JP4799985B2 - Detergent composition for automatic dishwasher - Google Patents

Description

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

  The technique which applies the high molecular compound which has a cationic group to the cleaning composition for automatic dishwashers is already known, and patent documents 1-3 can be referred to.

Further, polymer compounds containing —SO ₂ — as a monomer constituent unit in the molecule are already known, and Patent Documents 4 to 5 can be referred to.

On the other hand, the present applicant discloses that a high molecular compound containing —SO ₂ — as a monomer constituent unit in a molecule is blended in a cleaning agent (Patent Document 6).
WO99 / 58633 pamphlet International Publication No. 02/20709 Pamphlet European Patent Application No. 0998548 Japanese Patent Publication No.51-18280 Japanese Patent Publication No.53-10539 JP 2003-313600 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 with such a washing machine, there is a problem that white deposits known as so-called water spots are often formed on the dishes after washing / drying. This solution is strongly demanded.

Patent Document 1 discloses a technique of applying a cationic polymer compound or an amphoteric polymer compound as a cleaning agent technique for suppressing the formation of water spots. This publication is evaluated by directly adding an aqueous polymer together with a cleaning composition to an automatic dishwashing machine, and a technique using 5% by mass of polymer with respect to the composition is described in the examples. Yes. However, when this technique is applied to dishwashing with a large amount of dirt, there is a problem that the effect of suppressing the formation of water spots cannot be obtained. Further, even if the polymer content is increased for the purpose of improving the effect, the expected improvement effect cannot be obtained.

Patent Document 2 discloses a technique of applying a cationic polymer compound or an amphoteric polymer compound as a phosphoric acid scale formation inhibitor and Patent Document 3 as a fading or corrosion inhibitor. These publications are also evaluated by directly adding an aqueous polymer together with a cleaning composition to an automatic dishwasher, and a technique using 1.5 to 5% by mass of polymer with respect to the composition is implemented. It is described in the example. However, by adding a polymer compound containing —SO ₂ — as a monomer constituent unit in the molecule to the cleaning composition, it is possible to obtain a water spot formation suppressing effect when applied to dishwashing with a large amount of dirt. There is no suggestion of what can be done.

Patent Document 4 discloses that a polymer compound containing —SO ₂ — as a monomer constituent unit in the molecule is useful as a paint or an adhesive. Patent Document 5 discloses that a polymer compound containing —SO ₂ — as a monomer constituent unit is useful as a metal corrosion inhibitor. However, these publications do not suggest any effect of suppressing the formation of water spots when applied to dishwashing with a large amount of dirt, and the polymer compounds described in the examples of these publications are satisfactory. A water spot formation inhibitory effect cannot be obtained.

On the other hand, in Patent Document 6, when a polymer containing —SO ₂ — as a monomer constituent unit is used as a neutral to weakly acidic antifouling detergent, it is possible to remove dirt, prevent adhesion, and easily wash. However, satisfactory performance was not obtained even when used as a detergent composition for an automatic dishwasher.

  Therefore, the subject of this invention is providing the cleaning composition for automatic dishwashers which is excellent in the water spot formation inhibitory effect, when it applies to the dishwashing with much dirt amount.

The present invention has a monomer structural unit A having a cationic group and a monomer structural unit B represented by —SO ₂ —, and the monomer structural unit A is 10 to 99 mol% based on all monomer structural units. And a polymer (a) [hereinafter referred to as component (a)] having a molar ratio of monomer structural unit B / monomer structural unit A of 0.01 to 1, alkali agent (b) [hereinafter referred to as (b) And a detergent composition for an automatic dishwasher in which the pH of a 0.2 mass% aqueous solution at 20 ° C. is 9.0 to 14.0.

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for automatic dishwashers which is excellent in the water spot formation inhibitory effect when it applies to dishwashing with much dirt amount is provided.

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

  As the monomer used for constituting the monomer structural 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. The monomer structural unit A is contained in a proportion of 10 to 99 mol% with respect to all monomer structural units. Preferably it is contained in a proportion of 20 to 99 mol%, more preferably 30 to 90 mol%.

In the polymer of component (a), the monomer structural unit B is —SO ₂ —. As a method for introducing such a monomer structural 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 the 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.

  By adding the monomer structural unit B, a water spot formation inhibitory effect can be obtained even when applied to dishwashing with a large amount of dirt.

  In the present invention, a monomer derived from a monomer selected from the following (i) to (iv) for the purpose of further improving the water spot formation inhibiting effect even when applied to dishwashing with a large amount of dirt: It is preferable to contain the structural unit C.

(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 Salt, methallyl sulfonate, sulfopropyl methacrylate, mono-ω-methacryloyloxyalkyl phosphate (1 to 12 carbon atoms)
(Ii) 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-dimethylaminomethylacrylic acid (or methacrylic acid) amide, N-vinyl-2-caprolactam, N-vinyl-2-pyrrolidone-containing compound (iii) Acrylic acid (or methacrylic acid) alkyl (carbon Formula 1-5), ester group-containing compound selected from acrylic acid (or methacrylic acid) 2-hydroxyethyl, acrylic acid (or methacrylic acid) -N, N-dimethylaminoalkyl (C1-5), and vinyl acetate (Iv) ethylene, propylene, n-butylene, isobutylene, n-pentene, Soprene, 2-methyl-1-butene, n-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-butene, styrene, vinyltoluene Olefin compounds selected from α-methylstyrene

  Among these, the monomer constituent unit derived from the monomer (i) or (ii) is preferable from the viewpoint of the effect of suppressing the formation of water spots when applied to dishwashing with a particularly large amount of dirt, and among them, the monomer derived from the monomer (i) The structural unit is most preferred, and among these, acrylic acid or its sodium or potassium salt, methacrylic acid or its sodium or potassium salt, maleic acid or its sodium or potassium salt is preferred. Here, the counter ion of the monomer constituent unit derived from the monomer (i) may be a cationic group portion of the polymer to be contained.

  When the component (a) has a monomer structural unit C, the molar ratio of monomer structural unit C / monomer structural unit A is 0.05 to 1, more preferably 0.1 to 0. 75, especially 0.2 to 0.5 is preferred.

  The polymer of the component (a) 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, particularly Preferably, it is 5,000-60,000, and this weight average molecular weight is obtained by using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent and using polyethylene glycol as a standard substance by gel permeation chromatography. is there.

  In the polymer of component (a) used in the present invention, the monomer structural unit A, the monomer structural unit B, and preferably the monomer structural unit C may be present in either the main chain or the side chain in the polymer. . 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 structural unit A, the monomer structural unit B, and the monomer structural unit C.

  The component (a) is preferably 0.05 to 5% by mass, preferably 0.1 to 3% by mass, more preferably 0.25 to 2% by mass in the cleaning composition for an automatic dishwasher of the present invention. It is preferable to contain.

<(B) component>
The cleaning composition for an automatic dishwasher of the present invention contains an alkaline agent (component (b)). As a preferable alkali agent, in addition to an alkali metal such as sodium hydroxide or an alkaline earth metal hydroxide, an inorganic salt selected from carbonates and silicates can suppress variation in pH due to dirt. preferable. Particularly, carbonates include sodium carbonate and potassium carbonate. You may adjust using the commercially available dense ash whose average particle diameter is 50-600 micrometers. As the silicate, amorphous sodium silicate such as No. 1-3 sodium silicate can be used, or 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 product name “Prefeed” (δ-Na ₂ Crystalline sodium silicate marketed as Si ₂ O ₅ ) can also be used to impart alkalinity.

  The alkaline agent is preferably in the range of 1 to 80% by mass, more preferably 5 in the composition, so that the pH of the 0.2% by mass aqueous solution of the composition of the present invention at 20 ° C. is 9.0 to 14.0. -70 mass%, Most preferably, it contains 5-40 mass%.

  In the present invention, it is particularly preferable to use sodium silicate and sodium carbonate in combination. As the sodium silicate, layered sodium silicate is most preferably used. Sodium silicate is preferably obtained by granulating fine particles into an average particle diameter of 1 to 1000 μm, particularly 5 to 800 μm. Sodium carbonate is preferably granulated to have an average particle size of 50 to 600 μm, particularly 100 to 500 μm. Sodium silicate is preferably 1-20% by weight in the composition, more preferably 3-10% by weight, while sodium carbonate is preferably 1-80% by weight in the composition, more preferably 5-40% by weight. It is.

  The pH of the 0.2 mass% aqueous solution at 20 ° C of the detergent composition for an automatic dishwasher of the present invention is 9.0 to 14.0, preferably 9.5 to 14.0, more preferably 10. 0-12.0 alkalinity is shown. When the pH is within this range, good cleaning performance and sufficient water spot prevention effect can be obtained. In order to fully utilize the effect of the component (a), an appropriate pH is required. The pH is adjusted by the alkali agent and an acid agent (for example, an organic acid such as citric acid or a salt thereof).

<Other ingredients>
The cleaning composition for an automatic dishwasher of the present invention preferably contains an inorganic peroxide as the component (c) and an enzyme as the component (d).

  The component (c) is an inorganic peroxide. Specifically, percarbonate, preferably sodium percarbonate (hereinafter sometimes referred to as PC), perborate, preferably sodium perborate is suitable. Moreover, when employ | adopting a percarbonate, it is suitable to use the coated percarbonate from the point of storage stability.

  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 Patent No. 4131562 (PC coated with sodium perborate and alcohol ethylene oxide adduct), US Patent No. 4120812 (PC and sodium perborate coated 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 of the present invention can be prepared by conventional methods. 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 coated percarbonate has an average particle size of preferably 100 to 2000 μm, more preferably 250 to 1000 μm, from the viewpoint of the bleaching washing effect. Moreover, content in a composition becomes like this. Preferably it is 0.5-99 mass%, More preferably, it is 5-70 mass%, Most preferably, it is 5-50 mass%.

  In the present invention, it is preferable to contain an enzyme as the component (d), and examples include cellulase, protease, lipase, amylase, esterase, pectinase, lactase and peroxidase, and protease and amylase are particularly preferable.

  Examples of commercially available enzymes that can be used as proteases include alcalase, sabinase, evalase, cannase, esperase (Novo Nordisk Bioindustry Co., Ltd.), ovozyme, plafect, properase, and perfect OX (Genencore International). .

  Examples of commercially available enzymes that can be used as amylases include Lapidase (Gist-Brokers), Termamyl, Duramil, Steinzyme (Novo Nordisk Bioindustry Co., Ltd.), Plaster ST, Plaster OxAm (Genencor International). it can.

  In the present invention, these enzymes are preferably contained as granulated particles. The amount of enzyme protein in the granulated product is 1 to 30% by mass, preferably 2 to 25% by mass in the granulated product. The average particle size of the enzyme particles is 50 to 1000 μm, preferably 150 to 800 μm. Moreover, the content of the enzyme granulated product is preferably 0.1 to 10% by mass, more preferably 0.2 to 7% by mass, and particularly preferably 0.2 to 5% by mass in the composition.

  In the present invention, it is preferable to use protease and amylase in combination, and the amount of enzyme protein is amylase / protease (mass ratio) of 1/99 to 94/6, preferably 2/98 to 90/10, particularly preferably 20/80. ~ 80/20.

  In the cleaning composition for an automatic dishwashing machine of the present invention, blending polypropylene glycol having a weight average molecular weight of 600 to 5000, preferably 2000 to 4000, imparts a cleaning effect, and gives the tableware after washing. It is preferable because the residual fragrance can be suppressed. Polypropylene glycol is liquid at 20 ° C. Since polypropylene glycol is hydrophobic, when blending polypropylene glycol in a powder composition, in order to obtain sufficient dispersibility in water, 40% by mass or more of the powder components constituting the powder cleaning composition. It is preferable that polypropylene glycol is mixed with a corresponding amount of the components and blended so as to adjust to the whole.

  Polypropylene glycol is preferably contained in the composition in an amount of 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, particularly 1 to 5% by mass.

  In the present invention, optional components include surfactants, organic acid salts such as citrate and succinate, extenders such as sodium sulfate, dyes, fragrances, antifoaming agents, polyacrylic acid and salts thereof, Examples include acrylic acid / maleic acid copolymers and salts thereof, and bleach activators such as tetraacetylethylenediamine (TAED). These optional components may be added to each particle to such an extent that the stability and properties of the component are not impaired, and may be sprayed as a liquid or added as fine particles.

In addition, the measurement of the average particle diameter as described in this invention is 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.

<Preparation of detergent composition for automatic dishwasher>
Among the components shown in Table 1, after mixing powder components other than the surface modifier, liquid components such as fragrances and polypropylene glycol are mixed, and finally the surface modifier is added and further mixed. A detergent composition for a dishwasher was obtained.

<Cleaning conditions>
Washing machine used: An automatic dishwasher manufactured by Matsushita Electric Industrial Co., Ltd. (model NP-60SS5) was used, and the following tableware and detergent were put in and operated on a standard course. This washer was cleaned by gradually warming 2.2 L of water from 20 ° C. to 60 ° C., and then rinsing three times (no temperature rise), and finally rinsing (gradually rising from 20 ° C. to 70 ° C.). It is of a type that dries after warming and rinsing).
Contaminated dish: 10 sheets Uncontaminated glass cup: 9 Water used: 3.5 ° DH water Detergent composition added amount: 6 g

<Preparation of contaminated dishes>
The filtrate obtained by grinding the half-boiled fried egg and filtering through a net having a diameter of 1 mm was used as dirt. As an evaluation when the amount of dirt was large, 2.4 g per plate was applied as uniformly as possible to a magnetic dish having a diameter of 11 cm, and the one left for 1 hour was used for washing.

<Finished glass cup evaluation method>
The number of water spots formed on the washed glass cup was counted over a fluorescent lamp and evaluated according to the following criteria.
A: The average value of the number of water spots in nine glass cups is within 25. ○: The average value of the number of water spots in nine glass cups is 26 to 40. Δ: Water spots of nine glass cups. The average value of the numbers of 41 to 100 ×: The average value of the number of 9 glass cup water spots is 100 or more

1) Copolymer of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 50/25/25) (weight average molecular weight 30,000)
2) Copolymer of diallyldimethylammonium chloride and SO ₂ (molar ratio 50/50) (weight average molecular weight 30,000)
3) Copolymer of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 70/25/5) (weight average molecular weight 20,000)
4) Diallyldimethylammonium chloride and acrylic acid (molar ratio 69.5 / 30.5 copolymer (weight average molecular weight 450,000))
5) Socaran CP45 (BASF), average particle size 400 μm
6) Weight average molecular weight of about 3000, average condensation degree of about 50 (diol type, Wako Pure Chemical Industries, Ltd.)
7) Tokuseal NR (manufactured by Tokuyama Corporation, oil absorption capacity: 210-270 mL / 100 g)
8) Duramil 60T (Novo Nordisk Bio Industry Co., Ltd.)
9) Sabinase 18.0T (Novo Nordisk Bio Industry Co., Ltd.)
10) Sodium percarbonate whose surface is coated with sodium metaborate. Average particle size 700μm

Claims (4)

Monomer constituent unit A having a cationic group derived from the compound represented by the following general formula (1) and / or the compound represented by the general formula (2), and a monomer constituent unit represented by —SO ₂ —. B, a polymer comprising 10 to 99 mol% of monomer structural unit A with respect to all monomer structural units, and having a molar ratio of monomer structural unit B / monomer structural unit A of 0.01 to 1 (a ) And an alkaline agent (b), and the pH of the 0.2% by mass aqueous solution at 20 ° C. is 9.0 to 14.0.

[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. 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 polymer (a) is, according to claim 1 Symbol placement automatic dishwashing detergent composition containing a constituent unit having an anionic group as a further monomer unit C. Furthermore, the cleaning composition for automatic dishwashers of Claim 1 or 2 containing an enzyme. The cleaning composition for an automatic dishwasher according to any one of claims 1 to 3 , further comprising 0.1 to 10% by mass of polypropylene glycol.