JP2010037414A - Liquid detergent composition for dishwasher - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition for a dishwasher, the composition being excellent in both of foam-suppressing property and surface treating property. <P>SOLUTION: The liquid detergent composition for a dishwasher contains: (A) a polymer compound containing a structural unit derived from a cationic monomer and no SO<SB>2</SB>group, and having a weight average molecular weight of 100,000 to 10,000,000; and (B) a nonionic surfactant selected from general formula (B1) and general formula (B2). The formulae are: (B1) R<SP>1b</SP>-O-(EO)<SB>p</SB>-(PO)<SB>q</SB>-(EO)<SB>r</SB>-H, wherein R<SP>1b</SP>represents an 8-18C straight-chain alkyl group or the like, EO represents an oxyethylene group, PO represents an oxypropylene group, p, q and r each represents an average addition molar number with p ranging from 1 to 10, q ranging from 0.5 to 5 and r ranging from 1 to 10; and (B2) R<SP>2b</SP>-O-(EO)<SB>s</SB>-(PO)<SB>t</SB>-H, wherein R<SP>2b</SP>represents a 8-18C branched alkyl group or the like, EO represents an oxyethylene group, PO represents an oxypropylene group, and s and t each represents an average addition molar number with s ranging from 4 to 10 and t ranging from 2 to 10, satisfying 0.3≤(t/s)≤1.5. <P>COPYRIGHT: (C)2010,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.

  A dishwasher is a device that cleans dishes such as dirty dishes, glasses, and cooking utensils, and is used in kitchens such as homes, restaurants, coffee shops, school meals, and office meals. 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.

  As cleaning agents for dishwashers, those mainly composed of alkaline agents and nonionic surfactants are known. The alkaline agent solubilizes the soil mainly by hydrolysis, and the nonionic surfactant is mainly used for cleaning and removing the soil and further improving the cleaning ability of the oil soil. In the case of an automatic dishwasher, since the cleaning liquid is sprayed and washed at a higher pressure than the nozzle, if there is too much foaming of the surfactant, the foam overflows and the discharge pressure of the spray device decreases, so it is required to have low foam. The Patent Document 1 discloses a cleaning agent for an automatic dishwasher containing a low-foaming nonionic surfactant, a cleaning builder, and an aliphatic carboxylic acid. Patent Documents 2 and 3 disclose a dishwasher cleaning composition containing a polymer compound containing a predetermined monomer unit and a nonionic surfactant in order to obtain an excellent effect without using a rinse agent. The use of objects is disclosed.

In general, an aqueous liquid detergent using an alkali agent and a nonionic surfactant in combination causes white turbidity, separation, and the like, and has poor stability, so a solubilizer is used in combination. For example, Patent Document 4 discloses that a specific carboxylic acid is used as a solubilizer for a strong alkali agent and a nonionic surfactant.
JP-A-6-33100 JP 2007-119753 A JP 2007-99811 A JP 2000-96097 A

  However, a detergent composition for dishwashers, which has both an effect of suppressing foaming in the presence of dirt (foam suppression) and an effect of beautifully finishing the surface of tableware (surface treatment), at a higher level. It hasn't been found yet.

  The subject of this invention is providing the cleaning composition for dishwashers excellent in both foam suppression property and surface treatment property.

The present invention relates to a liquid detergent composition for a dishwasher comprising the following component (A) and component (B).
<(A) component>
A polymer compound containing a structural unit derived from a cationic monomer and containing no SO ₂ group and having a weight average molecular weight of 100,000 to 10,000,000.
<(B) component>
1 or more types of nonionic surfactant chosen from the nonionic surfactant represented by the following general formula (B1), and the nonionic surfactant represented by the following general formula (B2).
^R1b- O- (EO) _p- (PO) _q- (EO) _r- H (B1)
[Wherein, R ^1b 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. ]
^R2b- O- (EO) _s- (PO) _t- H (B2)
[Wherein, R ^2b 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. ]

  ADVANTAGE OF THE INVENTION According to this invention, the cleaning composition for dishwashers excellent in both foam suppression property and surface treatment property is provided.

<(A) component>
As the component (A), a polymer compound containing a structural unit derived from a cationic monomer and not containing an SO ₂ group and having a weight average molecular weight of 100,000 to 10,000,000 is used.

  The component (A) is preferably a cationic polymer containing a structural unit derived from a cationic monomer represented by the following formula (A1) and / or a cationic monomer represented by the following formula (A2).

[In formula, R ^<1a> , R ^{<2a >} , R ^{< 3a >} , R ^{< 7a>} , R ^<8a> , R ^<9a> 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 12a -, - CONHR 12a} -, - OCOR 12a -, - R 13a -OCO-R 12a - it is a group selected from. Here, R ^12a and R ^13a are each independently an alkylene group having 1 to 5 carbon atoms. R ^4a is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^1a R ^2a C═C (R ^3a ) —X—. R ^5a is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^6a 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 ^6a is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ^6a contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ^6a become anions. R ^10a is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^7a R ^8a C═C (R ^9a ) —Y—. R ^11a is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]

  Specifically preferred as the compound of the formula (A1) 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 (C1-3) quaternary ammonium salt, N, N-di (ω-alkenyl (C2-10))-N, N-dialkyl (C1-3) quaternary Ammonium salts are preferred, and diallyldimethylammonium salt is particularly preferred.

  Particularly preferred as the compound of the formula (A2) are acryloyl (or methacryloyl) aminoalkyl (1 to 5 carbon atoms) -N, N-dialkyl (1 to 3 carbon atoms) amine, acryloyl (or methacryloyl) oxyalkyl ( 1 to 5 carbon atoms-N, N-dialkyl (1 to 3 carbon atoms) amine, N- (ω-alkenyl (2 to 10 carbon atoms))-N, N-dialkyl (1 to 3 carbon atoms) amine, N, N-di (ω-alkenyl (2 to 10 carbon atoms))-N-alkyl (1 to 3 carbon atoms) amine, allylamine, diallylmethylamine, diallylamine are preferred, and in particular, allylamine, diallylmethylamine, Diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, acryloyl (or methacryloyl) oxye Till-N, N-dimethylamine is good.

  The structural unit derived from the formula (A1) and / or the formula (A2) is preferably contained in a proportion of 10 to 99 mol% with respect to the total monomer units. More preferably, it is contained in a proportion of 20 to 99 mol%, more preferably 30 to 90 mol%.

  The component (A) of the present invention can include a structural unit derived from an anionic monomer, and in that case, a cationic monomer, in particular, a cationic monomer of the formula (A1) and / or the formula (A2) and an anionic property. The molar ratio of the monomers is preferably cationic monomer / anionic monomer = 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)

  Moreover, the component (A) of the present invention can also contain a structural unit derived from a nonionic monomer. 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, the monomer unit derived from the monomer (i) or (ii) is particularly preferable from the viewpoint of finish, and the monomer unit derived from the monomer (i) is most preferable, and among these, acrylic acid or its sodium salt or potassium Preference is given to salts, 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.

  The component (A) of the present invention contains only a structural unit derived from a cationic monomer, especially a structural unit derived from the cationic monomer of the formula (A1) and / or the formula (A2) and an anionic monomer. It is preferable. From the viewpoint of surface adsorption power, the molar ratio of the cationic monomer to the anionic monomer is cationic monomer / anionic monomer = 10/90 to 90/10, further 30/70 to 90/10, and further 50/50 to 80/20, especially 50/50 to 70/30 are preferred.

  The component (A) of the present invention has a weight average molecular weight of 100,000 to 10,000,000, preferably 100,000 to 5,000,000, more preferably 100,000 to 1,000,000, still more preferably 100,000 to 500,000. The molecular weight is determined by gel permeation chromatography using polyethylene glycol as a standard substance using a mixed solvent of acetonitrile and water (phosphate buffer) as a developing solvent.

  In the component (A), a cationic monomer, an anionic monomer, or a nonionic monomer 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.

  The component (A) of the present invention is preferably a cationic polymer containing a structural unit derived from a cationic monomer represented by the formula (A1), and more preferably a cationic polymer having a structural unit derived from a diallyldimethylammonium salt. In particular, a copolymer of diallyldimethylammonium salt and acrylate, or a copolymer of diallyldimethylammonium salt, acrylate and acrylamide is preferred.

<(B) component>
(B) As a component, 1 or more types of nonionic surfactant chosen from the nonionic surfactant represented by the following general formula (B1) and the nonionic surfactant represented by the following general formula (B2) Is used.
^R1b- O- (EO) _p- (PO) _q- (EO) _r- H (B1)
[Wherein, R ^1b 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. ]
^R2b- O- (EO) _s- (PO) _t- H (B2)
[Wherein, R ^2b 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 (B1), R ^1b is preferably a linear alkyl group having 10 to 14 carbon atoms or a linear alkenyl group, 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, further 1 to 4.5, more preferably 1 to 2, preferably r = 2 to 8, p + r = 1 to 30, further 2 to 20, and further 4 to 15 Is preferred. Specific examples of the nonionic surfactant represented by formula (B1) 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 (hereinafter the same).

In the general formula (B2), R ^2b 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. Further, among the branched alkyl group or branched alkenyl group having 10 to 14 carbon atoms of R ^2b, a secondary alkyl group or secondary alkenyl group having 10 to 14 carbon atoms is preferable. In general formula (B2), s = 5-9 is preferable and t = 5-10 is preferable. Specific examples of the nonionic surfactant represented by formula (B2) 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 (B2), EO is added to a branched (preferably secondary) alcohol having a branched (preferably secondary) alkyl group or branched (preferably secondary) alkenyl group of R ^2b. Then, it can be synthesized by adding PO.

  Moreover, the weight average molecular weight of (B) component has preferable 200-5,000, More preferably, it is 200-2,000. Among the components (B), the compound of the general formula (B1) is available from Kao Corporation under the trade name “Emulgen”, and the compound of the general formula (B2) is Nippon Shokubai under the trade name “Softanol”. Available from Co., Ltd. The component (B) is preferably a nonionic surfactant of the general formula (B1) from the viewpoint of detergency.

<(C) component>
The liquid detergent composition for dishwashers of the present invention can contain a builder component. As the builder component, those having actions such as a metal chelate action, an alkali buffer action, an alkali action, and a solid particle dispersing action are known.

  Examples of inorganic builders include phosphates, carbonates, silicates, and sulfates. Specifically, sodium pyrophosphate, potassium pyrophosphate, sodium tripolyphosphate, sodium orthophosphate, sodium hexametaphosphate, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium sulfate, sodium silicate, potassium silicate, sodium metasilicate, hydroxide Examples thereof include sodium and potassium hydroxide.

  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, etc. 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.

<(D) component>
When the liquid detergent composition for a dishwasher of the present invention contains a builder component (C), from the viewpoint of improving stability by suppressing white turbidity and separation in a liquid state, (D) It is preferable to contain the fatty acid represented by the following general formula (D1) or a salt thereof (hereinafter referred to as the component (D)).
R ^1d —COOH (D1)
(Wherein R ^1d represents a linear aliphatic hydrocarbon group having 3 to 13 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 17 carbon atoms.)

  As the component (D), n-butyric acid, valeric acid, sorbic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, undecanoic acid and other linear fatty acids and salts thereof, or isobutyric acid, 2- Examples thereof include branched chain fatty acids such as ethylhexanoic acid, isopalmitic acid, and isostearic acid, and salts thereof. As the component (D), caprylic acid is preferable.

<(E) component>
It is preferable that the liquid detergent composition for dishwashers of this invention contains glycols as (E) component. As the component (E), ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (weight average molecular weight 200 to 1200), propylene glycol, dipropylene glycol, tripropiolene glycol, polypropylene glycol (weight average molecular weight 600 to 4000), 1,3-butanediol, 1,4-butanediol, polytetramethylene ether glycol (weight average molecular weight 650-1000), 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl- Examples include 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, and the like. Of these, propylene glycol and 1,4-butanediol are preferable.

<Other ingredients>
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 still more preferably, with respect to the liquid detergent composition for a dishwasher of the present invention. Is 1 to 10% by weight.

  In addition, nonionic surfactants other than component (B), anionic surfactants other than component (D), amphoteric surfactants, enzymes, bleaching agents, antifoaming agents, rust preventives, hydrotropes, surface modification A quality agent, a fragrance | flavor, etc. can be contained.

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

<Liquid detergent composition for dishwashers>
In the liquid 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%, from the viewpoints of surface finish and foam suppression. weight%. More preferably 0.1 to 3% by weight. More preferably, the content is 0.1 to 2% by weight.

  In the liquid 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, from the viewpoint of detergency. It is contained in an amount of 0.1 to 10% by weight, more preferably 2 to 5% by weight.

  The liquid detergent composition for a dishwasher of the present invention preferably contains the component (C) in an amount of 5 to 40% by weight. (C) As for content of a component, 10-30 weight% is more preferable in a composition, and 15-30 weight% is still more preferable.

  In the liquid detergent composition for a dishwasher of the present invention, the component (D) is preferably 0.01 to 50% by weight, more preferably 0.05 to 30% by weight, and more preferably 0.05 to 30% by weight, from the viewpoint of cloudiness and separation prevention. Preferably it contains 0.1 to 10 weight%, More preferably, it contains 2 to 5 weight%.

  In the liquid detergent composition for a dishwasher of the present invention, the component (E) is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, more preferably from the viewpoint of white turbidity and separation prevention. Preferably it contains 0.1 to 3 weight%, More preferably, it contains 0.5 to 2 weight%.

  Further, the liquid 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 when used, and the concentration of the component (A) in the cleaning liquid is the surface finish. From the viewpoints of properties and foam suppression properties, it is preferably 0.1 to 100 ppm (weight ratio), more preferably 0.5 to 80 ppm, still more preferably 1 to 50 ppm, and still more preferably 3 to 30 ppm. Moreover, when it contains (D) component, the density | concentration of (D) component in this washing | cleaning liquid is from a viewpoint of detergency, Preferably it is 0.1-1,000 ppm, More preferably, it is 0.5-500 ppm, More preferably Is 1 to 100 ppm, more preferably 5 to 50 ppm.

  Moreover, in the liquid detergent composition for tableware washing machines of this invention, the weight ratio of (A) component and (B) component is (A) / (B) = from a viewpoint of surface finish property and foam suppression property. 5/95 to 50/50, and more preferably 5/95 to 30/70.

  The liquid detergent composition for a dishwasher of the present invention is mixed and stirred when each component is liquid, and when it contains a solid, it is first dissolved in water and then mixed with other liquid components. However, depending on the composition, the order of addition and dissolution is not limited. The composition of the present invention contains water, and usually the balance of the composition is water.

  In the liquid detergent composition for a dishwasher of the present invention, the pH of a 1 wt% aqueous solution (25 ° C) is preferably 10 or more, and more preferably 10.5 to 13.5.

  In the case of washing with a commercial dishwasher using the liquid detergent composition for a dishwasher of the present invention, the composition is arbitrarily transferred into a commercial dishwasher by a supply device, and is appropriately transferred. The concentration of the correct cleaning solution is maintained. In the liquid composition of the present invention, a tube exclusively used for a commercial dishwasher is directly inserted into a container such as plastic filled with a detergent composition for a dishwasher, and is sucked and supplied. Thereafter, the cleaning liquid is supplied into the commercial dishwasher.

  The liquid detergent composition for a dishwasher of the present invention is used at a concentration in the cleaning liquid of 0.04 to 0.5% by weight, but from the viewpoint of economy and detergency, 0.05 to 0.3. % By weight is preferable, and further 0.1 to 0.2% by weight is preferable. The washing time of the 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, preferably 40 ° C. or higher, and more 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.

  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 liquid detergent composition for the dishwasher is supplied by the automatic supply device so as to obtain an appropriate concentration.

  The automatic supply device for the liquid detergent composition for a dishwasher is not limited, but is controlled by sensing the concentration of the washing liquid and receiving a signal. In the liquid composition of the present invention, the tube pump is driven to supply the required amount of the liquid detergent composition for a dishwasher.

  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 liquid detergent composition for a dishwasher having the composition shown in Table 1 was prepared, and the detergency, finish (drying speed and water spot), and foam suppression were evaluated by the following methods. The results are shown in Table 1.

[Detergency evaluation]
[1] Evaluation of detergency and preparation of model dirt On the center of a new 20 cm diameter porcelain dish, 2 g of egg yolk was uniformly applied with a brush in a circular shape with a diameter of about 10 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 The washing | cleaning composition (38L) of the dishwasher for business [SANYO DR53 by Sanyo Electric Co., Ltd.] 38g was put into the washing | cleaning composition for tableware washing machines, and it was made to melt | dissolve with 50 degreeC warm water. Four pieces of porcelain dishes coated with model dirt were set on a dedicated rack, washed with a washing solution at 50 ° C. for 1 minute, 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 erythrosine dye, and the detergency was evaluated according to the following criteria.

* Judgment criteria 4 for cleaning properties: No coloring marks were observed, completely removing dirt 3; Slight coloring marks were recognized, but most of the dirt was removed 2; Residual 1; 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, it was dried at 25 ° C. for 2 hours and used as model dirt for evaluation of the finish.

-Evaluation method The washing | cleaning composition (38L) of the dishwasher for business [SANYO DR53 by Sanyo Electric Co., Ltd.] 38g was put into the washing | cleaning composition for tableware washing machines, and it was made to melt | dissolve with 50 degreeC warm water. Four 8-ounce glasses coated with model dirt were set on a dedicated rack, washed with a washing solution at 50 ° C. for 1 minute, 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 rate 4; average per glass, drying in less than 1 hour 3; average per glass, drying in 1 hour or more, less than 1 hour 30 minutes 2; average per glass 1 hour 30 minutes or more and less than 2 hours, drying 1; average of 2 hours or more per glass

* Water spot criterion 4; The average number of water spots is less than 5 per glass 3; The average number of water spots is 5 or more and less than 10 2 per glass 2; The number of water spots is 10 or more on average per glass and less than 20 1; the average number of water spots is 20 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] Foam suppression evaluation / evaluation method 40g of milk, 20g of rapeseed oil, and 38g of detergent composition for dishwashers are put into a washing tank (38L) of a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] And it was made to melt | dissolve with 50 degreeC warm water. After washing with a washing solution at 50 ° C. for 1 minute, rinsing with rinsing water at 80 ° C. for 8 seconds without using a rinsing agent, and foaming in the washing machine immediately after the washing is suppressed according to the following criteria. Sex was evaluated.
4; Almost no bubbles are observed.
3; A thin bubble is observed.
2: Bubbles do not overflow from the inside of the washing machine, but thick bubbles are standing.
1; Thick bubbles are standing and the bubbles overflow from the washing machine.

(Note) The components in the table are as follows.
-High molecular compound (A1): a copolymer of diallyldimethylammonium chloride and acrylic acid (molar ratio 64/36), Merquat 280 (produced by Calgon, used as an aqueous solution with an effective content of 40% by weight, the amount of the aqueous solution in the table showed that.)
-High molecular compound (A2): a copolymer of diallyldimethylammonium chloride, acrylic acid and acrylic amide (molar ratio 31/34/35), Merquat 3330 (manufactured by Calgon, used as an aqueous solution with an effective content of 10% by weight, The inside indicates the amount of the aqueous solution.)
-High molecular compound (A3): a copolymer of diallyldimethylammonium chloride, acrylic acid and acrylic amide (molar ratio 16/66/18), Merquat 3333 (Calgon, used as an aqueous solution with an effective content of 10% by weight, table The inside indicates the amount of the aqueous solution.)
Nonionic surfactant (B1): a nonionic surfactant in which R ^1b is a linear alkyl group having 12 carbon atoms and p = 3, q = 1.5, and r = 3 in the general formula (B1) Nonionic surfactant (B2-1) B: Polyoxyethylene polyoxypropylene lauryl (branched) ether having a general formula (B2) structure (average ethylene oxide addition mole number 7, propylene oxide average addition mole number 8) .5, a block adduct in which a polyoxyethylene chain is bonded to a branched lauryl group (a branched alkyl group having 12 carbon atoms)
Nonionic surfactant (B2-2) C: polyoxyethylene polyoxypropylene lauryl (branched) ether having a general formula (B2) structure (average number of moles of added ethylene oxide, number of added moles of propylene oxide 4) .5, a block adduct in which a polyoxyethylene chain is bonded to a branched lauryl group (a branched alkyl group having 12 carbon atoms)
・ Fatty acid: Caprylic acid

Claims (5)

A liquid detergent composition for a dishwasher comprising the following component (A) and component (B).
<(A) component>
A polymer compound containing a structural unit derived from a cationic monomer and containing no SO ₂ group and having a weight average molecular weight of 100,000 to 10,000,000.
<(B) component>
1 or more types of nonionic surfactant chosen from the nonionic surfactant represented by the following general formula (B1), and the nonionic surfactant represented by the following general formula (B2).
^R1b- O- (EO) _p- (PO) _q- (EO) _r- H (B1)
[Wherein, R ^1b 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. ]
^R2b- O- (EO) _s- (PO) _t- H (B2)
[Wherein, R ^2b 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 tableware according to claim 1, wherein the component (A) is a polymer compound containing a structural unit derived from a cationic monomer represented by the following formula (A1) and / or a cationic monomer represented by the following formula (A2). A cleaning composition for a cleaning machine.

[In formula, R ^<1a> , R ^{<2a >} , R ^{< 3a >} , R ^{< 7a>} , R ^<8a> , R ^<9a> 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 12a -, - CONHR 12a} -, - OCOR 12a -, - R 13a -OCO-R 12a - it is a group selected from. Here, R ^12a and R ^13a are each independently an alkylene group having 1 to 5 carbon atoms. R ^4a is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^1a R ^2a C═C (R ^3a ) —X—. R ^5a is an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or a benzyl group, and R ^6a 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 ^6a is an alkyl group, a hydroxyalkyl group or a benzyl group, Z ⁻ represents an anion. When R ^6a contains a carboxyl group, a sulfonic acid group, or a sulfate group, Z ⁻ does not exist, and these groups in R ^6a become anions. R ^10a is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or R ^7a R ^8a C═C (R ^9a ) —Y—. R ^11a is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group. ]   The component (A) is a polymer compound that includes a structural unit derived from a cationic monomer and a structural unit derived from an anionic monomer, and the molar ratio of the cationic monomer to the anionic monomer is cationic monomer / anionic. Monomer = 10/90 to 90/10. The detergent composition for a dishwasher according to claim 1 or 2.   The cleaning composition for a dishwasher according to claim 3, wherein the component (A) contains only a structural unit derived from a cationic monomer and a structural unit derived from an anionic monomer as a structural unit.   Tableware washing | cleaning which wash | cleans tableware with a dishwasher using the cleaning composition for dishwashers of any one of Claims 1-4, and performs a rinsing process with the rinse water which does not contain a rinse agent after that. Method.