JP5688318B2 - Detergent composition for automatic dishwasher - Google Patents

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 acrylic acid polymer is used in combination. Patent Document 2 discloses a technique in which a sorbitan fatty acid ester type nonionic surfactant is applied to a rinse aid for an automatic dishwasher equipped with an automatic rinse aid feeder. It is described that a deodorizing effect can be obtained by using the product together.

JP 2005-154716 A JP 7-62397 A

  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, especially oil stains from reattaching to tableware, even in a shorter cleaning operation.

  Accordingly, an object of the present invention is to provide a detergent composition for an automatic dishwasher that is excellent in preventing the reattachment of dirt even in a shorter washing operation and can solve the problem of odor after the completion of washing using an automatic dishwasher. Is to provide.

In the present invention, (a) an ester of a fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol (hereinafter referred to as component (a)) is 0.01 to 10% by mass, (b) the following (b1) and (b2 ) And a polymer compound selected from (b3) [hereinafter referred to as the component (b)], and a 0.2% by weight aqueous solution having a pH of 9 or more at 25 ° C. is 9 or more. About.
(B1): 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 (b2): a monomer constituent unit having a cationic group and an anionic group Polymer compound (b3) containing a monomer structural unit having an acrylic acid-maleic acid copolymer or salt thereof

  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 washing | cleaning agent for automatic dishwashers which is excellent in the anti-reattachment property of dirt, such as oil stains, also solves the problem of the smell after completion | finish of washing | cleaning using an automatic dishwasher even in a shorter washing operation A composition 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, from the viewpoint of the effect of reducing odor after washing, lauric acid, 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 composition fatty acid and beef tallow fatty acid are preferable, oleic acid, linoleic acid, palm oil composition fatty acid and beef tallow fatty acid are more preferable, and oleic acid is particularly preferable.

  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 sorbitol is used as a starting material, a ring is formed during the esterification reaction to form 1,4-sorbitan fatty acid ester and 1,5-sorbitan fatty acid ester. Since esters and sorbitol fatty acid esters are also produced, they 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.

<(B) component>
The component (b) of the present invention is one or more polymers selected from the following (b1), (b2), and (b3) from the viewpoints of the anti-redeposition property of dirt and the effect of reducing odor after completion of washing. A compound. In the present invention, the following component (b1) is preferably contained as the component (b) from the viewpoint of the odor reduction effect after completion of washing, and from the viewpoint of preventing reattachment of dirt, the following component (b2) is contained. It is more preferable that the following (b2) component and (b3) component are contained, and that all of the following (b1), (b2) and (b3) are contained, preventing the reattachment of dirt and washing From the viewpoint of the effect of reducing odor after completion, it is particularly preferable.

(B1): Copolymer of unsaturated carboxylic acid having 3 to 6 carbon atoms or anhydride thereof and olefin having 2 to 12 carbon atoms [hereinafter referred to as component (b1)]
(B2): a polymer compound containing a monomer structural unit having a cationic group and a monomer structural unit having an anionic group [hereinafter referred to as component (b2)]
(B3): Acrylic acid-maleic acid copolymer or salt thereof (hereinafter referred to as component (b3))

  The component (b1) 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 (b1) 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, in the constituent monomer of the component (b1), 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 is 90 to 100 mol%, and further 95 to 100 mol. %, More preferably 98 to 100 mol%, and the component (b1) 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 (b1) 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 (b1) is a mixture of acetonitrile and 0.1M sodium chloride aqueous solution (mixing ratio of acetonitrile and sodium chloride aqueous solution is 30:70 by volume) as a developing solvent, and polyethylene by gel permeation chromatography. Glycol can be determined as a standard substance.

  The component (b2) of the present invention comprises a monomer constituent unit having a cationic group (hereinafter referred to as monomer constituent unit (b2-1)) and a monomer constituent unit having an anionic group [hereinafter monomer constituent unit (b2-2). It is a polymer compound containing

  As the monomer structural unit (b2-1), a monomer structural unit represented by general formula (b2-1-1) and / or general formula (b2-1-2) shown below is preferable.

[Wherein, R ^1b is a hydrogen atom or a methyl group, R ^2b is a hydrogen atom, a methyl group, or a hydroxy group, and R ^3b is the same or different and may be the same or different. It is an alkyl group. A is —COOR ^4b —, —CON (R ^6b ) R ^5b —, wherein R ^4b and R ^5b are alkylene groups having 2 to 5 carbon atoms, and R ^6b is a hydrogen atom or a methyl group. R ^7b 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 general formula (b2-1-1), R ^1b is preferably a hydrogen atom, and R ^2b is preferably a hydrogen atom or a methyl group. A is preferably —CON (R ^6b ) R ^5b —, R ^5b is preferably an alkylene group having 2 to 5 carbon atoms, and R ^6b is preferably a hydrogen atom. R ^3b is preferably the same or different methyl group, and B ⁻ is a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a phosphate ion, or a chain monocarboxylate ion having 1 to 12 carbon atoms. Benzene sulfonate ions which may be substituted by 1 to 3 alkyl groups having 1 to 3 carbon atoms are preferred, and chloro ions are particularly preferred.

In general formula (b2-1-2), R ^7b is preferably a methyl group, B ⁻ is a halogen ion, a sulfate ion, a phosphate ion, a chain monocarboxylate ion having 1 to 12 carbon atoms, or an alkyl having 1 to 3 carbon atoms A benzenesulfonate ion that may be substituted by 1 to 3 groups is preferred, and a chloro ion is particularly preferred. n is preferably 0.

  As the monomer structural unit (b2-2), a monomer structural unit represented by general formula (b2-2-1) shown below is preferable.

[Wherein, R ^8b is a hydrogen atom, a methyl group, or —COOM, and R ^9b is 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 (b2) 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 of the following general formula (b2-3-1) or general formula (b2-3-2) is preferable.

[Wherein, R ^10b and R ^13b are a hydrogen atom or a methyl group, and R ^11b and R ^14b are a hydrogen atom, a methyl group, or a hydroxy group. A, B ⁻ and M have the same meaning as described above, R ^12b and R ^15b are the same or different alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups, and R ^16b 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 (b2) of the present invention can be produced by subjecting a monomer corresponding to the monomer structural unit constituting the component (b2) to a normal polymerization reaction. Alternatively, the component (b2) may be finally obtained by post-processing the polymer compound.

Specific examples of the monomer corresponding to the monomer structural unit of the general formula (b2-1-1) 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 (C1-C3) 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 (b2-1-2), N, N-diallyl-N, N-dialkyl (carbon number 1 to 3) quaternary ammonium salt can be used.

  As monomers corresponding to the general formula (b2-2-1), 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, Mention may be made of maleic anhydride and styrene sulfonate.

  The polymer compound having the monomer structural unit of the general formula (b2-3-1) is an aminoalkyl (carbon number 2 to 5) dialkyl (carbon number 1 to 3) amine in a monomer structural unit obtained by polymerizing maleic anhydride in advance. Alternatively, a quaternizing agent such as methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide, etc. is reacted with N, N-dialkyl (C1-3) -N-alkanol (C2-5) amine. It can also manufacture by alkylating using.

  As a monomer corresponding to the general formula (b2-3-2), N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl ( 1 to 3) -N-carboxymethylammonium carbobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (carbon number) 1-3) -N- [2-hydroxysulfopropyl] ammonium sulfobetaine, N- [acryloyl (or methacryloyl, α-hydroxyacryloyl, or crotonoyl) aminoalkyl (2 to 3 carbon atoms)]-N, N-dialkyl (C1-C3) -N-sulfopropylammonium Ruphobetaine, 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-sulfopropylammonium sulfobetaine To mention That.

  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.

  Component (b2) of the present invention has a [ratio of total number of cationic groups] / [total number of moles of anionic group] 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. Further, when the anionic group is a carboxylic acid group, the preferred molar ratio is preferably 0.43 to 2.3, and particularly preferably 1.0 to 2.3.

  The component (b2) of the present invention includes a monomer structural unit (b2-1) having a cationic group and a monomer structural unit (b2-2) having an anionic group, preferably a general formula (b2-1-1). ) To the monomer constituent unit selected from the general formula (b2-3-1) (however, when the monomer constituent unit derived from sulfur dioxide described later is included), the component (b2) is constituted. Among all the monomer structural units to be used, a polymer compound of 50 to 100 mol%, preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 90 to 100 mol% is preferable.

  In the present invention, a monomer constitutional unit having a cationic group and a monomer constitutional unit having an anionic group, preferably a monomer constitution selected from general formula (b2-1-1) to general formula (b2-3-1) In addition to the units, a monomer constituent unit obtained by copolymerizing the monomer (b2-4) copolymerizable with these to such an extent that the effects of the present invention are not impaired may be included. 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 (b2) 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 (b-2) is most preferable.

  The component (b2) 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.

  The component (b2) 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, 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 component (b3) of the present invention is an 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 (b3), acrylic acid and a maleic acid copolymer or a salt thereof are used because they are 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. The component (b3) is preferably a salt of the copolymer.

  Component (b3) preferably has an acrylic acid / maleic acid molar ratio of 0.6 to 9, more preferably 1 to 4, and particularly preferably 1.5 to 4. In addition, the molar ratio of acrylic acid / maleic acid in the component (b3) can be determined by detecting the pyrolyzate of the copolymer by pyrolysis gas chromatography (PGC). In the constituent monomer of component (b3), the proportion of acrylic acid and maleic acid is preferably 90 to 100 mol%, more preferably 95 to 100 mol%, still more preferably 98 to 100 mol%, and substantially (b3 The component is preferably a copolymer of acrylic acid and maleic acid or a salt thereof.

  The component (b3) has a weight average molecular weight of 1,000 to 100,000, more preferably 10,000 to 90,000, particularly 50,000 to 80,000, and is excellent in oil stain cleaning power and recontamination property. From the point of view, it is preferable. The weight average molecular weight of the component (b3) is a mixed solution of water and acetonitrile containing phosphoric acid (the content of phosphoric acid is 0.1% by mass, and the mixing ratio of water and acetonitrile is 90:10 by volume ratio). Can be obtained as a standard substance by gel permeation chromatography.

<Cleaning composition for automatic dishwasher>
The cleaning composition for an automatic dishwashing machine of the present invention has a component (a) of 0.01 to 10% by mass, preferably 0.1%, from the viewpoint of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. ˜2 mass%, more preferably 0.3 to 1 mass%.

  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 (b1) from the viewpoint of the effect of reducing odor after the end of washing. More preferably, the content is 1 to 2% by mass.

  The detergent composition for an automatic dishwasher of the present invention is preferably 0.05 to 10% by mass, more preferably 0.3 to 10% by mass, from the viewpoint of preventing reattachment of dirt. More preferably, it contains 0.4-8 mass%. In addition, the content of the component (b2) 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. % Is preferred.

  The detergent composition for an automatic dishwasher of the present invention is preferably 0.05 to 10% by mass, more preferably 0.1 to 5% by mass of the component (b3) from the viewpoint of the odor reduction effect after completion of the cleaning. More preferably, the content is 0.5 to 2% by mass.

  The total mass of the component (b1), the component (b2), and the component (b3) is preferably 0.2 to 40% by mass from the viewpoints of the anti-reattachment property of dirt and the effect of reducing odor after completion of washing. -30 mass% is more preferable, and 2-20 mass% is still more preferable.

  The pH at 25 ° C. of the 0.2% by mass aqueous solution of the cleaning composition for an automatic dishwasher of the present invention is 9 or more from the viewpoints of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. , Preferably 10 or more, more preferably 11 or more. Moreover, the pH at 25 ° C. of the 0.2% by mass aqueous solution of the detergent composition for an automatic dishwasher of the present invention is preferably 14 or less, more preferably 13 in terms of safety and substrate damage. Hereinafter, it is more preferably 12 or less. This pH is measured according to JIS-Z-8802: 1984 “pH measurement method”.

  The ester compound easily undergoes hydrolysis under basic conditions. Under such conditions, the component (a), which is an ester compound, has a function as a nonionic surfactant, and prevents the reattachment of dirt and the effect of reducing odor after washing without an ester bond. It is surprising that it is superior to nonionic surfactants. The reason for this is not clear, but at the pH within the range of the present invention, the component (a) is not hydrolyzed at the initial stage of washing, functions sufficiently as a nonionic surfactant, emulsifies the dirt component, and is washed. Since hydrolysis is completed in the latter period and it is easy to be discharged from the interior of the automatic dishwasher, it is estimated that it is more effective than other types of nonionic surfactants.

  The detergent composition for an automatic dishwasher, in which a predetermined amount of the component (a) and the component (b) of the present invention are mixed, and the pH at 25 ° C. of a 0.2% by mass aqueous solution is 9 or more, In addition to exhibiting an excellent cleaning power, it is possible to prevent re-adhesion of removed oil stains and to reduce the odor in the cabinet after completion of cleaning.

  In the cleaning composition for an automatic dishwasher according to the present invention, the mass ratio of (a) / (b) is preferably 0.010 to 1 from the viewpoints of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. 0.0, more preferably 0.050 to 0.50, and still more preferably 0.10 to 0.30.

  The cleaning composition for an automatic dishwasher of the present invention preferably contains an alkaline agent (hereinafter referred to as component (c)). The component (c) is preferably an alkali metal carbonate and / or an alkali metal hydroxide from the viewpoint of preventing redeposition of dirt and an effect of reducing odor after washing, and includes sodium carbonate, potassium carbonate, sodium hydroxide, Potassium hydroxide is more preferable, sodium carbonate and potassium carbonate are more preferable, and sodium carbonate is particularly preferable.

  The content of the component (c) in the cleaning composition for an automatic dishwashing machine of the present invention is preferably 10 to 30% by mass from the viewpoint of preventing reattachment of dirt and the effect of reducing odor after washing, -25 mass% is more preferable.

  In the cleaning composition for an automatic dishwasher of the present invention, the mass ratio of (a) / (c) is preferably 0.010 to 0 from the viewpoint of preventing reattachment of dirt and the effect of reducing odor after completion of cleaning. .10, more preferably 0.015 to 0.050, and still more preferably 0.020 to 0.040.

  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 The total content is preferably 11 to 70% by mass, more preferably 12 to 50% by mass, still more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass.

  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) component and (e) component described later, hereinafter referred to as (d1) component] and water-soluble inorganic salts [provided that (c) component is And a compound selected from the following (hereinafter referred to as component (d2)) [hereinafter referred to as component (d)].

  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).

  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 the component (d) from the viewpoint of the effect of reducing odor after completion of washing. 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 particles (I) of the present invention, the component (d1) and the component (d2) may be used in combination, and the mass ratio of the component (d1) / (d2) improves the cleaning power and reduces the odor after completion of the cleaning. From the viewpoint of the effect, it is preferably 0.43 to 4.0, particularly preferably 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.), etc. 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.

  The particle (I) can contain the component (b), but the component (b1) and / or the component (b2) is blended with the particle (I), and the component (b3) is blended with the particle (I). First, it is preferable to mix in the composition as particles different from the particles (I). Accordingly, the particle (I) preferably contains the component (b1) and / or the component (b2), and more preferably contains the component (b1) and the component (b2). 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 still more preferably 10 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 (c) component with the washing | cleaning-agent composition for automatic dishwashers of this invention from a viewpoint of the reattachment prevention property of a stain | pollution | contamination, and the odor reduction effect after completion | finish of washing | cleaning. 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 with the washing | cleaning agent composition for automatic dishwashers of this invention 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.

  In addition, the detergent composition for an automatic dishwasher according to the present invention may contain a silicate or an aluminosilicate separately from the powder (Y) of the particles (I) from the viewpoint of oil stain cleaning properties. preferable. 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, as particles other than particles (I), particles (II) containing component (c), particles (III) containing aluminosilicates and / or silicates, particles containing inorganic peroxides It is preferable to contain one or more particles selected from (IV) and enzyme-containing particles (V), and it is particularly preferable to contain all of the particles (II) to (V). Moreover, you may contain arbitrary particles other than these particles.

  The particles (II) may be substantially composed of the component (c). Here, in the present invention, 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 component (c) 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%.

  Moreover, when mix | blending (b3) component separately from particle | grains (I), it can mix | blend in a composition as particle | grains (VI) containing (b3) component. The particles (VI) may be particles composed of the component (b3).

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, it is preferable to add a bleach activator as the component (f) from the viewpoint of further detergency and an improvement in odor reduction effect after completion of washing.

  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 as (f) component 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 (VII) containing the component (f), and the particles (VII) are substantially In addition, particles composed of the component (f) are preferable. The particles (VII) are preferably used so that the content of the component (f) in the composition falls within the above range.

  Other preferable components that can be blended in the cleaning composition for an automatic dishwasher of the present invention include dyes, fragrances, antifoaming agents and the like.

  The components 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. Alternatively, the particles (I) to (VII) may be added after being mixed and then sprayed as a liquid.

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 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 dishwasher of the present invention is a composition containing the component (a) and the component (b), the component (a), the component (b1), the component (b2), and ( d) Particles containing component (I), Particles containing component (c) (II), Particles containing aluminosilicate and / or silicate (III), and particles containing inorganic peroxide (IV), particles (V) containing enzyme, particles (VI) containing component (b3), and (e) component added separately from the above particles, ) / (B) is a mass ratio of 0.010 to 1.0, (a) / (c) is a mass ratio of 0.010 to 1.0, and (a), ( A detergent composition for an automatic dishwasher in which the total content of b) and (c) is 11 to 70% by mass is preferred.

Preferred embodiments of the present invention are 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 (b1) component in the composition Is contained in an amount such that the content is 1.0 to 2.0 mass%, the component (b2) is contained in an amount such that the content in the composition is 0.40 to 8.0 mass%, (D1) One or more of the components in particles (I) is 20 to 60% by mass, and one or more of (d2) is 30 to 60% by mass in particles (I), amorphous silicate, crystalline silicate, aluminosilicate Selected from the group consisting of silica, and alumina, powder (Y) covering particle (I) is 0.5 to 10% by mass in particle (I), and component (b-2) is 0.00 in particle (I). Particles containing 5 to 10% by mass, and the ratio of (d1) component / (d2) component is 0.67 to 1.0 by mass ratio.
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, the particles (VI) are composed of the component (b3) and have an average particle diameter of 50 to 1500 μm.
-Particle | grain (VII): Content in a composition is 0.1-5 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 0.01-5 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 polymer compound (b1) were added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min), and then mixed. Next, the component (a) was added, an aqueous solution of the polymer compound (b2) 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 particle (I ')>
(D1) Trisodium citrate, (d2) Sodium sulfate and polymer compound (b1) were added to a 30 L Nauter mixer (rotation: 110 r / min, revolution: 4 r / min), and then mixed. Next, the component (a ′) was added, an aqueous solution of the polymer compound (b2) 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>
* Examples 1 to 5 and Comparative Examples 1 and 4
Particle (II) and particle (VI) were added to particle (I) and then mixed. Next, (e1) polypropylene glycol was added and then mixed. The fragrance was then added and then mixed. In addition, particles (IV), particles (V-1), particles (V-2) and particles (VII), and sulfuric acid or After adding sodium hydroxide, mixing was performed to obtain 30 kg of a cleaning composition. For the particles (II) and (IV) to (VII), commercially available particulate products were used.

* Comparative Examples 2 and 3
Particle (II) and particle (VI) were added to particle (I ′) and then mixed. Next, (e1) polypropylene glycol was added and then mixed. The fragrance was then added and then mixed. Furthermore, particles (IV), particles (V-1), particles (V-2) and particles (VII) were added and then mixed to obtain 30 kg of a cleaning composition. For the particles (II) and (IV) 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.

<Measurement of adhesion amount of oil stains>
Built-in type 5 pieces of 2.0g beef tallow (Aldrich Japan Co., Ltd.) coated and dried on polypropylene resin dish (diameter 126mm, PP tableware C-32, manufactured by Kanto Plastic Industry Co., Ltd.) Set in a predetermined position of an automatic dishwasher (model number: NP-P45M1, manufactured by Panasonic Corporation) and put each of the pre-shrinked detergent composition into the 6.0g detergent inlet, to speed course Drove.

  After air-drying at room temperature all day and night, the amount of oil stains on the dish after washing with a precision balance was weighed. In this evaluation, it is judged that if the amount (average value) of oil stains per dish is 10 mg or less, it is excellent in cleaning performance against oil stains and prevention of reattachment of oil stains.

The mass% in a table | surface is a thing in a composition. The components in the table are as follows. The polymer compound (b2) in the table was used as an aqueous solution having a concentration of 25% by mass. The mass% of the polymer compound (b2) in the table is the mass% of the aqueous solution.
1) Sorbitan monooleate (manufactured by Kao Corporation, Rheodor SP-O10V)
2) Sorbitan monostearate (manufactured by Kao Corporation, Rheodor SP-S10V)
3) Sorbitan monopalmitate (manufactured by Kao Corporation, Rheodor SP-P10)
4) Diisobutylene / maleic acid copolymer (Rohm and Haas, Acusol 460ND, weight average molecular weight 15,000, diisobutene / maleic acid = 1.0 (molar ratio))
5) 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)
6) Polyoxyethylene (ethylene oxide average addition mole number = 4) oleyl ether 7) Alkyl glucoside (manufactured by Kao Corporation, Mydol 12, carbon number of alkyl group is 12, glucose average condensation degree 1.3)
8) Sodium carbonate (Central Glass Co., Ltd., dense ash)
9) Sodium percarbonate whose surface is coated with sodium metaborate (metaborate content: 3% by mass) (manufactured by Nippon Peroxide Co., Ltd., KCPZ)
10) Duramil 120T (manufactured by Novo Nordisk Bioindustry), average particle size 600 μm
11) Sabinase 18.0T (manufactured by Novo Nordisk Bioindustry), average particle size 600 μm
12) Socaran CP45 (manufactured by BASF), average particle size 400 μm, weight average molecular weight of about 70,000, acrylic acid / maleic acid = 2.3 (molar ratio), partial sodium salt 13) weight Average molecular weight of about 3000, average condensation degree of about 50 (diol type, manufactured by Wako Pure Chemical Industries, Ltd.)
14) PERACTIVE AN (manufactured by Clariant)
15) Sulfuric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
16) Sodium hydroxide (special grade, manufactured by Wako Pure Chemical Industries, Ltd.)

  When Examples 1 to 3 are compared with Comparative Example 1, if the pH of the 0.2 mass% aqueous solution is within the range of the present invention, it is excellent in the odor reduction effect after the end of washing and the anti-redeposition property of oil stains. I understand. When Example 2 and Comparative Examples 2 to 4 are compared, it can be seen that when component (a) is contained, the effect of reducing odor after completion of cleaning and the prevention of reattachment of oil stains are excellent.

Claims (8)

(A) 0.01 to 10% by mass of an ester of a fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol, (b) containing a polymer compound selected from the following (b1), (b2) and (b3) And a detergent composition for an automatic dishwasher having a pH of 9 or more at 25 ° C. of a 0.2 mass% aqueous solution,
As (b), (b1) containing 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,
A cleaning composition for automatic dishwashers.
(B1): 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 (b2): a monomer constituent unit having a cationic group and an anionic group Polymer compound (b3) containing a monomer structural unit having an acrylic acid-maleic acid copolymer or salt thereof (C) The cleaning composition for automatic dishwashers according to claim 1, comprising 10 to 30% by mass of an alkaline agent. The cleaning composition for an automatic dishwasher according to claim 2 , wherein the mass ratio of (a) / (c) is from 0.010 to 0.10. The cleaning composition for an automatic dishwasher according to any one of claims 1 to 3, comprising a compound selected from (e) a polyalkylene glycol of the following formula (e1) and a surfactant of the following formula (e2). .
^{H-O- (R 1e O)} n -H (e1)
[Wherein R ^1e represents an ethylene group or a propylene group. n shows the average addition mole number of an ethyleneoxy group or a propyleneoxy group, and is the number of 10-1000. ]
^R2e- O-[( ^R3eO ) _l / ( ^R4eO ) _m ] -H (e2)
[Wherein, R ^2e is a hydrogen atom or a hydrocarbon group having 8 to 22 carbon atoms, R ^3e is an ethylene group, and R ^4e 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, respectively, and are 1 to 100, respectively. ] The cleaning composition for an automatic dishwasher according to claim 4, wherein (e) is (e1) . The cleaning composition for an automatic dishwasher according to claim 4 or 5, wherein (e) is polypropylene glycol . The cleaning composition for an automatic dishwasher according to any one of claims 1 to 6 , comprising (b1), (b2) and (b3) as (b). (A) it is an automatic dishwasher detergent composition of any one of claims 1 to 7 carbon atoms in the fatty acids are sorbitan fatty acid ester is 8 to 22.