), monomer structural units represented by the following general formula (g1) and / or general formula (g2) are preferable.

[Wherein, R ¹¹ is a hydrogen atom or a methyl group, R ¹² is a hydrogen atom, a methyl group, or a hydroxy group, and R ¹³ is the same or different alkyl group having 1 to 3 carbon atoms or a hydroxy group. It is an alkyl group. A is —COOR ¹⁴ —, —CON (R ¹⁵ ) R ¹⁶ —, wherein R ¹⁴ and R ¹⁶ are alkylene groups having 2 to 5 carbon atoms, and R ¹⁵ is a hydrogen atom or a methyl group. R ²¹ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group which may be the same or different, and n is a number of 0 or 1. B ⁻ is an anionic group. ]

In the general formula (g1), R ¹¹ is preferably a hydrogen atom, and R ¹² is preferably a hydrogen atom or a methyl group. A is preferably —CON (R ¹⁵ ) R ¹⁶ —, R ¹⁶ is preferably an alkylene group having 2 to 5 carbon atoms, and R ¹⁵ is preferably a hydrogen atom. R ¹³ is preferably a methyl group, B ⁻ is a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a phosphate ion, a chain monocarboxylic acid ion having 1 to 12 carbon atoms, A benzenesulfonate ion optionally substituted with 1 to 3 alkyl groups is preferred, and a chloro ion is particularly preferred.

In the general formula (g2), R ²¹ is preferably a methyl group, B ⁻ is a halogen ion, a sulfate ion, a phosphate ion, a chain monocarboxylic acid ion having 1 to 12 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. A benzenesulfonic acid ion which may be substituted by 3 is preferable, and a chloro ion is particularly preferable. n is preferably 0.

  As the monomer structural unit (g2), a monomer structural unit represented by the following general formula (g3) is preferable.

[Wherein, R ³¹ represents a hydrogen atom, a methyl group, or —COOM, and R ³² represents a hydrogen atom, a methyl group, or a hydroxy group. Z is -COOM, a -ph-SO ₃ M. Here, M is a hydrogen atom, an alkali metal or an alkaline earth metal, and ph represents a benzene ring. ]

    The component (g) of the present invention may have a structure having a cationic group and an anionic group in one monomer constituent unit. Specifically, the monomer structural unit represented by the following general formula (g4) or general formula (g5) is preferable.

[Wherein, R ⁴¹ and R ⁵¹ are a hydrogen atom or a methyl group, and R ⁴² and R ⁵² are a hydrogen atom, a methyl group, or a hydroxy group. A, B ⁻ and M have the same meaning as described above, R ⁴³ and R ⁵³ are the same or different alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups, and R ⁵⁴ is —CH ₂ COO. _{^{-, -C 3 H 6 SO 3}} -, -CH 2 CH (OH) CH 2 -SO 3 - is a group selected from. ]

    The component (g) of the present invention can be produced by subjecting a monomer corresponding to the monomer structural unit constituting the component (g) to a normal polymerization reaction. Alternatively, the component (g) may be finally obtained by subjecting the polymer compound to post-treatment.

Specific examples of the monomer corresponding to the monomer structural unit represented by the general formula (g1) include acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 5 carbon atoms) -N, N, N— Trialkyl (1 to 3 carbon atoms) quaternary ammonium salt, acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 5 carbon atoms) -N, N, N-trialkyl (1 carbon atom) -3) A quaternary ammonium salt can be mentioned. As the salt, a salt corresponding to the above-mentioned B ⁻ is preferable.

  As a monomer corresponding to the general formula (g2), an N, N-diallyl-N, N-dialkyl (C1-3) quaternary ammonium salt can be used.

  As monomers corresponding to the general formula (g3), acrylic acid or a salt thereof, methacrylic acid or a salt thereof, crotonic acid or a salt thereof, α-hydroxyacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, Mention may be made of styrene sulfonates.

  The polymer compound having the monomer structural unit of the general formula (g4) is an aminoalkyl (2 to 5 carbon) dialkyl (1 to 3 carbon) amine, or N, N added to a monomer structural unit obtained by polymerizing maleic anhydride in advance. -Dialkyl (1 to 3 carbon atoms)-N-alkanol (2 to 5 carbon atoms) amine is reacted, followed by alkylation using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide Can also be manufactured.

  As a monomer corresponding to the general formula (g5), N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) 3) -N-carboxymethylammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)] -N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 carbon atom) -3) -N-sulfopropyl] ammonium sulfo Tine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-carboxymethylammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N- [2-hydroxysulfopropyl] ammonium Sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) oxyalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (1 to 3 carbon atoms) -N-sulfopropyl] ammonium sulfone Can mention betaine

  In the present invention, as a monomer structural unit having a cationic group, a monomer structural unit obtained by polymerizing an N, N-diallyl-N, N-dialkyl (C 1-3 quaternary ammonium salt), or N, Monomer composition in which N-diallyl-N-alkyl (1 to 3 carbon atoms) monomer structural unit is alkylated using a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide. Monomer constituent unit obtained by polymerizing a monomer selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, or maleic anhydride as a monomer constituent unit having an anionic group. Is preferred.

  The (g) component of the present invention has a molar ratio of [total number of moles of cationic groups] / [total number of moles of anionic groups] of 0.43 to 9.0, preferably 0.67 to 2. 3, More preferably, a polymer compound of 1.0 to 2.3 is preferable. In addition, when the anionic group is a carboxylic acid group, the preferred molar ratio is 0.43 to 2.3, particularly 1.0 to 2.3.

  The component (g) of the present invention comprises a monomer structural unit (g1) having a cationic group and a monomer structural unit (g2) having an anionic group, preferably from the general formula (g1) to the general formula (g5). 50 to 100 mol% of the total monomer constituent units selected (however, in the case of including the monomer constituent units derived from sulfur dioxide described later, the amount is also included) in the total monomer constituent units constituting the component (g) The polymer compound is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol%.

  In the present invention, in addition to the monomer structural unit having a cationic group and the monomer structural unit having an anionic group, preferably the monomer structural unit selected from the general formula (g1) to the general formula (g5), the effect of the present invention. The monomer constituent unit obtained by copolymerizing the monomer (g3) copolymerizable with these may be included to such an extent that the above is not impaired. Specifically, acrylamide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic acid) amide, N, N-dimethylaminoethyl acrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone, acrylic acid (or methacrylic acid) alkyl (1 to 5 carbon atoms), acrylic acid (Or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (1 to 5 carbon atoms), vinyl acetate, ethylene, propylene, N-butylene, isobutylene, N-pentene, Isoprene, 2-methyl-1-butene, N-hexene, 2-methyl-1- Nthene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, α-methylstyrene, allylamine, N, N-diallylamine, N, N-diallyl- N-alkyl (C1-C5) amine, ethylene oxide, propylene oxide, 2-vinylpyridine, 4-vinylpyridine, and sulfur dioxide can be mentioned.

  In the present invention, a compound obtained by copolymerizing 1 to 15 mol% of sulfur dioxide in the component (g) is most preferable. That is, a polymer compound containing 1 to 15 mol% of a monomer constituent unit derived from sulfur dioxide in all monomer constituent units constituting the component (g) is most preferable.

  The component (g) of the present invention may be obtained by any polymerization method, but a radical polymerization method is particularly preferred, and this can be carried out in a lump, solution, or emulsion system.

  Component (g) of the present invention preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 2,000 to 500,000, still more preferably 3,000 to 100,000, and particularly preferably. The weight average molecular weight can be determined by gel permeation chromatography using polyethylene glycol as a standard substance using a 50 mM lithium bromide dimethylformamide solution as a developing solvent.

  The content of the component (g) in the cleaning composition for an automatic dishwasher of the present invention is 0.05 to 10% by mass, further 0.3 to 10% by mass, and further 0.4 to 8% by mass. preferable. Furthermore, it is preferable to mix | blend (g) component in particle | grains (I).

  The component (b), the component (c), and the component that can be optionally blended may be added to each particle to the extent that the stability and properties of the component are not impaired, or may be blended separately as other particles. Good. Alternatively, after mixing the particles (I) to (VI), etc., they may be added by spraying as a liquid. When using the particle | grains containing (c) component separately from particle | grains (I), this particle | grain may be a particle | grain which consists of (c) component.

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

  The liquid detergent composition for an automatic dishwasher according to the present invention has a pH of 0.2% by weight diluted aqueous solution (JIS-Z-8802: 1984 “pH measurement method”) from the viewpoint of odor reduction effect after completion of washing. At 25 degreeC, Preferably it is 8-13, More preferably, it is 9-12, More preferably, it is 10-11. The ester compound easily undergoes hydrolysis under basic conditions. It is surprising that the component (a), which is an ester compound, has a function as a surfactant under such conditions and exhibits an effect on the deodorizing performance after washing.

The average particle diameter, primary particle diameter, and bulk density described in the present invention are measured as follows.
<Measuring method of average particle size>
The average particle diameter is a median diameter, and is determined using a sieve specified in JIS Z 8801. For example, using a 9-stage sieve and a saucer having openings of 2000 μm, 1400 μm, 1000 μm, 710 μm, 500 μm, 350 μm, 250 μm, 180 μm, and 125 μm, a low-tapping machine (made by HEIKOSEISAKUSHO, tapping: 156 times / minute, rolling: 290 And a 100 g sample is vibrated for 5 minutes, and then the proportion of particles of each particle size is measured from the mass fraction according to the size of the sieve opening to determine the average particle size.

<Measurement method of primary particle size>
The particle size of 3,000 particles is measured with a scanning or transmission electron microscope, and the average particle size is obtained.

<Method for measuring bulk density>
The bulk density is measured by a method defined by JIS K 3362.

  The cleaning composition for an automatic dishwashing machine of the present invention is a composition containing (a) component, (b) component and (c), wherein the particles (I) and (b) containing the component (I) ), Particles (II) containing alkali metal carbonates and / or alkali metal hydroxides, particles (III) containing aluminosilicates and / or silicates, and inorganic peroxides Particle (IV), particle (V) containing enzyme, particle (VI) containing component (c), and component (e) added separately from the above particles, The mass ratio of a) / [(b) + (c)] is 0.080 to 1.0, and the total content of (a), (b), and (c) in the composition is 0.00. A detergent composition for an automatic dishwasher that is 8 to 11% by mass is preferred.

The most preferred embodiment of the present invention is shown below.
Particle (I): average particle diameter of 100 to 500 μm, containing (a) component in an amount such that the content in the composition is 0.3 to 1% by mass, and (b) component in the composition Is contained in an amount of 1.0 to 2.0 mass%, and further, at least one (d1) component is contained in the particle (I) at 20 to 60 mass%, and at least one (d2) is contained in the particles ( I) Powder (Y) covering particle (I), selected from 30 to 60% by mass, amorphous silicate, crystalline silicate, aluminosilicate, silica, alumina in particle (I) 0.5 to 10% by mass, 0.5 to 10% by mass of component (g) in particles (I), and the ratio of (d1) component / (d2) component is 0.67 to 1.0 by mass ratio. Is a particle.
Particle (II): The content in the composition is 10 to 30% by mass.
However, the particles (II) are sodium carbonate (light ash, dense ash) having an average particle size of 100 to 500 μm.
-Particle | grain (III): Content in a composition is 3-10 mass%.
However, the particles (III) are crystalline layered sodium silicate having an average particle diameter of 5 to 800 μm.
Particle (IV): The content in the composition is 20 to 40% by mass.
However, the particles (IV) are sodium percarbonate having an average particle diameter of 250 to 1000 μm.
-Particle | grain (V): Content in a composition is 0.2-5 mass%.
However, the particles (V) contain particles (V-1) containing amylase and / or particles (V-2) containing protease, and have an average particle size of 150 to 800 μm.
-Particle | grain (VI): Content in a composition is 0.5-2 mass%.
However, particle | grains (VI) consist of (c) component, and are average particle diameters of 50-1500 micrometers.
Particle (VII): The content in the composition is 0.5 to 2% by mass.
The particles (VII) contain a bleach activator and have an average particle size of 50 to 1500 μm.
-Other particle | grains: Content in a composition is 0-5 mass%.
The other particles are particles having an average particle diameter of 50 to 1500 μm, are particles for increasing added value, and can contain, for example, a fragrance that exhibits deodorizing performance. Furthermore, after mixing said particle | grains, it is preferable to add (e) component so that content of (e) component in a composition may be 0.4-3 mass%, and to mix after that.

  In addition, the composition containing the particles preferably has an average particle size of each particle as much as possible in order to prevent the particles from being divided into layers by vibration or the like (generally classification). For example, the average particle diameter of each particle used for preparation in the composition is preferably in the range of 300 to 400 μm.

<Production Method of Particle (I)>
(D1) Trisodium citrate, (d2) Sodium sulfate and (b) Diisobutylene / maleic acid copolymer are added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min), and then mixed. did. Next, (a) sorbitan oleic acid monoester was added, an aqueous solution of the polymer compound (g1) was added, and then mixed. Next, amorphous silica was added and then mixed to obtain particles (I). In addition, the addition amount of each component was made into the quantity calculated from the mixture ratio shown in Table 1 corresponding to 30 kg of cleaning composition.

<Production method of cleaning composition>
Particle (II), particle (III) and particle (VI) were added to particle (I) and then mixed. Next, (e1) polypropylene glycol is added and mixed, then particles (IV), particles (V-1), particles (V-2), particles (VII) and perfume are added, then mixed and washed 30 kg of an agent composition was obtained. As the particles (II) to (VII), commercially available particulate products were used.

<PH measurement>
Using a pH meter (D-52S, pH electrode 6367-10D, manufactured by HORIBA, Ltd.), 0.2 mass prepared with deionized water of the cleaning composition prepared according to JIS Z-8802: 1984. The pH value at 25 ° C. of the% diluted solution was measured.

<Odor intensity test>
As model dirt, oil sardine (Iwashi Oil Pickled, Nippon Suisan Co., Ltd.) 2.0 g, Yakiniku sauce (golden taste, medium spicy, Ebara Food Industry Co., Ltd.) 5.0 g, retort curry (Bon curry gold 21, Each 3.5g of dry, made by Otsuka Foods Co., Ltd. is placed in a ceramic dish (catalog number: 558-3-60, onion 9 bowl rim meat dish, tableware catalog storehouse No. 5), and natto (okame natto, domestically produced) Apply 1.3g of medium grain natto mini, manufactured by Takano Foods Co., Ltd. to ceramic bowl (catalog number: 562-53-31, 3.6 soup bowl (white), tableware catalog No. 5) After passing through the tap water (25 ° C) that had been dried for 1 hour in the tank, place it in a predetermined position on the built-in type automatic dishwasher (model number: NP-P45M1, manufactured by Panasonic Corporation). Tsu was collected.

  Each cleaning composition that had been shrunk in advance was charged into a 6.0 g cleaning agent inlet, and was operated on a standard course (amount of tap water used in the cleaning process: 3 liters).

After the operation, panel odors (seven men and women in their 20s to 40s) performed odor sensory evaluation, scored according to the evaluation criteria in the following 6 levels, and obtained the total score of each panel. The total score of 7 panelists is shown in the table. In this evaluation, if the total score is 14 or less, it is determined that there is no problem of odor after the completion of cleaning.
(Evaluation criteria)
0: Odorless 1: I do not know what the smell is, but I feel something gently 2: I know what the smell is. A weak smell that feels easy.
3: Smell clearly felt.
4: Strong smell.
5: Unusable smell.

<Preventing re-adhesion of oil stains>
3.0 g of beef tallow (Aldrich Japan Co., Ltd.) is placed in a built-in type automatic dishwasher (model number: NP-P45M1, manufactured by Panasonic), and slide glass (Super Frost White, Matsunami) is placed in the glass holder in the cabinet. Fix 3 sheets (manufactured by Glass Kogyo Co., Ltd.), put each cleaning composition, which has been shrunk in advance, into the 6.0g cleaning agent inlet, and run in the standard course (use tap water in the cleaning process) Amount: 3 liters).

  After drying, the contact angle of water with the slide glass surface was measured with a contact angle meter (model number: CA-X150, manufactured by Kyowa Interface Science Co., Ltd.), and the average value was obtained (n = 9). The results are shown in the table. In this evaluation, if the contact angle (average value) is 30 ° or less, it is judged that the oil stain re-adhesion preventing property is excellent.

The mass% in a table | surface is a thing in a composition. The components in the table are as follows. The polymer compound (g1) in the table was used as an aqueous solution having a concentration of 25% by mass. The mass% of the polymer compound (g1) in the table is the mass% of the aqueous solution.
1) Sorbitan monooleate (manufactured by Kao Corporation, Rheodor SP-O10V)
2) Diisobutylene / maleic acid copolymer (Rohm and Haas, Acusol 460ND, weight average molecular weight 15,000, diisobutene / maleic acid = 1.0 (molar ratio))
3) A copolymer polymerized at a molar ratio of N, N-diallyl-N, N-dimethylammonium chloride / maleic acid / sulfur dioxide = 66.7 / 26.7 / 6.6 (weight average molecular weight 20,000, PH of 25 mass% aqueous solution (25 ° C) 2.0)
4) Tokuseal NR (manufactured by Tokuyama), primary particle size: 20 nm
5) Sodium carbonate (Central Glass Co., Ltd., dense ash)
6) Pre-feed (made by Tokuyama Siltech)
7) Sodium percarbonate whose surface is coated with sodium metaborate (metaboric acid content: 3% by mass) (manufactured by Nippon Peroxide Co., Ltd., KCPZ)
8) Duramil 120T (manufactured by Novo Nordisk Bioindustry), average particle size 600 μm
9) Sabinase 18.0T (manufactured by Novo Nordisk Bioindustry), average particle size 600 μm
10) Socaran CP45 (manufactured by BASF), average particle size 400 μm, weight average molecular weight about 70,000, acrylic acid / maleic acid = 2.3 (molar ratio), partial sodium salt 11) weight Average molecular weight of about 3000, average condensation degree of about 50 (diol type, manufactured by Wako Pure Chemical Industries, Ltd.)
12) PERACTIVE AN (manufactured by Clariant)

  When Examples 1 to 3 and Comparative Examples 1 and 2 are compared, if (a) / [(b) + (c)] is within the scope of the present invention, the effect of reducing odor after washing and re-staining of oil stains It turns out that it is excellent in adhesion prevention. When Examples 4 and 5 are compared with Comparative Examples 3 and 4, if (a) + (b) + (c) is within the scope of the present invention, the effect of reducing odor after washing and the prevention of oil stain reattachment It is understood that it is excellent.

Claims (4)

(A) an ester of a fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol, (b) a copolymer of an unsaturated carboxylic acid having 3 to 6 carbon atoms or an anhydride thereof and an olefin having 2 to 12 carbon atoms, ( c) An acrylic acid-maleic acid copolymer or salt thereof having an acrylic acid / maleic acid molar ratio of 0.6-9 and a weight average molecular weight of 1,000-100,000, or (a) / [( b) + (c)] is a mass ratio of 0.080 to 1.0, and the total content of (a), (b), and (c) is 0.8 to 11% by mass. A cleaning composition for a cleaning machine. The cleaning composition for an automatic dishwasher according to claim 1, wherein (a) is a sorbitan fatty acid ester having 14 to 22 carbon atoms in the fatty acid. (B) is a copolymer having a weight average molecular weight of 5,000 to 50,000 obtained by polymerizing maleic acid and / or maleic anhydride and an olefin having 3 to 9 carbon atoms in a molar ratio of 0.1 to 10. Item 3. A cleaning composition for an automatic dishwasher according to Item 1 or 2. The cleaning composition for an automatic dishwasher according to claim 3, wherein the olefin having 3 to 9 carbon atoms is isobutylene and / or diisobutylene.