JP6247092B2 - Liquid detergent composition for automatic dishwasher and dishwashing method - Google Patents

Description

  The present invention relates to a liquid detergent composition for an automatic dishwasher and a method for washing dishes.

Dirt that adheres strongly to dishes such as oil stains and tea astringent stains, and stains that are a combination of lipids and proteins, such as semi-boiled egg yolks, adhere firmly to the dishes when dried. It is difficult to perform cleaning. Therefore, when washing such stains with an automatic dishwasher, pretreatment such as pre-immersing the dishes in water or lightly washing the hands is necessary, which is troublesome.
Moreover, when it wash | cleans with an automatic dishwasher, there exists a problem of the reattachment of the stain | pollution | contamination in which the stain | pollution | contamination once washed adheres to tableware again.
Therefore, a detergent containing a cationic polymer has been developed as a detergent for an automatic dishwasher that can remove dirt without performing a pretreatment that requires labor.
For example, Patent Documents 1 and 2 describe a dishwasher cleaning composition containing a water-soluble polymer compound containing a cationic group and a surfactant.
Patent Document 3 describes a liquid detergent composition containing a non-crosslinked polycarboxylic acid polymer, a specific alkyl glycoside compound, and cationized cellulose.

JP 2006-143843 A JP 2007-254586 A JP 2011-080053 A

The cleaning agent described in Patent Document 1 is a cleaning agent that imparts a drying acceleration effect to a hard surface around water, and the cleaning agent described in Patent Document 2 suppresses the formation of water spots. For example, sufficient studies have not been made on detergency against tea astringent stains, stains in which lipids and proteins are combined, and reattachment of stains.
In addition, Patent Document 3 has been studied for cleaning power such as tea astringent stains, glass fogging, and oil stains, but the cleaning power is not sufficient and further improvement is desired.

  The present invention shows excellent cleaning performance against oil stains, tea astringent stains, and soils in which lipids and proteins are combined and dried and firmly adhered to the tableware surface, and suppresses the reattachment of stains. Provided are a liquid detergent composition for an automatic dishwasher and a method for washing dishes.

That is, the gist of the present invention is as follows.
[1] The following cationic polymer (a), the following anionic polymer (b), a chelating agent (c), a nonionic surfactant (d), and water (e) The amount is 0.1% by mass or more and 20% by mass or less, and the mass ratio of the component (b) to the component (a) ((b) / (a)) is 0.01 or more and 60 or less, The automatic dishwasher whose mass ratio ((c) / (a)) of said (c) ingredient to said (a) ingredient is 0.4 or more and 30 or less, and pH at 20 ° C is 6 or more and 9 or less Liquid detergent composition.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)

[2] Containing the following cationic polymer (a), the following anionic polymer (b), a chelating agent (c), a nonionic surfactant (d), and water (e), the concentration of the component (a) Is 1 ppm or more and 1,000 ppm or less, the mass ratio ((b) / (a)) of the component (b) to the component (a) is 0.01 or more and 60 or less, and the component (a) Washing | cleaning method of the tableware which makes the surface of tableware contact the washing water whose mass ratio ((c) / (a)) of said (c) component with respect to is 0.4 or more and 30 or less.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)

  According to the present invention, oil stains, tea astringent stains, and lipids and proteins are complexed, and show excellent cleaning performance against stains that are dried and firmly adhered to the tableware surface. The liquid detergent composition for automatic dishwashers which can be suppressed, and the washing | cleaning method of tableware can be provided.

[Liquid detergent composition for automatic dishwashers]
The liquid detergent composition for an automatic dishwasher of the present invention comprises the following cationic polymer (a), the following anionic polymer (b), a chelating agent (c), a nonionic surfactant (d), and water (e ), The content of the component (a) is 0.1% by mass or more and 20% by mass or less, and the mass ratio of the component (b) to the component (a) ((b) / (a) ) Is 0.01 or more and 60 or less, the mass ratio ((c) / (a)) of the component (c) to the component (a) is 0.4 or more and 30 or less, and the pH at 20 ° C. Is 6 or more and 9 or less.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)

<(A) component>
The component (a) has one or more cationic groups selected from the following general formulas (a-1) to (a-5), and has a degree of cationization of 0.25 mol% or more and 5 mol%. The following is a cationic polymer.

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)

R ^{1 to} R ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, and the carbon number of the alkyl group is preferably 1 or more from the viewpoint of suppressing the reattachment of dirt, and preferably 4 Below, more preferably 3 or less, and still more preferably 2 or less.
Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, various butyl groups, various pentyl groups, and various hexyl groups. Among these, a methyl group is preferable. The “various” means various isomers including n-, sec-, tert-, and iso-.

Z ⁻ is an anion, and the anion includes a hydroxy ion; a halide ion such as a chloride ion, a bromide ion, or an iodide ion; and two or more carbon atoms such as an acetate ion, a propionate ion, or a butyrate ion, Lower fatty acid ions of 4 or less; lower alkyl sulfate ions of 1 to 3 carbon atoms such as methyl sulfate ion and ethyl sulfate ion. Among these, from the viewpoint of suppressing the reattachment of dirt, hydroxy ions and halide ions are preferable, hydroxy ions, chloride ions and bromide ions are more preferable, and chloride ions are still more preferable.

m represents an integer of 1 or more and 10 or less. When m is 1 or more and 10 or less, the cleaning performance is improved. From the viewpoint of cleaning performance, m is preferably 2 or more, and is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and even more preferably 3 or less.
n represents an integer of 0 or more and 10 or less. If n is 0 or more and 10 or less, the cleaning performance is improved. From the viewpoint of cleaning performance, n is preferably 1 or more, more preferably 2 or more, and is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and even more preferably 3 or less.

The cationic polymer having a cationic group represented by the general formulas (a-1) to (a-5) can be obtained, for example, by polymerizing a monomer having the cationic group and a polymerizable monomer. it can.
Examples of the polymerizable monomer include olefins such as propylene, 1-butene, 1-pentene and 1-hexene, styrenes such as styrene and p-methylstyrene, and acrylic esters such as ethyl acrylate and butyl acrylate. Derivatives, fatty acid vinyls such as vinyl acetate and isopropenyl acetate, and the like.
Moreover, it can also manufacture by making the compound which has the said cationic group react with semisynthetic water-soluble polymers, such as hydroxyethyl cellulose and soluble starch.
In the present invention, from the viewpoint of improving the reattachment performance of soil, and from the viewpoint of availability, cationically modified polyvinyl alcohol produced by polymerizing vinyl acetate and the monomer having the cationic group, hydroxyethyl cellulose, and the above A cation-modified hydroxyl ethyl cellulose obtained by reacting a compound having a cationic group is preferred.

(Cation-modified polyvinyl alcohol)
Cationic modified polyvinyl alcohol is polyvinyl alcohol having the cationic group in the main chain or side chain. The cation-modified polyvinyl alcohol is obtained by copolymerizing diallyldimethylammonium chloride, (3-acrylamidopropyl) trimethylammonium chloride, and the like with vinyl acetate when polymerizing the raw material vinyl acetate. Can be obtained.
In addition, vinyl acetate is copolymerized with a monomer having another reactive group, and after saponification, the reactive group is used to react with the compound containing the cationic group to cationize polyvinyl alcohol. May be.

(Cation-modified hydroxyethyl cellulose)
The cation-modified hydroxyl ethyl cellulose can be obtained, for example, by a method in which raw material cellulose and ethylene oxide are reacted to obtain hydroxyethyl cellulose, and then this hydroxyethyl cellulose is reacted with a cationizing agent to be cationized.

  Cellulose used as raw material cellulose includes chemically pure cellulose, wood such as various wood chips; pulps such as wood pulp produced from wood; papers such as newspaper and cardboard; rice straw and corn Various cellulose-containing raw materials such as plant stems and leaves such as stems; plant shells such as rice husks, palm shells, and coconut shells can be used.

  As a cationizing agent, from the viewpoint of availability, chlorides or bromides of glycidyltrimethylammonium or glycidyltriethylammonium, chlorides such as 3-chloro-2-hydroxypropyltrimethylammonium and 3-chloro-2-hydroxypropyltriethylammonium Bromide such as 3-bromo-2-hydroxypropyltrimethylammonium and 3-bromo-2-hydroxypropyltriethylammonium, glycidyltrimethylammonium chloride or 3-chloro-2-hydroxypropyltrimethylammonium chloride is more preferable, More preferred is 3-chloro-2-hydroxypropyltrimethylammonium chloride. These cationizing agents may be used alone or in combination of two or more.

The degree of cationization of the cationic polymer is 0.25 mol% or more, preferably 0.35 mol% or more, more preferably 0.45 mol% or more, further preferably 0.6 mol% or more, from the viewpoint of suppressing the reattachment of dirt. More preferably 0.8 mol% or more, still more preferably 1.0 mol% or more, and 5 mol% or less from the viewpoint of uniformly adsorbing the polymer to the tableware and suppressing the reattachment of dirt, Preferably it is 4 mol% or less, More preferably, it is 3 mol% or less, More preferably, it is 2 mol% or less.
The degree of cationization can be determined by colloid titration using potassium polyvinyl sulfate (PVSK).

The average molecular weight of the cationic polymer is preferably 10,000 Da or more, more preferably 30,000 Da or more, still more preferably 50,000 Da or more, and even more preferably 70,000 Da or more, from the viewpoint of improving detergency. From the viewpoint of suppressing the reattachment of dirt, it is preferably 2,000,000 Da or less, more preferably 1,500,000 Da or less, still more preferably 1,000,000 Da or less, and still more preferably 800,000 Da or less. is there.
The average molecular weight of the cationic polymer can be determined by gel permeation chromatography using polystyrene as a standard substance.

  The content of the component (a) in the liquid detergent composition for an automatic dishwasher is 0.1% by mass or more, preferably 0.5% by mass or more, more preferably from the viewpoint of suppressing the reattachment of dirt. Is 1% by mass or more, more preferably 1.5% by mass or more, and from the viewpoint of cleaning performance, 20% by mass or less, preferably 15% by mass or less, more preferably 13% by mass or less, still more preferably 10%. It is 7 mass% or less, More preferably, it is 7 mass% or less.

<(B) component>
The component (b) is an anionic polymer having a structural unit derived from an anionic group-containing monomer selected from acrylates, methacrylates, and maleates. In the present invention, the polymer containing both the cationic group and the anionic group is the component (a).
Examples of the salt of acrylic acid, methacrylic acid, or maleic acid include sodium salt, potassium salt, ammonium salt, and alkanol ammonium salt.
The anionic polymer may be a polymer composed only of the anionic group-containing monomer, or may be a copolymer of an anionic group-containing monomer and a monomer other than the anionic group-containing monomer.
Examples of monomers other than the anionic group-containing monomer include (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N-diethyl ( N-substituted (meth) acrylamides such as meth) acrylamide, isopropyl (meth) acrylamide, tert-butyl (meth) acrylamide, vinyl ethers such as methyl vinyl ether and butyl vinyl ether, styrene, olefinic hydrocarbons such as ethylene, propylene and isobutylene Kind. These may be used individually by 1 type and may be used in combination of 2 or more type.
Among these, (meth) acrylic acid alkyl esters such as methyl (meth) acrylate and ethyl (meth) acrylate are preferable.
In the present specification, “(meth) acryl” means “acryl or methacryl”.

When the anionic polymer is a copolymer of an anionic group-containing monomer and a monomer other than the anionic group-containing monomer, the content of the anionic group-containing monomer in the anionic polymer is preferably 40% by mass or more. More preferably, it is 50 mass% or more, More preferably, it is 60 mass% or more, More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 100 mass%.
In addition, content of the anionic group containing monomer in an anionic polymer can be computed from the compounding quantity at the time of superposition | polymerization.

  An anionic polymer can be manufactured by the method of homopolymerizing an anionic group containing monomer, or the method of copolymerizing an anionic group containing monomer and other monomers. Specifically, the monomer is obtained by radical polymerization in the presence of a radical initiator.

The weight average molecular weight of the anionic polymer is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and preferably 500,000 or less, from the viewpoint of cleaning performance. Preferably it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 35,000 or less.
In addition, the weight average molecular weight of the anionic polymer in this specification is a value obtained by using polystyrene as a standard substance by gel permeation chromatography.

The mass ratio ((b) / (a)) of the component (b) to the component (a) is 0.01 or more and 60 or less. When the mass ratio ((b) / (a)) is within the above range, the cleaning performance for dry semi-ripe egg yolk stains can be improved, and the reattachment of stains can be suppressed.
The mass ratio ((b) / (a)) is preferably 0.5 or more, more preferably 1.5 or more, and further preferably 3 or more, from the viewpoint of cleaning performance, and suppresses the reattachment of dirt. In view of the above, it is preferably 50 or less, more preferably 30 or less, and still more preferably 10 or less.

<(C) component>
Examples of chelating agents include citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1 , 3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, and hydroxyethylethylenediaminedicarboxymethylglutamic acid Alternatively, a salt thereof, tripolyphosphoric acid or a salt thereof can be used.
Among these, citric acid, malic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid and tripolyphosphoric acid, or salts thereof are preferable.
These chelating agents may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable from the viewpoint of cleaning performance to use one kind selected from citric acid, malic acid or salts thereof and one kind selected from methylglycine diacetic acid, glutamic acid diacetic acid or salts thereof.

The mass ratio ((c) / (a)) of the component (c) to the component (a) is 0.4 or more and 30 or less. When the mass ratio ((c) / (a)) is within the above range, the cleaning performance is improved and the reattachment of dirt can be suppressed.
The mass ratio ((c) / (a)) is preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, and preferably 28 or less, from the viewpoint of suppressing the reattachment of dirt. More preferably, it is 20 or less, More preferably, it is 10 or less, More preferably, it is 5 or less.

<Nonionic surfactant (d)>
As the nonionic surfactant (d), polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, sorbitan monostearate, polyoxyethylene alkylamine and the like are preferable from the viewpoint of cleaning performance.
Among these, from the viewpoint of cleaning performance, the average added mole number of EO is preferably 2 or more, more preferably 3 or more, and from the viewpoint of suppressing foaming, preferably 30 or less, more preferably 18 or less, and further Preferably, it is 10 or less, more preferably 6 or less, even more preferably 5 or less, even more preferably 4 or less, and the carbon number of the alkyl group is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more. And preferably a polyoxyethylene alkyl ether having 18 or less, more preferably a polyoxyethylene having an average addition mole number of EO of 3 or more and 18 or less, and an alkyl group having 12 or more and 18 or less carbon atoms. An alkyl ether is mentioned.
Specifically, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and polyoxyethylene lauryl ether are preferable. One of these nonionic surfactants may be used alone, or two or more thereof may be used in combination.
The content of the nonionic surfactant in the liquid detergent composition for an automatic dishwasher is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more. And preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less.

<Water (e)>
As water constituting the liquid detergent composition for automatic dishwashers, tap water, distilled water, or deionized water can be used, and among these, the storage stability of the liquid detergent composition for automatic dishwashers can be used. From the viewpoint of properties, distilled water or deionized water is preferred.

<Enzyme (f)>
The liquid detergent composition for an automatic dishwasher of the present invention preferably contains an enzyme from the viewpoint of improving the cleaning performance. As the enzyme, one or more selected from amylase, protease, lipase, cellulase, esterase, and peroxidase can be used, and a commercially available product can be used. Any enzyme may be appropriately selected in consideration of storage stability with other components. Among these, amylases are preferred because they are expected to act on gelatinized starch that is difficult to remove with other surfactants. A protease is also preferable because it exhibits a remarkable effect on a denatured protein that is difficult to remove with a surfactant or the like. In the present invention, it is most preferable to use amylase and protease in combination.
When the liquid detergent composition for an automatic dishwasher contains an enzyme, the content of the enzyme is preferably 0.2% by mass or more, more preferably 0.4% by mass or more, and further preferably 0.8% by mass. More preferably, it is 1.0% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

<PH>
The pH at 20 ° C. of the liquid detergent composition for an automatic dishwasher is 6 or more and 9 or less from the viewpoint of detergency and safety. When the pH is within this range, the detergency against dried semi-ripe egg yolk stains is improved, and the storage stability is also excellent. In the present invention, the pH is preferably 6.5 or more, more preferably 7 or more, and preferably 8.6 or less, more preferably 8.2 or less, from the viewpoint of storage stability of the cleaning composition. More preferably, it is 7.8 or less. The pH is a value obtained by measuring a stock solution of a liquid detergent composition for an automatic dishwasher, that is, a liquid detergent composition itself for an automatic dishwasher.

<Optional component>
In the liquid detergent composition for an automatic dishwasher, other components that can be used in ordinary detergents can be blended. Examples include pH adjusters, alkali agents, surfactants other than the component (d), solvents, enzyme stabilizers such as calcium salts and formic acid, fragrances, antibacterial agents, antifungal agents, and dyes. it can.

(PH adjuster)
As the pH adjuster, one or more selected from inorganic acids such as hydrochloric acid and sulfuric acid, sodium hydroxide, potassium hydroxide, and monoethanolamine can be used.
Among these, hydrochloric acid, sulfuric acid, and monoethanolamine are preferable. In addition, you may use the below-mentioned alkali agent as a pH adjuster.

(Alkaline agent)
As the alkali agent, alkali metal carbonates, alkali metal silicates, amine compounds and the like can be used.
The alkali metal carbonate is preferably one or more selected from sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate. Moreover, you may use the anhydrous salt of sodium carbonate known as soda ash.
As the alkali metal silicate, crystalline layered sodium silicate (manufactured by Tokuyama Siltec Co., Ltd., trade name “pre-feed”) or the like can be used. An amorphous material may be used. Alkali metal silicate is also effective as an antioxidant for tableware.
An alkanolamine can be mentioned as an amine compound. In the present invention, primary alkanolamines are particularly preferred, and specific examples include monoethanolamine. Of these alkali agents, alkali metal carbonates are preferred.
When the liquid detergent composition for an automatic dishwasher contains an alkali agent, the content of the alkali agent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 2% by mass or more. And, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

(Surfactant)
Examples of the surfactant include nonionic surfactants other than the component (d), anionic surfactants, amphoteric surfactants, and cationic surfactants.
In the present invention, bleaching agents, bleach activators, and the like that are generally blended as cleaning agents for automatic dishwashers may be blended as cleaning auxiliary components that further improve detergency.

(solvent)
The liquid detergent composition for an automatic dishwasher of the present invention is preferably an aqueous solution, but a solvent other than water may be used. Examples of solvents other than water include ethanol, polyethylene glycol, polypropylene glycol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and 3-methyl-3-methoxy. One or more selected from butanol, phenoxyethanol, phenyl glycol, phenoxyisopropanol, butyl diglycol (diethylene glycol monobutyl ether), dibutylene glycol, and benzyl alcohol can be used.
When using a solvent other than water, the amount of the solvent in the liquid detergent composition for an automatic dishwasher is preferably 3% by mass or more, more preferably 5% by mass or more, from the viewpoint of improving the stability of the composition. Further, it is preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less from the viewpoint of inexpensive production.

  Since the liquid cleaning composition for automatic dishwashers of the present invention has higher cleaning performance than conventional ones, the amount used can be reduced. Further, since the amount of use can be reduced, the container can be made compact, and the amount of packaging material used can be reduced.

The liquid detergent composition for an automatic dishwasher of the present invention can be obtained by mixing each component, and the aqueous solution of the component (c) is added to the aqueous solution of the component (c) and mixed. Then, it is preferable to prepare by adding and mixing the aqueous solution of the component (b). Preparation in this order is preferable because each component is stably present in the solution. About another component, it is preferable to add, after mixing said (a)-(c) component.
The aqueous solution of the component (a) and the concentration of the component (c) at the time of mixing are preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of stability in the solution of each component. More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less.

[How to wash dishes]
The tableware washing method of the present invention contains the following cationic polymer (a), the following anionic polymer (b), a chelating agent (c), a nonionic surfactant (d), and water (e), The concentration of the component (a) is 1 ppm or more and 1,000 ppm or less, and the mass ratio of the component (b) to the component (a) ((b) / (a)) is 0.01 or more and 60 or less. A cleaning method for tableware, wherein cleaning water having a mass ratio ((c) / (a)) of component (c) to component (a) is 0.4 or more and 30 or less is brought into contact with the surface of the tableware.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)

  The concentration of the component (a) in the washing water is 1 ppm or more, preferably 10 ppm or more, more preferably 50 ppm or more, and further preferably 100 ppm or more from the viewpoint of improving washing performance, and increases washing performance and cost. From the viewpoint of balance with the above, it is 1,000 ppm or less, more preferably 900 ppm or less, still more preferably 850 ppm or less.

  In the dishwashing method of the present invention, the mass ratio ((b) / (a)) of the component (b) to the component (a) is 0.01 or more and 60 or less, and the (c) ) Component mass ratio ((c) / (a)) is 0.4 or more and 30 or less. The preferred ranges and effects of these mass ratios are the same as the aforementioned preferred ranges and effects.

<Examples 1-7, Comparative Examples 1-6>
100 g of the liquid detergent composition for an automatic dishwasher of Example 1 was prepared according to the following procedure so as to have the ratio shown in Table 1.
A 20% by weight cationic polymer aqueous solution was added to the 20% by weight chelating agent aqueous solution and stirred for 5 minutes, and then 40% by weight anionic polymer aqueous solution was added thereto and stirred for 5 minutes. Subsequently, the liquid detergent composition for automatic dishwashers was prepared by adding a nonionic surfactant, a pH adjuster, etc. and stirring for 5 minutes.

The liquid detergent composition for automatic dishwashers prepared in Examples and Comparative Examples was subjected to the following evaluation.
<PH measurement>
The pH value at 20 ° C. was measured according to JIS Z-8802: 2011 using a pH meter (manufactured by Horiba, Ltd., “F-52”, pH electrode 6367-10D). In addition, as a measurement solution, the liquid detergent composition for automatic dishwashers prepared in the above Examples and Comparative Examples was used as it was without diluting. The results are shown in Table 1.

<Evaluation of cleanability of oil stains>
-Preparation of test dish (1) Tallow (manufactured by Sigma Aldrich Japan Co., Ltd.) was uniformly dissolved in a hot water bath.
(2) 1.0 g of beef tallow as described in (1) above with a dropper on a polypropylene dish (PP tableware “C-39 meat dish (diameter 230 mm × 17 mm)”, manufactured by Kimoto Kitchenware Co., Ltd.) It was dropped and allowed to cool at 25 ° C. for 30 minutes or longer and solidified to prepare a test dish.
・ Cleaning test (1) Put a dirty polypropylene dish (PP dish) in the lower basket (large dish storage) in the dishwasher so that the surface with the dirt applied is on the inside of the dish tray groove. Two sheets were set up.
(2) Two polypropylene dishes with dirt and two clean polypropylene dishes without dirt were alternately placed.
(3) The liquid detergent composition for an automatic dishwasher prepared in the above examples and comparative examples was charged so that the concentration in the cleaning liquid at the time of cleaning was 0.67% by mass, and then washed on a standard course.

-Evaluation method About the oil film which remained on the polypropylene plate surface by five evaluators, it evaluated according to the following evaluation criteria. The results are shown in Table 1.
・ Evaluation criteria A: The dish was completely washed B: Part of the front and back of the dish was nulled C: Most of the dish was nulled

<Detergency evaluation for tea astringent stains>
-Preparation of test tableware (1) Three commercially available tea tea bags ("Nitto tea DAY & DAY tea bag" manufactured by Mitsui Norin Co., Ltd.) were prepared for 1 L of hot water.
(2) A tea bag was put in boiling water and the tea liquid was boiled for 10 minutes.
(3) The tea bag was taken out and the black tea liquid was stirred to make it uniform.
(4) Take 100 g each of tea solution (excluding bubbles) in melamine hot water cups (tumbler, small MN-17 (diameter 74 mm, height 80 mm), 200 mL purchased from DAIWA), leave it for 1 hour, Was excluded.
(5) The test tableware was dried as it was at 25 ° C. for a whole day and night.

Washing test The dishwasher (Panasonic Corporation, model number “NP-TR3”) was prepared so that the concentration of the liquid detergent composition for automatic dishwashers prepared in the examples and comparative examples was 0.67% by mass in the washing liquid. (Desktop type)) was put into a dedicated detergent container (amount of tap water used: 3L).
Four melamine hot water bottles were placed in a basket on the dishwasher and the test dishes were washed on a standard course.

Evaluation method The tea astringent remaining on the surface of the test tableware was visually observed by five evaluators and evaluated according to the following evaluation criteria. The results are shown in Table 1.
(Evaluation criteria)
A: The bath was completely washed B: The waterline was slightly visible C: The waterline was clearly left

<Evaluation of detergency of dried soft-boiled egg yolk stains>
-Preparation of test dish (1) The chicken eggs (5 pieces) were broken and the egg yolks were separated using an egg yolk separator.
(2) Five egg yolks were put into the screw tube (No. 8) and heated in a water bath (73 to 75 ° C.) for 10 minutes.
(3) The screw tube was taken out from the water bath and allowed to stand at 25 ° C. for 1 hour, and the half-boiled egg yolk was scraped into a tea strainer and strained.
(4) Line up 1kg of egg yolks after thoroughly mixing the half-boiled egg yolk and draining it from the lower part of the tea strainer. Was applied uniformly.
(5) The soft-boiled egg yolk applied to the ceramic dish was dried at 25 ° C. for a whole day and night to prepare a test dish.

Washing test Dishwasher (Panasonic Corporation, model number) so that the concentration of the liquid detergent composition for automatic dishwashers prepared in the examples and comparative examples is 0.67% by mass in the washing liquid at the time of washing. “NP-P45M2PS” (built-in type)) was put into a dedicated detergent container and washed in a speedy course. In addition, two soiled ceramic dishes were set up in every other rightmost dish tray groove in the lower right part of the dishwasher. Two soiled ceramic dishes and two clean ceramic dishes without dirt were placed alternately.
-Evaluation method By 5 evaluators, the egg yolk remaining on the surface of the ceramic dish was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1.
・ Evaluation criteria A: The dish was completely washed B: Some egg yolk spots remained in the form of dots C: Most of the applied yolk remained unwashed

<Reattachment evaluation>
(Preparation of defatted particles)
30 g of curry powder (manufactured by House Foods Co., Ltd.) was added to 1 L of 100 ppm aqueous solution of Emulgen 105 (manufactured by Kao Corporation), stirred for 10 minutes, and then subjected to suction filtration using a stainless mesh (200 mesh). The same operation was performed 5 times on the particles on the mesh. Furthermore, in order to remove the adsorbed surfactant, the particles on the mesh were added to 1 L of ion exchange water and stirred for 10 minutes. The same operation was performed 5 times, followed by lyophilization. The obtained particles were subjected to evaluation as degreased particles.
(Washing operation)
200 mg of the degreased particles was put into a detergent inlet of a dishwasher (Panasonic Corporation, model number “NP-P45M2PS” (built-in type)). Tableware is set in all dish trays in an automatic dishwasher, and the concentration of the liquid detergent composition for an automatic dishwasher prepared in the above examples and comparative examples in the cleaning liquid at the time of cleaning is 0.67% by mass. After being introduced, it was operated on the standard course. After the washing, the amount of adhering particles was measured for four beverage tableware set at the end in the automatic dishwasher, and the reattachment evaluation of dirt was performed according to the following evaluation criteria. The results are shown in Table 1.
Evaluation criteria A: The amount of reattached particles was less than 4.0 mg.
B: The amount of reattached particles was 4.0 to 6.0 mg.
C: The amount of reattached particles exceeded 6.0 mg.

Details of the compounds described in the table are as follows.
<Cationic polymer>
CM-318, manufactured by Kuraray Co., Ltd., average molecular weight 90 kDa, degree of cationization 1.7 mol%, p: q: r in the following formula (I) is 88.5: 9.8: 1.7

  HP-1, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., average molecular weight 90 kDa, cationization degree 0.9 mol%, p: q: r in the following formula (II) is 86.8: 12.3: 0.9

  Poiz-C60H, manufactured by Kao Corporation, average molecular weight 600 kDa, degree of cationization 0.49 mol%

<Anionic polymer>
Poiz-520, manufactured by Kao Corporation, Na acrylate / Na maleate copolymer, m: n in the following formula (III) is 70:30, weight average molecular weight 21,000

<Chelating agent>
Dissolvine GL-47S, Akzo Nobel Co., Ltd. Malic acid, manufactured by Fuso Chemical Industry Co., Ltd.

<Nonionic surfactant>
Polyoxyethylene alkyl ether (sec-C12-14 (EO) 3), effective content 100%, Nippon Shokubai Co., Ltd. alkylglycoside (C10,12,14), effective content 40%, Kao Corporation polypropylene glycol, average Molecular weight 3000, effective content 100%, manufactured by Kao Corporation Polyoxyethylene alkyl ether (C12 (EO) 5), effective content 100%, manufactured by Kao Corporation

<Enzyme>
Termamyl Ultra 300L, Novozymes Japan Co., Ltd. Everlase 16L, Novozymes Japan Co., Ltd.

  As is apparent from Table 1, the liquid detergent composition for an automatic dishwasher of the present invention exhibits excellent cleaning performance against oil stains, tea astringent stains, and soils in which lipids and proteins are combined, and stains. Can be suppressed.

Claims (6)

The following cationic polymers (a), the following anionic polymers (b), the following chelating agent (c), a nonionic surfactant (d), and contain water (e), the content of the component (a) 0.1% by mass or more and 20% by mass or less, and the mass ratio of the component (b) to the component (a) ((b) / (a)) is 1.5 or more and 60 or less, Liquid detergent for automatic dishwashing machine whose mass ratio ((c) / (a)) of said (c) component with respect to a) component is 1 or more and 30 or less, and pH at 20 degreeC is 6 or more and 9 or less Composition.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)
(C) component: citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1 , 3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethylglutamic acid and tripolyphosphoric acid, or those A chelating agent that is one or more selected from the salts of

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)   Furthermore, the liquid detergent composition for automatic dishwashers of Claim 1 which contains an enzyme as (f) component.   The liquid detergent composition for automatic dishwashers according to claim 1 or 2, wherein the cationic polymer has an average molecular weight of 10,000 Da or more and 2,000,000 Da or less.   The liquid detergent composition for automatic dishwashers according to any one of claims 1 to 3, wherein the cationic polymer is one or more selected from cation-modified polyvinyl alcohol and cation-modified hydroxyl ethyl cellulose.   The chelating agent is one or more selected from citric acid, malic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, glutamic acid diacetic acid and tripolyphosphoric acid, or a salt thereof, A liquid detergent composition for an automatic dishwasher according to claim 1. The following cationic polymers (a), contains the following anionic polymers (b), the following chelating agent (c), a nonionic surfactant (d), and water (e), wherein the concentration of component (a) 1ppm As mentioned above, it is 1,000 ppm or less, the mass ratio ((b) / (a)) of the component (b) to the component (a) is 1.5 or more and 60 or less, and the component relative to the component (a) (C) A method for cleaning tableware, wherein cleaning water having a mass ratio of components ((c) / (a)) of 1 or more and 30 or less is brought into contact with the surface of the tableware.
Component (a): having one or two or more cationic groups selected from the following general formulas (a-1) to (a-5), and having a degree of cationization of 0.25 mol% to 5 mol% Certain cationic polymer (b) component: Anionic polymer having one or more structural units derived from an anionic group-containing monomer selected from acrylate, methacrylate and maleate (provided that (a) (Excluding ingredients)
(C) component: citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetic acid, glutamic acid diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, nitrilotriacetic acid, 1,3-propanediamine triacetic acid, 1 , 3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, dihydroxyethylglycine, hydroxyethylethylenediaminedicarboxymethylglutamic acid and tripolyphosphoric acid, or those A chelating agent that is one or more selected from the salts of

(Wherein R ^{1 to} R ¹⁴ each independently represents an alkyl group having 1 to 6 carbon atoms, Z ⁻ represents an anion independently, and m represents an integer of 1 to 10 independently. N represents an integer of 0 or more and 10 or less independently.)