JP2007119753A - Detergent composition for dish washer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent composition for a dish washer, without using a rinsing agent, speeding up the drying of the dishes at the same time with the removal of soil, enabling the reduction of water spots, and further in the case of repeatedly washing by the same detergent composition, capable of maintaining excellent finishing property. <P>SOLUTION: This detergent composition for the dish washer is provided by containing (A) a polymeric compound containing (a) a monomer unit having ≥1 kind of a group selected from an amino group and a quaternary ammonium group and (b) a monomer unit expressed by -SO<SB>2</SB>- in its molecule and containing 10-99 mol% monomer unit (a) based on the total monomer units and also 0.01-1 molar ratio of the monomer unit (b)/the monomer unit (a), and (B) a nonionic surfactant. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a detergent composition for use in a dishwasher. In particular, the present invention relates to a detergent composition for use in a commercial dishwasher. The cleaning composition for a dishwasher according to the present invention reduces the water spot by accelerating the drying of dishes and glasses at the same time as removing dirt in the cleaning of tableware such as ceramics, glass and plastic without using a rinse agent. Enable.

  A dishwasher is a facility for washing dishes such as dirty dishes, glasses and cooking utensils, and is used in kitchens such as homes, restaurants and coffee shops. In general, dishwashing is performed in the order of washing process-rinsing process. In the washing process, a non-foaming or low-foaming dishwasher cleaner different from a dishwashing detergent for hand washing is used. In addition, a rinsing agent is used in the rinsing process for commercial dishwashers used in kitchens such as restaurants and coffee shops.

  Rinse agents are used to speed up the drying of dishes and reduce the appearance of white spots called water spots. The water spot is dried before water droplets adhering to the surface of the tableware flow down, and hardness components such as calcium, magnesium and silica are deposited on the surface of the tableware. Especially in the case of glass tableware, the beauty is greatly impaired.

  Generally, nonionic surfactants such as glycerin fatty acid ester and sorbitan fatty acid ester are blended in the rinsing agent, and the rinsing water is emulsified to lower the surface tension with the tableware so that water droplets can easily flow down. As a result, the drying of the tableware is accelerated, and the water spot can be reduced. Therefore, rinsing agents are used in restaurants and coffee shops where tableware is frequently used.

  However, although the rinsing agent has an effect of reducing the water spot, it is never satisfactory, and a restaurant or a coffee shop is wiping with a towel to remove the water spot attached to the tableware. Moreover, since the rinse agent is used in the rinsing process, a supply device different from the cleaning agent used in the cleaning process is required. Furthermore, it is necessary to purchase a rinsing agent and to manage inventory, which is a big burden at restaurants and coffee shops.

Patent Document 1 contains a positively charged polymer, a water-soluble polymer that suppresses phosphate scale formation, and exhibits excellent cleaning effect and glass appearance even in the absence of sodium chloride or a rinse aid composition. A composition is disclosed. Patent Documents 2 and 3 disclose that a cationic or amphoteric polymer is used as a detergent for a dishwasher.
JP-T-2004-508456 WO99 / 58633 pamphlet European Patent Application No. 0835925

  Accordingly, an object of the present invention is to provide a dishwasher for cleaning dishes such as ceramics, glass, plastics, etc. without using a rinsing agent, and at the same time removing the stains and at the same time drying the dishes to reduce the water spot. It is to provide a cleaning composition. It is another object of the present invention to provide a cleaning composition for a dishwasher that can maintain excellent finish even when the tableware is repeatedly cleaned with the same cleaning composition.

The present invention includes (A) a monomer unit (a) having at least one group selected from an amino group and a quaternary ammonium group and a monomer unit (b) represented by —SO ₂ — in the molecule. And a polymer compound containing 10 to 99 mol% of the monomer unit (a) with respect to all the monomer units and having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1 [hereinafter, The present invention relates to a dishwasher cleaning composition containing (A) component] and (B) a nonionic surfactant (hereinafter referred to as component (B)).

  The present invention also relates to a tableware cleaning method, in which tableware is cleaned with a dishwasher using the detergent composition for a dishwasher of the present invention, and then rinsed with rinsing water containing no rinse agent. .

  According to the present invention, when used for washing tableware such as ceramics, glass, plastic, etc., it is possible to accelerate the drying of the tableware and reduce the water spot without using a rinsing agent in the rinsing water etc. A dishwasher cleaning composition is provided. In addition, the composition of the present invention can maintain excellent finish even when the tableware is repeatedly washed with the same detergent composition, and is excellent in sustainability of the effect.

<(A) component>
In the component (A), the molar ratio of the monomer unit (b) / monomer unit (a) is 0.01 to 1, preferably 0.03 to 0.75, particularly preferably 0.05 to 0.5. It is.

  As the monomer used for constituting the monomer unit (a), one or more selected from the compound represented by the following general formula (1) and the compound represented by the general formula (2) are preferable.

[Wherein, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 3 carbon atoms. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ⁶ become anions. Examples of the anion of Z ⁻ include a halogen ion, a sulfate ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms, and a hydroxy ion. Can be mentioned. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ]

  Specifically preferred as the compound of the general formula (1) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, acryloyl. (Or methacryloyl) oxyalkyl (C1-5) -N, N, N-trialkyl (C1-3) quaternary ammonium salt, N- (ω-alkenyl (C2-10))-N , N, N-trialkyl (carbon number 1 to 3) quaternary ammonium salt, N, N-di (ω-alkenyl (carbon number 2 to 10))-N, N-dialkyl (carbon number 1 to 3) 4 A quaternary ammonium salt is preferred, and diallyldimethylammonium salt is particularly preferred.

  Particularly preferred as the compound of the general formula (2) are acryloyl (or methacryloyl) aminoalkyl (C1-5) -N, N-dialkyl (C1-3) amine, acryloyl (or methacryloyl) oxyalkyl. (C1-5) -N, N-dialkyl (C1-3) amine, N- (ω-alkenyl (C2-10))-N, N-dialkyl (C1-3) amine N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine and diallylamine are preferable, and allylamine and diallylmethylamine are particularly preferable. , Diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, acryloyl (or methacryloyl) oxy Ethyl-N, N-dimethylamine is good.

  From the viewpoint of surface adsorption power, the component (A) is 10 to 99 mol%, preferably 30 to 90 mol%, more preferably 50 to 90 mol%, particularly preferably the monomer unit (a) based on the total monomer units. 60 to 80 mol% is contained. This mol% is calculated by [number of moles of monomer unit (a) / number of moles of all monomer units] × 100.

In the polymer of component (A), the monomer unit (b) is —SO ₂ —, and as a method for introducing such a monomer unit into the polymer, a predetermined amount of SO ₂ gas is added to the compound of the general formula (1). And / or blown into a solution containing the compound of general formula (2), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dilauroyl peroxide, azobisisobutyronitrile, azobisisovaleronitrile, 2, Polymerization initiation selected from 2'-azobis (2-amidinopropane), t-butyl hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, persulfate, and hydrogen peroxide It is obtained by polymerizing using an agent. A solvent can be used at the time of polymerization. Specifically, alcohols selected from water, methanol, ethanol and propanol, ketones selected from acetone and methyl ethyl ketone, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylimidazo Lydinone, acetonitrile, propionitrile, toluene, xylene and hexane can be used. The polymerization temperature varies depending on the combination of the solvent and the initiator, and is preferably -20 to 200 ° C, preferably -10 to 100 ° C. In the present invention, it is possible to polymerize with light or radiation, and it is possible to polymerize efficiently by irradiating light with a wavelength of 300 to 450 nm.

  From the viewpoint of finish, the molar ratio of monomer unit (b) / monomer unit (a) is 0.01 to 1, preferably 0.03 to 0.75, more preferably 0.05 to 0.5. is there.

  The component (A) of the present invention can be included as a structural unit derived from an anionic monomer (hereinafter referred to as a monomer unit (c)). In this case, the molar ratio of the monomer unit (a) to the monomer unit (c) Is preferably monomer unit (a) / monomer unit (c) = 10/90 to 90/10, more preferably 30/70 to 90/10, and particularly preferably 50/50 to 80/20. Examples of the anionic monomer include monomers selected from the following (i).

  (I) Acrylic acid or its salt, methacrylic acid or its salt, maleic acid or its salt, maleic anhydride, styrene sulfonate, 2-acrylamido-2-methylpropane sulfonate, allyl sulfonate, vinyl sulfonic acid Compound selected from salt, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (C1-12)

  In addition, the component (A) of the present invention can also be included as a structural unit derived from a nonionic monomer (hereinafter referred to as monomer unit (d)). Examples of the nonionic monomer include monomers selected from the following (ii) to (iv).

  (Ii) Acrylic (or methacrylic) amide, N, N-dimethylaminopropylacrylic acid (or methacrylic acid) amide, N, N-dimethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic acid (or methacrylic) Acid) amide, N, N-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound

  (Iii) 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 carbon atom) -5), ester group-containing compound selected from vinyl acetate

  (Iv) ethylene, propylene, n-butylene, isobutylene, n-pentene, isoprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl Olefin compounds selected from -1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene, and α-methylstyrene

  Among these, from the viewpoint of finish, a monomer unit derived from the monomer (i) or (ii) is particularly preferable, and a monomer unit derived from the monomer (i) is most preferable. Among these, acrylic acid or its sodium salt or Preference is given to potassium salt, methacrylic acid or its sodium or potassium salt, maleic acid or its sodium or potassium salt. Here, the counter ion of the monomer unit derived from the monomer (i) may be a cationic group portion of the polymer to be contained.

  When the component (A) has the monomer unit (d), the molar ratio of the monomer unit (d) / monomer unit (a) is 0.05 to 1, and more preferably 0.1 to 0.00 from the viewpoint of finish. 75, especially 0.2 to 0.5 is preferred.

  The polymer of the present invention preferably has a weight average molecular weight of 1,000 to 6,000,000, more preferably 1,000 to 500,000, still more preferably 1,000 to 100,000, and particularly preferably 5,000. The weight average molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance with a mixed solvent of acetonitrile and water (phosphate buffer solution) as a developing solvent.

  In the polymer of the component (A) used in the present invention, the monomer unit (a), the monomer unit (b), and preferably the monomer units (c) and (d) are present in either the main chain or the side chain in the polymer. It does not matter if it exists. These may be randomly polymerized, block polymerized, or graft polymerized. In the present invention, it is most preferable to use a polymer composed only of the monomer unit (a), the monomer unit (b) and the monomer unit (c).

<(B) component>
The component (B) is not particularly limited, but glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene Examples include alkyl ether, polyoxyethylene dialkyl ether, polyoxyethylene glycol, polyoxyethylene oxypropylene glycol, polyoxypropylene oxyethylene oxypropylene glycol and the like.

From the viewpoint of detergency, a nonionic surfactant represented by the following general formula (3) [hereinafter referred to as component (B1)] is preferably used.
_{^{R 14 - (AO) n -R}} 15 (3)
[In formula, R <^14> , R < ¹⁵ > is respectively independently a hydrogen atom or a C1-C24 hydrocarbon group. n is an average addition mole number, and is a number of 1-500. AO is the same or different and is an oxyethylene group, an oxypropylene group, or an oxybutylene group. ]

In the general formula (3) of the component (B1), R ¹⁴ and R ¹⁵ are each independently preferably a hydrogen atom or a linear or branched alkyl group having 1 to 24 carbon atoms, more preferably a hydrogen atom, Or a linear or branched alkyl group having 6 to 18 carbon atoms, particularly preferably a hydrogen atom, or a linear or branched alkyl group having 8 to 14 carbon atoms. Moreover, in general formula (3), n is an average addition mole number, Preferably it is 1-400, More preferably, it is 1-350, More preferably, it is 1-200, Most preferably, it is a number of 1-100. Moreover, in General formula (3), AO is the same or different, Preferably they are an ethylene group and a propylene group.

Furthermore, from the viewpoint of detergency, non-foaming property and low-foaming property, one type selected from the nonionic surfactant represented by the following general formula (4) and the nonionic surfactant represented by the general formula (5) The above nonionic surfactant [hereinafter referred to as component (B2)] is preferred.
HO (CH ₂ CH ₂ O) _a (CH (CH ₃ ) CH ₂ O) _b (CH ₂ CH ₂ O) _c H (4)
HO (CH (CH ₃ ) CH ₂ O) _d (CH ₂ CH ₂ O) _e (CH (CH ₃ ) CH ₂ O) _f H (5)
[Wherein, a, b, c, d, e and f are the average number of moles added, each independently a number of 1 to 350. ]

  In the general formulas (4) and (5), a, b, c, d, e and f are the average number of moles added of ethylene oxide (hereinafter referred to as EO) or propylene oxide (hereinafter referred to as PO). Yes, each independently a number from 1 to 350.

  The component (B2) preferably contains 10 mol% or more of EO in the total of EO and PO, and a, b, c, d, e and f are preferably selected so as to satisfy this.

  Moreover, 1,000-15,000 are preferable and, as for the weight average molecular weight of (B2) component, More preferably, it is 1,500-6,000. The component (B2) is available from BASF under the trade names “Pluronic” and “Pluronic R”. As the component (B2), a nonionic surfactant represented by the formula (5) is preferable from the viewpoint of low foamability.

In addition, from the viewpoint of finish, one or more nonionic surfactants selected from nonionic surfactants represented by the following general formula (6) and nonionic surfactants represented by the general formula (7) [ (Hereinafter referred to as component (B3)) is preferred.
_{^{R 16 -O- (EO) p -}} (PO) q - (EO) r -H (6)
[Wherein R ¹⁶ represents a linear alkyl group having 8 to 18 carbon atoms or a linear alkenyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q, and r represent average addition mole numbers, respectively, p = 1-10, q = 0.5-5, r = 1-10. ]
R ¹⁷ —O— (EO) _s — (PO) _t —H (7)
[Wherein, R ¹⁷ represents a branched alkyl group having 8 to 18 carbon atoms or a branched alkenyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. s and t each represent an average added mole number, s = 4 to 10, t = 2 to 10, and 0.3 ≦ (t / s) ≦ 1.5. ]

In the general formula (6), R ¹⁶ is preferably a linear alkyl group having 10 to 14 carbon atoms or a linear alkenyl group, and more preferably a linear alkyl group having 10 to 14 carbon atoms, and p = 2 to 8 is preferable. Q = 0.5 to 4.5, more preferably 1 to 4.5, and particularly preferably 1 to 2, r = 2 to 8 is preferable, p + r = 1 to 30, further 2 to 20, and particularly 4 to 15 are preferable. . Specific examples of the nonionic surfactant of the general formula (6) include polyoxyethylene (3) polyoxypropylene (1.5) polyoxyethylene (3) lauryl ether, polyoxyethylene (5) polyoxypropylene (1 .5) Polyoxyethylene (5) lauryl ether, polyoxyethylene (5) polyoxypropylene (4.5) polyoxyethylene (5) lauryl ether, and the like. Here, regarding the said compound, the inside of () is the average addition mole number of ethylene oxide or propylene oxide (the same applies hereafter).

In the general formula (7), R ¹⁷ is preferably a branched alkyl group having 10 to 14 carbon atoms or a branched alkenyl group, and more preferably a branched alkyl group having 10 to 14 carbon atoms. Among the branched alkyl groups having 10 to 14 carbon atoms or branched alkenyl groups represented by R ^17, a secondary alkyl group or secondary alkenyl group having 10 to 14 carbon atoms is preferable. In General formula (7), s = 5-9 is preferable and t = 5-10 is preferable. Specific examples of the nonionic surfactant of the general formula (7) include polyoxyethylene (7) polyoxypropylene (8.5) -sec-dodecyl ether, polyoxyethylene (7) polyoxypropylene (8.5). -Sec-tridecyl ether, polyoxyethylene (7) polyoxypropylene (8.5) -sec-tetradecyl ether, and the like.

In the compound of the general formula (7), EO is added to a branched (preferably secondary) alcohol having a branched (preferably secondary) alkyl group or branched (preferably secondary) alkenyl group of R ^17. Then, it can be synthesized by adding PO.

  Further, the weight average molecular weight of the component (B3) is preferably 200 to 5,000, more preferably 200 to 2,000. Among the components (B3), the compound of general formula (6) is available from Kao Corporation under the trade name “Emulgen”, and the compound of general formula (7) is Nippon Shokubai under the trade name “Softanol”. Available from Co., Ltd. As the component (B3), a nonionic surfactant represented by the general formula (6) is preferable from the viewpoint of finish.

  The dishwasher cleaning composition of the present invention can contain a compound called a builder. As the action mechanism of the builder, a metal chelate action, an alkali buffer action, and a solid particle dispersion action are important.

  Examples of inorganic builders include phosphates, carbonates, silicates, and sulfates. Specific examples include sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium orthophosphate, sodium hexametaphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate, sodium silicate, potassium silicate, sodium metasilicate, and the like. It is done.

  Examples of the organic builder include (a) ethane-1,1-diphosphonic acid, ethane-1,2-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2 -Phosphonic acid salts such as triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, (b) 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2 , 3,4-tricarboxylic acid, salts of phosphonocarboxylic acids such as α-methylphosphonosuccinic acid, (c) salts of amino acids such as aspartic acid and glutamic acid, (d) nitrilotriacetate, ethylenediaminetetraacetate Aminopolyacetate, (e) diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, cyclopentane-1,2 3,4-tetracarboxylic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid, tetrahydrofuran-2,2,5,5-tetracarboxylic acid, citric acid, lactic acid, tartaric acid, oxalic acid, sulfosuccinic acid, apple Examples thereof include salts of acids and organic acids such as gluconic acid, (f) polyacrylic acid salts, polyacrylic acid / polymaleic acid copolymer polymers and salts thereof.

  From the viewpoint of detergency, ion sequesterability, and anti-recontamination property, the total builder amount is preferably 10 to 99.9% by weight, more preferably 20 to 99, based on the detergent composition for dishwashers of the present invention. % By weight, particularly preferably 30 to 95% by weight.

  Moreover, the organic polymer compound of the powder which has the water absorption by a hydrogen bond can be contained. Specifically, dextrin, carrageenan, xanthan gum, guar gum, pectin, locust bin gum, or derivatives thereof, polysaccharides such as modified starch, methylcellulose, carboxymethylcellulose, synthetic polymer compounds such as polyvinyl alcohol, polyacrylamide, polyethylene oxide, etc. Is mentioned. From the viewpoint of storage stability, these are preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight, and particularly preferably 1 to the detergent composition for a dishwasher of the present invention. -10% by weight.

  In addition, anionic surfactants, nonionic surfactants other than component (B), amphoteric surfactants, enzymes, bleaching agents, antifoaming agents, rust preventives, hydrotropes, surface modifiers, fragrances, etc. Can be contained.

  As the above components, those described in International Publication No. 99/58633 pamphlet can be referred to.

<Cleaning composition for dishwasher>
In the detergent composition for a dishwasher of the present invention, the component (A) is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, from the viewpoint of finish. More preferably 0.1 to 3% by weight. Particularly preferably, the content is 0.5 to 2% by weight.

  In the detergent composition for a dishwasher of the present invention, the component (B) is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight, and still more preferably 0, from the viewpoint of detergency. 0.1 to 20% by weight, particularly preferably 0.5 to 10% by weight.

  In addition, the detergent composition for a dishwasher of the present invention is preferably used as a cleaning liquid diluted to an appropriate concentration with water or the like in use, and the concentration of the component (A) in the cleaning liquid is finished. From a viewpoint of property, Preferably it is 0.1-100 ppm (weight ratio), More preferably, it is 0.5-80 ppm, More preferably, it is 1-50 ppm, Most preferably, it is 3-30 ppm. The concentration of the component (B) in the cleaning liquid is preferably 0.1 to 1,000 ppm, more preferably 0.5 to 500 ppm, still more preferably 1 to 100 ppm, and particularly preferably 5 from the viewpoint of cleaning power. -50 ppm.

  In the detergent composition for a dishwasher according to the present invention, the weight ratio of the component (A) to the component (B) is (A) / (B) = 20/1 to 1 from the balance between the finish and the cleanability. / 20, 10/1 to 1/10, 5/1 to 1/5, 3/1 to 1/5, 3/1 to 1/2, especially 1.5 / 1 to 1/2. preferable.

  When the component (B) is the component (B3), the weight ratio of the component (A) to the component (B3) in the detergent composition for a dishwasher according to the present invention is such that the finish, washability and economy are high. (A) / (B3) = 20/1 to 1/20, further 10/1 to 1/10, further 5/1 to 1/10, further 3/1 to 1/10, 2/1 to 1/10, further 1/1 to 1/10, more preferably 1/2 to 1/8, and particularly preferably 1/4 to 1/6.

  In the case of washing with a commercial dishwasher using the detergent composition for a dishwasher of the present invention, the composition is arbitrarily transferred into a commercial dishwasher by a supply device, and the proper composition is transferred. The concentration of the cleaning solution is maintained. When the product form of the dishwasher detergent composition is liquid, the tube dedicated to the dishwasher for business use is directly inserted into a plastic container filled with the dishwasher detergent composition. Supplied. When the form of the detergent composition for a dishwasher is solid or powder, the plastic dish or the like container filled with the detergent composition for a dishwasher is placed in a predetermined direction. Set or transfer the dishwasher cleaning composition filled in a pouch container etc. to a commercial dishwasher hopper, spray water or warm water with a spray or shower, etc. The cleaning solution dissolved and sprayed is supplied to the inside of the commercial dishwasher.

  The cleaning composition for a dishwasher of the present invention is used at a concentration of 0.04 to 0.5% by weight in the cleaning liquid, but from the viewpoint of economy and cleaning properties, 0.05 to 0.3% by weight. % Is preferable, and 0.07 to 0.25% by weight is more preferable. The washing time for tableware is preferably 10 seconds to 3 minutes, more preferably 20 seconds to 2 minutes, from the viewpoint of detergency. The cleaning temperature of the cleaning liquid is very important for improving the cleaning performance in a short time, and is preferably 40 ° C. or more, and particularly preferably 40 to 70 ° C. After the dishes are washed, they are usually rinsed quickly with water, warm water or hot water at 70-90 ° C. in the same commercial dishwasher. The cleaning composition for a dishwasher of the present invention can speed up drying of dishes and reduce water spots without using a rinse agent, so that rinsing can be performed with water, warm water or 70-90 ° C. It can be done only with hot water.

  In a commercial dishwasher, when washing dishes continuously, the cleaning liquid is circulated with a pump and repeatedly used for washing.

  In the case of continuously washing dishes with a commercial dishwasher, the concentration of the washing liquid decreases with the number of washings due to carry-out of the washing liquid by tableware or carry-over of rinsing water to the washing tank. In order to maintain an appropriate concentration of the cleaning liquid, the dishwasher cleaning composition is supplied to an appropriate concentration by an automatic supply device.

  The automatic supply apparatus for the dishwasher cleaning composition is not particularly limited, but the product form of the dishwasher cleaning composition is liquid by sensing the concentration of the cleaning liquid and receiving a signal. If it is, if it is powder or solid, spray water or warm water on the dishwasher detergent composition in the form of a spray or shower to obtain the required amount of dishwasher detergent. Supply the composition.

  This automatic supply device is preferably used for business use with a very large number of cleanings per day, and has the advantage that it saves a lot of time compared to manual feeding for each cleaning frequency. It becomes easy to maintain a proper concentration in the middle (during washing).

  A detergent composition for a dishwasher having the composition shown in Table 1 was prepared, and the washability and finishability (drying speed and water spot) were evaluated by the following methods. The results are shown in Table 1.

[1] Evaluation of detergency and production of model dirt On the center of a new 20 cm diameter porcelain dish, 4 g of egg yolk was uniformly applied with a brush in a circular shape with a diameter of about 16 cm and placed in an electric dryer set at 80 ° C. . After 30 minutes, a porcelain dish coated with egg yolk was taken out, and naturally cooled was used as model dirt for evaluation of detergency.

Evaluation Method 19 g of the dishwasher detergent composition was put into a washing tank (38 L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] and dissolved in hot water at 50 ° C. Four pieces of porcelain dishes coated with model dirt were set on a dedicated rack, washed for 40 seconds with a cleaning solution at 50 ° C., and then rinsed with rinsing water at 80 ° C. for 8 seconds without using a rinse agent. The porcelain dish was taken out from the dedicated rack, colored with a 1% by weight aqueous solution of erythrosin dye, and the detergency was evaluated according to criteria 1 shown below.

* Judgment criteria for cleanability ◎: No colored traces are observed, dirt is completely removed ○: Slightly colored traces are observed, but most of the dirt is removed Δ; Residual x: Mostly colored marks are observed and a lot of dirt remains.

  The results are shown in Table 1. It was revealed that the detergent composition for a dishwasher of the present invention is excellent in detergency.

[2] Finishability Evaluation / Production of Model Dirt After applying 1 g of milk to a new 8 ounce glass, the product dried at 60 ° C. for 2 hours was used as the model dirt for evaluation of the finish.

Evaluation method 19 g of the detergent composition for a dishwasher was placed in a washing tank (38 L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] and dissolved in hot water at 50 ° C. Four 8-ounce glasses coated with model dirt were set on a dedicated rack, washed with a cleaning solution at 50 ° C. for 40 seconds, and then rinsed with rinsing water at 80 ° C. for 8 seconds without using a rinse agent. An 8 ounce glass was taken out from the dedicated rack and dried at 25 ° C. The finishing criteria related to the drying speed and water spot were evaluated according to the following criteria.

* Criteria for drying speed A: Average per glass, dried in less than 1 hour ○; Average, per glass 1 hour or more, less than 1 hour 30 minutes Δ; Average per glass 1 hour 30 minutes or more and less than 2 hours, dried x; average of 2 hours or more per glass

* Judgment criteria for water spots ◎; The average number of water spots is less than 10 per glass ○: The average number of water spots is 10 or more and less than 20 per glass Δ; The number of water spots is 20 to less than 40 on average per glass ×; the number of water spots on average 40 or more per glass

  The results are shown in Table 1. It became clear that the cleaning composition for dishwashers of the present invention accelerates drying and reduces water spots without using a rinse agent in the rinsing water.

[3] Finishing property evaluation after repeated washing 1 kg of a detergent composition for dishwashers was charged in a dedicated hopper (EW-9000 manufactured by Kao Corporation) of a commercial dishwasher. Next, using an automatic supply device (KPR-2000 manufactured by Kao Corporation), the concentration of the cleaning liquid was set to 0.05% by weight, and a commercial dishwasher (SANYO manufactured by SANYO) DR53). Washing was repeated as described below, and the finishing properties related to the drying speed and water spot were evaluated according to the criteria shown above.

  Four 8-ounce glasses coated with model dirt were set on a dedicated rack, washed with a cleaning solution at 50 ° C. for 40 seconds, and then rinsed with rinsing water at 80 ° C. for 8 seconds without using a rinse agent. After removing 8 ounce glass from the dedicated rack and drying at 25 ° C., model dirt was again applied to the 8 ounce glass by the method described above. The above-mentioned cycle was repeated 20 times using the cleaning solution in a circulating manner to evaluate the finish.

  The results are shown in Table 1. It became clear that the cleaning composition for a dishwasher of the present invention accelerates drying and reduces water spots even after 20 cycles of cleaning.

(Note) The components in the table are as follows. Further, in a part of the comparative examples, the weight ratio (A) / (B) was calculated using the polymer compound D as the component (A).
-Modified starch: oxidized starch (Lactway 2, manufactured by Matsutani Chemical Co., Ltd.)
Polymer compound A: a copolymer of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 70/25/5) (used as an aqueous solution having an effective content of 25% by weight, and the amount of the aqueous solution is shown in the table) .)
Polymer compound B: copolymer of diallyldimethylammonium chloride and SO ₂ (molar ratio 50/50) (used as an aqueous solution having an effective content of 50% by weight, the amount of the aqueous solution is shown in the table)
Polymer compound C: a copolymer of diallyldimethylammonium chloride, maleic acid, and SO ₂ (molar ratio 50/25/25) (used as an aqueous solution having an effective content of 25% by weight, and the amount of the aqueous solution is shown in the table) .)
-High molecular compound D: a copolymer of diallyldimethylammonium chloride and acrylic acid (molar ratio 64/36), Merquat 280 (Calgon, used as an aqueous solution with an effective content of 40% by weight. The amount of the aqueous solution is shown in the table. )
・ Nonionic surfactant A: PO / EO / PO block polymer, Pluronic RPE2520 (BASF)
・ Nonionic surfactant B: EO / PO / EO block polymer, Pluronic PE9200 (BASF)
Nonionic surfactant C: aliphatic alcohol alkoxylate, Plurafac LF403 (manufactured by BASF)
Nonionic surfactant D: branched chain aliphatic alcohol alkoxylate, softanol 70H [manufactured by Nippon Shokubai Co., Ltd., in general formula (3), R ¹⁴ is a secondary alkyl group having 12 to ¹⁴ carbon atoms, and R ¹⁵ is (Hydrogen atom, n = 7)
Nonionic surfactant E: polyoxyethylene (EO average addition mole number 5) lauryl ether, Emulgen 106 [manufactured by Kao Corporation]
Nonionic surfactant F: Emulgen LS106 [manufactured by Kao Corporation, in general formula (6), R ¹⁶ is a linear alkyl group having 12 to 14 carbon atoms, p = 3, q = 1.5, r = 3 things]
Nonionic surfactant G: Softanol EP7085 [manufactured by Nippon Shokubai Co., Ltd., in general formula (7), R ¹⁷ is a secondary alkyl group having 12 to 14 carbon atoms, s = 7, t = 8.5 ]
・ Acrylic acid / maleic acid copolymer, sodium salt: Sokalan CP5 Granules (BASF)

Claims (7)

(A) The monomer unit has a monomer unit (a) having at least one group selected from an amino group and a quaternary ammonium group, and a monomer unit (b) represented by —SO ₂ — in the molecule. A polymer compound containing 10 to 99 mol% of (a) with respect to all monomer units and having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1, and (B) nonionic properties A detergent composition for a dishwasher comprising a surfactant. The dishwasher according to claim 1, wherein the monomer unit (a) of the polymer compound (A) is derived from a compound represented by the following general formula (1) and / or a compound represented by the general formula (2). Detergent composition.

[In formula, R < ¹ >, R < ² >, R < ³ >, R < ⁷ >, R <^8> , R <^9> is respectively independently a hydrogen atom, a hydroxyl group, or a C1-C3 alkyl group. X, Y are each independently an alkylene group having 1 to 12 carbon ^{atoms, -COOR 12 -, - CONHR 12} -, - OCOR 12 -, - a group selected from - R ¹³ -OCO-R ^12. Here, R ¹² and R ¹³ are each independently an alkylene group having 1 to 5 carbon atoms. R ⁴ is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ¹ R ² C═C (R ³ ) —X—. R ⁵ is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ⁶ is an alkyl group having 1 to 10 carbon atoms that may be substituted with a hydroxy group, a carboxyl group, a sulfonic acid group, or a sulfate group. When it is an alkyl group or a benzyl group, and R ⁶ is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ⁶ contains a carboxyl group, a sulfonic acid group or a sulfate ester group, Z − does not exist and these groups in R ⁶ become anions. R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ⁷ R ⁸ C═C (R ⁹ ) —Y—. R ¹¹ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group. ] The detergent composition for a dishwasher according to claim 1 or 2, wherein the (B) nonionic surfactant is a nonionic surfactant represented by the following general formula (3).
_{^{R 14 - (AO) n -R}} 15 (3)
[In formula, R <^14> , R < ¹⁵ > is respectively independently a hydrogen atom or a C1-C24 hydrocarbon group. n is an average addition mole number, and is a number of 1-500. AO is the same or different and is an oxyethylene group, an oxypropylene group, or an oxybutylene group. ] The (B) nonionic surfactant is at least one selected from a nonionic surfactant represented by the following general formula (4) and a nonionic surfactant represented by the general formula (5). The cleaning composition for dishwashers in any one of Claims 1-3.
HO (CH ₂ CH ₂ O) _a (CH (CH ₃ ) CH ₂ O) _b (CH ₂ CH ₂ O) _c H (4)
HO (CH (CH ₃ ) CH ₂ O) _d (CH ₂ CH ₂ O) _e (CH (CH ₃ ) CH ₂ O) _f H (5)
[Wherein, a, b, c, d, e and f are the average number of moles added, each independently a number of 1 to 350. ] The (B) nonionic surfactant is at least one selected from a nonionic surfactant represented by the following general formula (6) and a nonionic surfactant represented by the general formula (7). The cleaning composition for dishwashers in any one of Claims 1-3.
_{^{R 16 -O- (EO) p -}} (PO) q - (EO) r -H (6)
[Wherein R ¹⁶ represents a linear alkyl group having 8 to 18 carbon atoms or a linear alkenyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. p, q, and r represent average addition mole numbers, respectively, p = 1-10, q = 0.5-5, r = 1-10. ]
R ¹⁷ —O— (EO) _s — (PO) _t —H (7)
[Wherein, R ¹⁷ represents a branched alkyl group having 8 to 18 carbon atoms or a branched alkenyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group. s and t each represent an average added mole number, s = 4 to 10, t = 2 to 10, and 0.3 ≦ (t / s) ≦ 1.5. ] The weight ratio of the (A) polymer compound to the (B) nonionic surfactant is (A) / (B) = 20/1 to 1/20. Detergent composition for dishwashers. Tableware washing | cleaning which wash | cleans tableware with a dishwasher using the cleaning composition for dishwashers of any one of Claims 1-6, and performs a rinsing process with the rinse water which does not contain a rinse agent after that. Method.