JP2009155615A - Liquid detergent composition for dishwashers - Google Patents

Abstract

Disclosed is a liquid detergent composition for a dishwasher that has high detergency, excellent stability, and can improve the anticorrosion and scale adhesion prevention properties of alumite.
During (A) a molecule, and an amino group and a quaternary monomer units having groups one or more selected from an ammonium group (a), -SO ₂ - and represented by the monomer unit (b) Yes A polymer compound containing 10 to 99 mol% of the monomer unit (a) with respect to the total monomer units and having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1; B) A liquid detergent composition for a dishwasher containing the fatty acid represented by the general formula (B1) or a salt thereof in a weight ratio of (A) / (B) = 10/90 to 30/70.
[Selection figure] None

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 Document 2 discloses a detergent composition for a dishwasher 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. It is disclosed to use.

  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 3 discloses that a specific carboxylic acid is used as a solubilizer for a strong alkali agent and a nonionic surfactant.

  However, if the content of alkali agent, nonionic surfactant, and inorganic salt is increased, the product becomes cloudy or separated, resulting in non-uniform cleaning, which causes variations in cleaning properties and the like.

  Examples of the materials of tableware to be washed such as restaurant, coffee shop, school / business lunch, etc. include ceramics, glass, plastic, anodized. Since anodized tableware is corroded by alkali, repeated washing causes whitening or browning. Therefore, the corroded tableware is discarded and replenished, but the cost of re-purchasing is borne.

In tap water, hardness components such as Ca and Si are present. These combine with carbon dioxide gas in the air to form a carbonic acid carbonate and a carbonic acid Si salt and adhere to the inside of the washing machine. As a result, the aesthetics in the washing machine tub are damaged, and the sensing concentration of the washing liquid is poor, and the signal cannot be received. As a result, density control is poor.
JP-A-6-33100 JP 2007-119753 A JP 2000-96097 A

  An object of the present invention is to provide a liquid detergent composition for a dishwasher that has high detergency, is excellent in stability without white turbidity or separation, and can improve the anticorrosion property and anti-scale adhesion property of alumite. is there.

This invention contains the following (A) component and (B) component, and the weight ratio of (A) component and (B) component is (A) / (B) = 10 / 90-30 / 70. The present invention relates to a liquid detergent composition for a dishwasher.
<(A) component>
The molecule 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 —, and the monomer unit (a) Is a high molecular compound having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1, wherein the monomer unit (a) is A polymer compound derived from a compound represented by the following general formula (1) and / or a compound represented by the general formula (2).

[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 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. ]

<(B) component>
Fatty acid represented by the following general formula (B1) or a salt thereof.
R-COOH (B1)
(In the formula, R represents a linear aliphatic hydrocarbon group having 3 to 13 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 17 carbon atoms.)

  ADVANTAGE OF THE INVENTION According to this invention, the liquid cleaning composition for tableware washing machines which has high washing | cleaning property, is excellent in stability without white turbidity, isolation | separation, etc., and can improve the corrosion prevention property of alumite and scale adhesion prevention property is provided.

<(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, more preferably 0.05 to 0.5. It is.

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

[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 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 a diallyldimethylammonium salt is 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 preferred, and allylamine and diallylmethylamine are also preferred. , Diallylamine, acryloyl (or methacryloyl) aminopropyl-N, N-dimethylamine, acryloyl (or methacryloyl) oxy Ethyl-N, N-dimethylamine is good.

  From the viewpoint of the anticorrosion property and scale adhesion prevention property of the alumite, the component (A) is a monomer unit (a) of 10 to 99 mol%, preferably 30 to 90 mol%, more preferably 50 to 90 mol% based on all monomer units. The mol% is contained, more preferably 60 to 80 mol%. 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. Moreover, in this invention, it can superpose | polymerize also with light and a radiation, and also can superpose | polymerize efficiently by irradiating the light with a wavelength of 300-450 nm.

  From the viewpoints of anodizing and anti-scale adhesion, the monomer unit (b) / monomer unit (a) molar ratio is 0.01 to 1, preferably 0.03 to 0.75, more preferably 0.8. It is 05-0.5.

  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 even more 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 anodizing and anti-scale adhesion, a monomer unit derived from the monomer (i) or (ii) is preferable, and a monomer unit derived from the monomer (i) is most preferable, and among these, acrylic acid Or its sodium salt or potassium salt, methacrylic acid or its sodium salt or potassium salt, maleic acid or its sodium salt or potassium salt is preferable. 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 a monomer unit (d), the molar ratio of the monomer unit (d) / monomer unit (a) is 0.05 to 1, more preferably 0.1 to 0.75 from the viewpoint of finish. Further, 0.2 to 0.5 is preferable.

  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 still more preferably 5, The weight average 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 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>
Component (B) is a fatty acid represented by the above general formula (B1) or a salt thereof, n-butyric acid, valeric acid, sorbic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, undecanoic acid Linear fatty acids such as these and salts thereof, or branched chain fatty acids such as isobutyric acid, 2-ethylhexanoic acid, isopalmitic acid, and isostearic acid, and salts thereof. As the component (B), caprylic acid is preferable.

<(C) component>
The liquid detergent composition for a dishwasher of the present invention preferably contains a nonionic surfactant as the component (C) from the viewpoint of detergency. Component (C) includes 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 alkyl ether, polyoxy Examples include ethylene dialkyl ether, polyoxyethylene glycol, polyoxyethylene oxypropylene glycol, and polyoxypropylene oxyethylene oxypropylene glycol.

As the component (C), a nonionic surfactant represented by the following general formula (3) [hereinafter referred to as the component (C1)] 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 (C1), 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, more 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, More 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 (C2)] 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) fH (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 added moles 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 (C2) 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.

  The weight average molecular weight of the component (C2) is preferably 1,000 to 15,000, more preferably 1,500 to 6,000. The component (B2) is available from BASF under the trade names “Pluronic” and “Pluronic R”. The component (D2) is preferably a nonionic surfactant of formula (5) from the viewpoint of low foaming properties.

In addition, from the viewpoint of detergency, one or more nonionic surfactants selected from the nonionic surfactant represented by the following general formula (6) and the nonionic surfactant represented by the general formula (7) [ Hereinafter, it is referred to as (C3) component].
_{^{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, 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 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 (hereinafter the same).

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 (C3) is preferably 200 to 5,000, more preferably 200 to 2,000. Among the components (C3), the compound of the general formula (6) is available from Kao Corporation under the trade name “Emulgen”, and the compound of the general formula (7) is Nippon Shokubai under the trade name “Softanol”. Available from Co., Ltd. As the component (C3), a nonionic surfactant represented by the general formula (6) is preferable from the viewpoint of detergency.

<(D) 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.

<(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.

  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, an anionic surfactant other than the component (B), an amphoteric surfactant, an enzyme, a bleaching agent, an antifoaming agent, a rust preventive agent, a hydrotrope agent, a surface modifier, a fragrance and the like 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 viewpoint of anodized anticorrosion and scale adhesion prevention. weight%. More preferably 0.1 to 3% by weight. More preferably, it contains 0.5 to 2% by weight.

  In the liquid detergent composition for a dishwasher of the present invention, the component (B) is preferably from 0.01 to 50% by weight, more preferably from 0.05 to 30% by weight, further 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 (C) 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 (D) in an amount of less than 20% by weight. (D) As for content of a component, 10-19 weight% is more preferable in a composition, and 15-18 weight% is still more preferable.

  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, from the viewpoint of white turbidity and prevention of separation. Preferably it contains 0.1 to 3 weight%, More preferably, it contains 0.5 to 2 weight%.

  In addition, 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 an anodized anticorrosion From the viewpoint of the property and anti-scale adhesion property, 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. The concentration of the component (C) 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 still more preferably, from the viewpoint of cleaning power. 5 to 50 ppm.

  In the liquid detergent composition for a dishwasher according to the present invention, the weight ratio of the component (A) to the component (B) is (A) / (B) from the balance between anodized anticorrosive property, anti-scale adhesion property and solution stability. ) = 10/90 to 30/70, preferably 15/85 to 25/75.

  Moreover, in the liquid detergent composition for tableware washing machines of this invention, the weight ratio of (A) component and (C) component is (A) / (C from the balance of alumite anticorrosive property, scale adhesion prevention property, and washability. ) = 5/95 to 50/50, more preferably 10/90 to 40/60, and further preferably 15/85 to 30/70.

  Moreover, in the liquid detergent composition for tableware washing machines of this invention, the sum total of content of (A) component and (D) component is less than 20 weight%, Furthermore, 10-19.5 weight%, More preferably 15- 19% by weight is preferred.

  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 dishwasher and 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 0.1 to 0.2% by weight is more 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, solution stability, anodized anticorrosion and scale adhesion prevention were evaluated by the following methods. The results are shown in Table 1.

[1] Detergency test The cleaning composition is transferred into a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] by a supply device and adjusted so that the concentration is maintained at 0.1 to 0.15%. did.

-Preparation of model dirt On the center of a new 20 cm diameter porcelain dish, 4 g of egg yolk was uniformly applied in a circular shape with a brush 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 liquid 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 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 erythrosine dye, and the detergency was evaluated according to the following criteria.

* Judgment criteria for cleaning performance ○: Slightly colored traces are observed, but most of the dirt is removed Δ; Clearly colored traces are observed, and about half of the dirt remains; x: Mostly stained traces are observed, and many stains are observed Residual

  The results are shown in Table 1. It became clear that the liquid detergent composition for dishwashers of this invention is excellent in detergency.

(2) Solution stability test The liquid detergent composition for a dishwasher was stored in a 100 cc bottle made of polypropylene under the condition of 40 cc × 30 days after being placed in a 100 cc bottle, and then transferred to a glass beaker. The appearance was visually observed and the solution stability was determined according to the following criteria.
Judgment criteria ○: Transparent (cloudy, no separation)
Δ: Slightly cloudy ×: Separation

  The results are shown in Table 1. It became clear that the liquid detergent composition for dishwashers of this invention is excellent in solution stability.

(3) Anodized anticorrosion test A liquid detergent composition for a dishwasher was diluted with ion-exchanged water so as to have a concentration of 0.05% by weight or 0.1% by weight to prepare a diluted solution. An alumite test piece (2 cm × 5 cm) was washed with ethanol (99% product) and dried. 20 cc of the diluted solution was sampled in a 50 cc glass screw tube, and an alumite test piece was immersed therein. At that time, the test piece is immersed so that about half of the test piece is immersed. The screw tube containing the alumite test piece is placed in a dryer at 50 ° C. and 70 ° C. and allowed to stand for 15 hours. After completion, after washing with ion-exchanged water and drying, the appearance was visually observed, and anodized anticorrosion was determined according to the following criteria.
Judgment criteria ○: No change △: Slightly changed to white ×: Changed to white

  The results are shown in Table 1. It became clear that the liquid detergent composition for dishwashers of this invention is excellent in the anodized anti-corrosion effect.

(4) Scale adhesion prevention test The liquid detergent composition for a dishwasher is transferred into a commercial dishwasher [SANYO DR53 manufactured by Sanyo Electric Co., Ltd.] by a supply device, and 0.1 to 0.15 weight % Concentration was adjusted to be maintained. For washing and rinsing with a washing machine, an aqueous sodium silicate solution (41.5% product) is added to and mixed with ion-exchanged water so that the Si content is 25 ppm, and then adjusted with hydrochloric acid (special grade). After (7-8), a solution of 10000 ° dH (Ca / Mg = 7/3: German hardness) was added and hardness adjusting water adjusted to 6 ° dH was used.

Ten SUS304 test pieces (3 cm × 5 cm) washed and dried with ethanol were set inside the washing machine, washed with a washing solution at 50 ° C. for 40 seconds, and then rinsed with rinse water at 80 ° C. for 10 seconds. These steps were taken as one cycle and repeated 500 cycles. After the completion, the appearance of the test piece was visually observed, and the scale adhesion preventing property was determined according to the following criteria.
Judgment criteria ○: No change △: Surface gloss slightly changed ×: Surface gloss changed greatly

  The results are shown in Table 1. It became clear that the liquid detergent composition for dishwashers of this invention is excellent in scale adhesion prevention property.

(Note) The components in the table are as follows.
Polymer compound: copolymer of diallyldimethylammonium chloride, maleic acid and SO ₂ (molar ratio 70/25/5) [effective amount of 25% by weight aqueous solution, effective amount in composition is in the table Using numerical values, (A) / (B) (weight ratio) and (A) + (D) (% by weight) were calculated based on the numerical values. ]
Nonionic surfactant A: PO / EO / PO block polymer, Pluronic RPE2520 (manufactured by BASF)
Nonionic surfactant B: 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 C: polyoxyethylene (EO average addition mole number 5) lauryl ether, Emulgen 106 [manufactured by Kao Corporation]
Nonionic surfactant D: 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 E: 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 ]

Claims (5)

The following (A) component and (B) component are contained, and the weight ratio of the (A) component and the (B) component is (A) / (B) = 10 / 90-30 / 70. Liquid detergent composition.
<(A) component>
The molecule 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 —, and the monomer unit (a) Is a high molecular compound having a monomer unit (b) / monomer unit (a) molar ratio of 0.01 to 1, wherein the monomer unit (a) is A polymer compound derived from a compound represented by the following general formula (1) and / or a compound represented by the general formula (2).

[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 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. ]
<(B) component>
Fatty acid represented by the following general formula (B1) or a salt thereof.
R-COOH (B1)
(In the formula, R represents a linear aliphatic hydrocarbon group having 3 to 13 carbon atoms or a branched aliphatic hydrocarbon group having 3 to 17 carbon atoms.)   The liquid detergent composition for a dishwasher according to claim 1, further comprising (C) a nonionic surfactant. (C) One or more nonionic surfactants selected from nonionic surfactants represented by the following general formula (6) and nonionic surfactants represented by the following general formula (7): The liquid detergent composition for a dishwasher according to claim 2, which is a surfactant.
_{^{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 liquid detergent composition for a dishwasher according to any one of claims 1 to 3, further comprising (D) a builder component, wherein the content of the (D) builder component is less than 20% by weight. Furthermore, the liquid cleaning composition for tableware washing machines of any one of Claims 1-4 containing (E) glycols.