JP6644490B2 - Liquid detergent composition for tableware - Google Patents

Description

  The present invention relates to a liquid dishwashing detergent composition.

Examples of the stains adhering to tableware include oil stains, starch stains such as rice grains, protein stains such as eggs, and pigment stains such as tea. Among these, dirt, which is a complex of lipid and protein represented by soft-boiled eggs, is hard to remove because it adheres firmly to the dishes and is difficult to remove by washing with an automatic dishwasher. Become. In addition, there is a problem that oil stains are difficult to clean and reattach to tableware.
Such dry stains and oil stains are difficult to wipe off with a cloth or kitchen paper before washing with the automatic dishwasher, and the stains remain even after washing with the automatic dishwasher. There is a need to do.

Patent Literature 1 discloses that a nonionic surfactant (A) having a hydrophilic-lipophilic balance (HLB) of 1 to 7.0 is 0.1 to 10% by mass, and at least one compound of carbonate and silicate A detergent composition for an automatic dishwasher, which contains 5 to 70% by mass of (B) and 5 to 20% by mass of percarbonate (C), and has a pH of 9 to 13 at 0.1% by mass of an aqueous solution of 0.1% by mass at 25 ° C. Is disclosed.
Patent Literature 2 discloses a detergent containing decyl sulfate and condensed phosphate at a predetermined mass ratio.

JP 2014-1111697 A JP 2014-065812 A

  In Patent Literature 2, a large amount of condensed phosphate is used in combination with decyl sulfate, but when the condensed phosphate is reduced, the foam suppressing property is reduced.

  The present invention provides a liquid detergent composition for dishes which has good foam suppressing properties and excellent detergency against complex stains of protein and lipid even when hard water is used.

The present invention provides (a) an anionic surfactant represented by the following general formula (a1) [hereinafter, referred to as a component (a)] of 1.5% by mass or more, and (b) a compound represented by the following general formula (b1). 0 to 2% by mass of anionic surfactant [hereinafter referred to as "component (b)"], and (c) a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms or a salt thereof. The present invention relates to a liquid detergent composition for dishes, which contains a polymer (hereinafter, referred to as a component (c)) containing a structural unit derived from water, and has a pH (20 ° C) of 6 or more.
R ¹ -O- (PO) _m1 -SO ₃ -M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number from 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]
_{^{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[Wherein, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents an average addition mole number of PO, and a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]

  Advantageous Effects of Invention According to the present invention, it is possible to provide a dishwashing liquid detergent composition which has good foam suppressing properties and is excellent in detergency against complex stains of protein and lipid even when hard water is used.

The component (a) of the present invention is an anionic surfactant represented by the following general formula (a1).
R ¹ -O- (PO) _m1 -SO ₃ -M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number from 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]

In the general formula (a1), R ¹ is an alkyl group or an alkenyl group having 10 carbon atoms from the viewpoint of detergency, and may be linear or branched. R ¹ is preferably a linear alkyl group having 10 carbon atoms.
m1 represents the average number of moles of PO added, and is 0 or more, and from the viewpoint of detergency and defoaming properties, is 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and still more preferably 0 or less. 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less. It is also preferable that m1 is 0.
M ¹ is a hydrogen atom or a cation, and examples of the cation forming a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Alkali metal ions include sodium ion, potassium ion and lithium ion, and alkanolammonium ions include monoethanolammonium ion, diethanolammonium ion and triethanolammonium ion. Of these, sodium ions or potassium ions are preferred, and sodium ions are more preferred.

  Two or more different components (a) may be used.

Incidentally, the compound represented by the general formula (a1) can be obtained by sulfating a raw material alcohol represented by R ¹ O— (PO) _m1 H. However, as long as the present invention is not impaired, R ¹ O Raw material alcohol in which ethylene oxide is slightly added _to- (PO) _m1H may be used.

The component (b) of the present invention is an anionic surfactant represented by the following general formula (b1).
^{_{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[Wherein, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents an average addition mole number of PO, and a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]

In the general formula (b1), R ² is an alkyl group or an alkenyl group having 12 or more and 14 or less carbon atoms from the viewpoint of detergency and defoaming property, and may be linear or branched. . R ¹ is preferably a linear alkyl group.
m2 represents the average number of moles of PO added and is 0 or more, and from the viewpoint of detergency and defoaming property, is 1.5 or less, preferably 1.0 or less, more preferably 0.7 or less, and further preferably 0 or less. 0.5 or less, more preferably 0.3 or less, even more preferably 0.1 or less. It is also preferable that m2 is 0.
M ² is a hydrogen atom or a cation, and examples of the cation forming a salt include an alkali metal ion, an alkanol ammonium ion, and an ammonium ion. Alkali metal ions include sodium ion, potassium ion and lithium ion, and alkanolammonium ions include monoethanolammonium ion, diethanolammonium ion and triethanolammonium ion. Of these, sodium ions or potassium ions are preferred, and sodium ions are more preferred.

  Two or more different components (b) may be used.

  The component (c) of the present invention is a polymer containing a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms or a structural unit derived from a salt thereof.

  The component (c) is a polymer containing a structural unit derived from a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms or a salt thereof (hereinafter, referred to as the component (c1)). It is united. The carbon number of the component (c1) is the total carbon number of the carboxylic acid.

  The component (c1) is one or two selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid, salts thereof, and acid anhydrides thereof. More than a species.

  The component (c1) is preferably one or more selected from acrylic acid, methacrylic acid, maleic acid, salts thereof and maleic anhydride from the viewpoint of detergency, more preferably acrylic acid, maleic acid And one or more selected from salts thereof. The salt is at least one selected from a sodium salt, a potassium salt, an alkanolamine salt, and an ammonium salt. The salt may be formed by using a salt type compound as a monomer, or may be formed by neutralization after polymerization.

  The proportion of the component (c1) in all the monomers of the component (c) is preferably 90 mol% or more, more preferably 95 mol% or more, further preferably 98 mol% or more, from the viewpoint of detergency. Preferably it is 100 mol% or less.

The component (c) includes a structural unit derived from acrylic acid or a salt thereof [hereinafter, referred to as a structural unit (c _AA )] and a structural unit derived from maleic acid or a salt thereof, or maleic anhydride [hereinafter, a structural unit (c _MA )] Is preferably included. That is, the component (c1) preferably contains acrylic acid or a salt thereof and maleic acid or a salt thereof or maleic anhydride. From the viewpoint of storage stability and detergency, the total ratio of the structural unit (c _AA ) and the structural unit (c _MA ) is preferably 90 mol% or more, more preferably 90 mol% or more, of the structural units derived from the component (c1). Is 95 mol% or more, more preferably 98 mol% or more, and preferably 100 mol% or less, and may be 100 mol%.

When the component (c) contains the structural unit (c _AA ) and the structural unit (c _MA ), the molar ratio of the structural unit (c _AA ) / the structural unit (c _MA ) is preferably 0 from the viewpoint of detergency. 0.6 or more, more preferably 1 or more, still more preferably 1.5 or more, and preferably 9 or less, more preferably 4 or less, and still more preferably 3 or less.

  The component (c) is a polymer containing a constituent unit derived from the component (c1), but may contain a constituent unit other than the constituent unit derived from the component (c1). That is, the component (c) is a copolymer containing a monomer copolymerizable with the component (c1), specifically, a structural unit derived from the component (c1) and a structural unit derived from the component (c2) described later. It may be united.

The component (c2) is one or two or more monomers selected from olefins having 2 to 12 carbon atoms, alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group, and styrene. .
The olefin having 2 to 12 carbon atoms is one or more selected from ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene, and is preferably butylene, isobutylene, diisobutylene, pentene, and hexene. And at least one member selected from the group consisting of diisobutylene. The carbon number of the olefin is 2 or more, preferably 4 or more, and 12 or less, preferably 6 or less.
The alkyl (meth) acrylate in which the carbon number of the alkyl group is 1 or more and 12 or less is preferably 2 or more, more preferably 4 or more, and preferably 12 or less, and more preferably 8 or less. .

  The molar ratio of the component (c1) to the component (c2) (component (c1) / component (c2)) is preferably 0.1 or more, more preferably 0.2 or more, still more preferably 0.3 or more, and preferably It is 10 or less, more preferably 5 or less, and still more preferably 3 or less.

  In the component (c), the total ratio of the structural units derived from the component (c1) and the structural units derived from the component (c2) is preferably 90 mol% or more, more preferably 95 mol, from the viewpoint of storage stability. % Or more, more preferably 98% or more, and preferably 100% or less.

From the viewpoint of detergency, the weight average molecular weight of the component (c) is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, still more preferably 40,000 or more, even more preferably 55,000 or more, and From the viewpoint of force and storage stability, it is preferably 250,000 or less, more preferably 200,000 or less, further preferably 150,000 or less, still more preferably 100,000 or less, still more preferably 80,000 or less, and still more preferably 65,000 or less.
In addition, the weight average molecular weight of the component (c) is such that when the polymer of the component (c) is a copolymer of acrylic acid and / or methacrylic acid and maleic acid or a salt thereof, a mixed solvent of acetonitrile and water (phosphoric acid) Buffer solution) as a developing solvent and polyethylene glycol as a standard substance, which can be determined by gel permeation chromatography.
Further, when the polymer of the component (c) is a copolymer of the component (c1) and the component (c2), for example, a diisobutylene-maleic acid copolymer, the weight average molecular weight is acetonitrile and 0.1 M sodium chloride. It can be determined by gel permeation chromatography using a mixture with an aqueous solution (acetonitrile: aqueous sodium chloride solution (volume ratio) = 30: 70) as a developing solvent and polyethylene glycol as a standard substance.

  The component (c) is preferably polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, an acrylic acid-maleic acid copolymer or a salt thereof, methacrylic acid-maleic acid copolymer or a salt thereof from the viewpoint of detergency. Salts, and one or more polymers selected from diisobutylene-maleic acid copolymers or salts thereof, more preferably polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, and acrylic acid-maleic acid copolymer. It is at least one polymer selected from the group consisting of a methacrylic acid-maleic acid copolymer and a salt thereof, and more preferably an acrylic acid-maleic acid copolymer or a salt thereof. Further, as the component (c), two or more of the above polymers may be used as a mixture.

<Water>
The cleaning composition for hard surfaces of the present invention is a liquid cleaning composition containing water. Any of the above-mentioned components may be dissolved, dispersed, or emulsified in water. As the water, ion-exchanged water or distilled water from which metal components have been removed, or hypochlorous acid sterilized water in which hypochlorous acid is dissolved in an amount of about 0.5 ppm to about 10 ppm can be used. Water is the balance of the composition, and is contained in an amount of 100% by mass as a whole.

<Composition of liquid detergent composition for tableware>
The dishwashing liquid detergent composition of the present invention comprises the component (a) in an amount of 1.5% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and still more preferably 4% by mass or more, from the viewpoint of detergency. % By mass or more, and from the viewpoint of foam suppression, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, even more preferably 6% by mass or less. % By mass or less. Incidentally, (a) the content of the component (mass%), sodium salt conversion, i.e., M ¹ in the general formula (a1) is calculated based on the amount of compound in terms of sodium ion.

The dishwashing liquid detergent composition of the present invention comprises the component (b) in an amount of 0% by mass or more and 2% by mass or less, preferably 1.5% by mass or less, from the viewpoints of detergency and foam control. The content is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0% by mass. Incidentally, (b) the content of the component (mass%), sodium salt conversion, i.e., M ² in the general formula (b1) is calculated based on the amount of compound in terms of sodium ion.

  In the dishwashing liquid detergent composition of the present invention, the component (c) is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 3% by mass or more, further preferably from the viewpoint of detergency. Is at least 4% by mass, more preferably at least 6% by mass, even more preferably at least 8% by mass, even more preferably at least 8.5% by mass, and from the viewpoint of storage stability, preferably at most 20% by mass. , More preferably 15% by mass or less, further preferably 12% by mass or less, even more preferably 11% by mass or less.

In the dishwashing liquid detergent composition of the present invention, the component (a) / component (c) has a mass ratio of component (a) / component (c) of preferably 0.05 from the viewpoint of detergency and storage stability. Or more, more preferably 0.1 or more, still more preferably 0.2 or more, still more preferably 0.3 or more, even more preferably 0.4 or more, even more preferably 0.5 or more, and detergency and From the viewpoint of foam suppression, it is preferably 10 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, still more preferably 2 or less, and still more preferably 1 or less. The mass ratio of the component (a) / the component (c) is obtained by converting the content of the component (a) into a sodium salt, that is, a compound in which M ¹ in the general formula (a1) is a sodium ion. It is calculated based on:

  The dishwashing liquid detergent composition of the present invention preferably contains a nonionic surfactant as the component (d) from the viewpoint of storage stability and washability.

  Examples of the nonionic surfactant include (1) polyoxyalkylene monoalkyl or alkenyl ether, (2) alkyl polyglycoside (glycoside type nonionic surfactant), (3) aliphatic alkanolamide, and (4) sorbitan. One or more selected from the group consisting of a nonionic surfactant, (5) alkyl monoglyceryl ether, (6) fatty acid monoglyceride, and (7) sucrose fatty acid ester is preferable, and two or more may be used.

  The nonionic surfactant is more preferably at least one selected from the group consisting of (1) polyoxyalkylene monoalkyl or alkenyl ether, and (2) alkyl polyglycoside from the viewpoints of detergency and foam suppression. Yes, from the viewpoint of detergency, (2) an alkyl polyglycoside is more preferable, and from the viewpoint of foam suppressing properties, (1) polyoxyalkylene monoalkyl or alkenyl ether is more preferable.

The above-mentioned nonionic surfactant is more specifically shown.
(1) Polyoxyalkylene monoalkyl or alkenyl ether In the nonionic surfactant (1), the carbon number of the alkyl group or alkenyl group is preferably 6 or more, more preferably 8 or more, still more preferably 10 or more. It is even more preferably 12 or more, and preferably 22 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.

  In the nonionic surfactant (1), the average addition mole number of the alkylene oxide is preferably more than 0, more preferably 1 or more, still more preferably 3 or more, and preferably 50 or less, more preferably 30 or less. , More preferably 20 or less, even more preferably 10 or less.

  The alkylene oxide is preferably at least one selected from ethylene oxide, propylene oxide, and butylene oxide, and more preferably at least one selected from ethylene oxide and propylene oxide.

Preferred examples of the nonionic surfactant (1) include a nonionic surfactant represented by the following general formula (d1).
^{_{R 11 O [(C 2 H}} 4 O) l / (C 3 H 6 O) n] H (d1)
[In the formula, R ¹¹ represents a hydrocarbon group having 6 to 22 carbon atoms. l and n represent the average number of moles added, l represents a number of 0 or more and 30 or less, n represents a number of 0 or more and 30 or less, and 1 and n do not become 0 at the same time. “/” Indicates that the oxyethylene group and the oxypropylene group may be added to either random or block regardless of order. ]

The carbon number of R ^{11 in} the general formula (d1) is preferably 8 or more, more preferably 10 or more, and still more preferably 12 or more, and preferably 18 or less, more preferably 16 or less, and still more preferably. Is 14 or less.

R ¹¹ is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.

Examples of the alkyl group include various octyl groups (including a 2-ethylhexyl group), various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups (lauryl groups), various tridecyl groups, various tetradecyl groups, Examples include various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, and various octadecyl groups.
Examples of the alkenyl group include various octanyl groups, various nonanyl groups, various decanyl groups, various undecanyl groups, various dodecanyl groups, various tridecanyl groups, various tetradecanyl groups, various pentadecanyl groups, various hexadecanyl groups, various heptadecanyl groups, various octadecanyl groups (for example, Oleyl group and linole group). In addition, "various" means various isomers including n-, sec-, tert-, and iso-.

L and n in the above general formula (c1) are each independently preferably 1 or more, more preferably 2 or more, and preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and further more Preferably it is 10 or less, more preferably 5 or less.
Further, the HLB value of the polyoxyalkylene monoalkyl or alkenyl ether, and the nonionic surfactant represented by the general formula (d1) is preferably 5 or more, more preferably 7 or more, and preferably 19 or more. Or less, more preferably 15 or less, still more preferably 13 or less.
Here, the HLB value is defined by the following Griffin equation.
HLB value = 20 × Mw / M
(In the formula, M is the molecular weight of the nonionic surfactant, and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.) In the general formula (d1), the hydrophilic portion is It is the sum of oxyethylene groups and oxypropylene groups.

(2) Alkyl polyglycoside (glycoside type nonionic surfactant)
The nonionic surfactant (2) is preferably a nonionic surfactant represented by the following general formula (d2).
R ²¹ (OR ²² ) _x G _y (d2)
Wherein, R ²¹ represents a linear or branched carbon atoms chains 8 to 18, preferably 12 to 14 alkyl, alkenyl or alkylphenyl group, preferably an alkyl group, R ²² is the number of carbon atoms It represents an alkylene group of 2 or more and 4 or less, and G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. x represents the average number of moles added, and is a number from 0 to 5 inclusive. y represents a number whose average value is 1 or more and 5 or less. ]

In the general formula (d2), R ²¹ is a linear or branched alkyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 14 or less carbon atoms.

  In the general formula (d2), x is preferably 0 or more and 2 or less, and more preferably 0. y is preferably 1.1 or more, and preferably 1.5 or less, more preferably 1.4 or less. Here, y is a value measured by the proton NMR method.

  In the general formula (d2), G is a residue derived from one or more monosaccharides selected from glucose and fructose from the viewpoint of their availability and cost. G is a residue derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a glucose monosaccharide.

(3) Fatty acid alkanolamide The nonionic surfactant of (3) is preferably a nonionic surfactant represented by the following general formula (d3).

[In the formula, R ³¹ represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, preferably 10 to 18 carbon atoms, and R ³² and R ³³ may be the same or different and each represent a hydrogen atom or a methyl group. , P represents a number from 1 to 3, and q represents a number from 0 to 3. ]

(4) Sorbitan nonionic surfactant The nonionic surfactant (4) is a nonionic surfactant represented by the following general formula (d4-I) and the following general formula (d4-II) And at least one nonionic surfactant selected from nonionic surfactants represented by

[Wherein, R ⁴¹ represents an alkylene group having 2 to 4 carbon atoms, R ⁴² independently represents an alkyl group or an alkenyl group having 1 to 14 carbon atoms, and the alkyl group and the alkenyl group are Any of a chain, a branched chain and a ring may be used, f, g, and h each represent an average number of moles added, and the sum of f, g, and h is a number of 3 or more and 50 or less. ]

In the above formula (d4-I) or (d4-II), R ⁴¹ is an alkylene group having 2 to 4 carbon atoms, preferably an ethylene group or a propylene group, and more preferably an ethylene group.

  In the general formula (d4-I) or (d4-II), f, g, and h are each independently preferably 0 or more, and preferably 50 or less, more preferably 30 or less. The sum of f, g, and h is preferably 3 or more, more preferably 4 or more, and preferably 50 or less, and more preferably 30 or less.

(5) Alkyl monoglyceryl ether The nonionic surfactant (5) is preferably an alkyl monoglyceryl having a linear or branched alkyl group having 6 to 22 carbon atoms, more preferably 10 to 14 carbon atoms. Glyceryl ether.

(6) Fatty acid monoglyceride The nonionic surfactant (6) is preferably a fatty acid glycerin monoester having a linear or branched alkyl group having 8 to 22 carbon atoms, more preferably 10 to 14 carbon atoms. It is.

(7) Sucrose fatty acid ester The nonionic surfactant (7) is a sucrose fatty acid ester having a linear or branched alkyl group having 8 to 18 carbon atoms, more preferably 12 to 14 carbon atoms. .

  In the dishwashing liquid detergent composition of the present invention, component (d) is preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and still more preferably from the viewpoint of storage stability and cleanability. 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 8% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass, from the viewpoint of detergency and foam control. %, More preferably 1% by mass or less, even more preferably 0.7% by mass or less.

  The content of water in the dishwashing liquid detergent composition of the present invention is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 98% by mass or less. It is more preferably at most 95% by mass, further preferably at most 93% by mass.

  In the dishwashing liquid detergent composition of the present invention, the pH of a 0.2% by mass aqueous solution is 20 ° C, from the viewpoint of detergency, 6 or more, more preferably 7 or more, and preferably from the same viewpoint. It is 11 or less, more preferably 10 or less, and still more preferably 9 or less.

  The pH at 20 ° C. of the dishwashing liquid detergent composition of the present invention is 6 or more, more preferably 7 or more, and preferably 11 or less, more preferably 10 or less, and still more preferably 9 or less, from the viewpoint of detergency. It is.

  The viscosity at 20 ° C. of the dishwashing liquid detergent composition of the present invention is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and preferably 100 mPa · s or less, from the viewpoint of convenience during use. More preferably, it is 80 mPa · s or less.

  The dishwashing liquid detergent composition of the present invention includes a solvent, a hydrotrope, a dispersant, a pH adjuster, a thickener, a viscosity adjuster, a fragrance, a coloring agent, and an oxidizing agent as long as the object of the present invention is not impaired. Components such as an inhibitor, a preservative, a foam inhibitor, a bleaching agent, and a bleaching activator (however, those which do not correspond to the components (a) to (d)) can be added.

The liquid detergent composition for dishwashing of the present invention can be used for both dishwashers, automatic dishwashers, and handwashing. Liquid detergent compositions for dishwashers, and further automatic dishwashers It is suitable as a liquid detergent composition for use. Further, it is suitably used for washing with a commercial dishwasher. Tableware includes cooking utensils, washing utensils, and the like.
In the case of washing with a dishwasher and a commercial dishwasher, the liquid detergent composition for dishes of the present invention is used as a washing liquid mixed with water. At that time, the composition is arbitrarily transferred into the dishwasher by the supply device to maintain a proper concentration of the washing liquid. The liquid dishwashing liquid detergent composition of the present invention is supplied, for example, by directly inserting a tube dedicated to a commercial dishwasher into a container made of plastic or the like filled with the composition and sucking it up. Thereafter, the cleaning liquid is supplied into the commercial dishwasher.

  The washing liquid prepared from the dishwashing liquid detergent composition of the present invention is preferably prepared from the viewpoint of economy, usually at a constant concentration in a storage tank provided in an automatic washing machine.

  According to the present invention, a washing liquid for an automatic washing machine prepared by diluting the liquid dishwashing composition for dishes of the present invention to 320 times (mass ratio, the same applies hereinafter) to 770 times or less with water, and automatic washing using the washing liquid A washing method for washing dishes by a machine is provided. In this washing method, a step of preparing a washing solution for an automatic washing machine by diluting the liquid dishwashing composition of the present invention 320 times or more and 770 times or less with water, and a dishwasher using the washing solution, Washing the dishes with an automatic dishwasher may be included. The dilution ratio at the time of using the dishwashing liquid detergent composition of the present invention is preferably 770 times (mass ratio, the same applies hereinafter), preferably 700 times or less, more preferably 600 times or less, still more preferably 550 times. Hereinafter, it is more preferably 530 or less, and preferably 320 or more, more preferably 400 or more, further preferably 450 or more, and further preferably 470 or more.

  The concentration of the dishwashing liquid detergent composition of the present invention in a washing solution when used is preferably 0.13% by mass or more, more preferably 0.14% by mass or more, and further more preferably, from the viewpoint of economy and detergency. Is 0.17% by mass or more, more preferably 0.18% by mass or more, still more preferably 0.19% by mass or more, and from the same viewpoint, preferably 0.31% by mass or less, more preferably 0% by mass or less. 0.25% by mass or less, more preferably 0.22% by mass or less, even more preferably 0.21% by mass or less.

  Further, the washing time is preferably 10 seconds or more, more preferably 20 seconds or more, and still more preferably 30 seconds or more from the viewpoint of cleanability, and preferably 3 minutes or less from the viewpoint of productivity and economy. , More preferably 2 minutes or less, even more preferably 1 minute or less.

The washing temperature of the washing solution is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of productivity and washability, and, from the viewpoint of washability, preferably 80 ° C. or lower, more preferably 70 ° C. or lower. It is.
After the dishes are washed, usually in the same dishwasher and further automatically with a dishwasher, quickly, with water, hot water or hot water, for example, hot water of 60 ° C. or more and 80 ° C. or less, 5 minutes or more, 40 minutes Hereinafter, rinsing is performed.

  In a dishwasher, the washing liquid is usually circulated by a pump and used repeatedly.

  With respect to the above-described embodiment, the present invention further discloses the following dishwashing liquid composition.

<1>
(A) 1.5% by mass or more of an anionic surfactant represented by the following general formula (a1) [hereinafter, referred to as a component (a)]; and (b) an anionic surfactant represented by the following general formula (b1). A structural unit derived from a carboxylic acid or a salt thereof having an ionic surfactant [hereinafter referred to as a component (b)] in an amount of from 0% by mass to 2% by mass and (c) a reactive unsaturated group having 3 to 6 carbon atoms. A liquid detergent composition for dishes, comprising a polymer [hereinafter, referred to as a component (c)] and water, and having a pH (20 ° C) of 6 or more.
R ¹ -O- (PO) _m1 -SO ₃ -M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number from 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]
_{^{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[Wherein, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents an average addition mole number of PO, and a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]

<2>
(1) m1 of the component (a) is 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.3 or less, and still more preferably 0.1 or less. The liquid detergent composition for dishes according to <1>.

<3>
The liquid detergent composition for dishes according to <1> or <2>, wherein m1 of the component (a) is 0.

<4>
(A) M ^{1 of the} component is at least one selected from an alkali metal ion, an alkanol ammonium ion, and an ammonium ion, preferably a sodium ion, a potassium ion, a lithium ion, a monoethanol ammonium ion, a diethanol ammonium ion, and Any of the above <1> to <3>, which is at least one selected from triethanolammonium ions, more preferably at least one selected from sodium ions and potassium ions, and still more preferably sodium ions. A liquid detergent composition for dishes according to the above.

<5>
(B) The liquid detergent composition for tableware according to any one of <1> to <4>, wherein R ^{2 of the} component is a linear or branched alkyl group or alkenyl group having 12 to 14 carbon atoms. object.

<6>
The component (b) wherein m2 is 1.0 or less, preferably 0.7 or less, more preferably 0.5 or less, still more preferably 0.3 or less, and still more preferably 0.1 or less. > The liquid detergent composition for dishes according to any one of <5>.

<7>
(B) The liquid detergent composition for dishes according to any one of <1> to <6>, wherein m2 of the component is 0.

<8>
(B) M ^{2 of the} component is one or more selected from alkali metal ions, alkanol ammonium ions, and ammonium ions, preferably sodium ions, potassium ions, lithium ions, monoethanol ammonium ions, diethanol ammonium ions, and Any of the above <1> to <7>, which is at least one selected from triethanolammonium ions, more preferably at least one selected from sodium ions and potassium ions, and still more preferably sodium ions. A liquid detergent composition for dishes according to the above.

<9>
Component (c) contains a structural unit derived from a carboxylic acid having a reactive unsaturated group having 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, or a salt thereof (hereinafter, referred to as component (c1)). The liquid detergent composition for dishes according to any one of the above <1> to <8>, which is a united product.

<10>
Component (c1) is one or two selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, crotonic acid, citraconic acid, salts thereof, and acid anhydrides thereof. The liquid detergent composition for dishes according to <9>, which is at least one kind.

<11>
The component (c1) is one or more selected from acrylic acid, methacrylic acid, maleic acid, salts thereof, and maleic anhydride, and preferably one or more selected from acrylic acid, maleic acid, and salts thereof. The liquid cleaning composition for dishes according to <9> or <10>, which is at least two kinds.

<12>
The proportion of the component (c1) in all the monomers of the component (c) is 90 mol% or more, preferably 95 mol% or more, more preferably 98 mol% or more, and 100 mol% or less. 9> The liquid detergent composition for dishes according to any one of <11>.

<13>
(C1) The liquid detergent composition for dishes according to any one of <9> to <12>, wherein the composition comprises acrylic acid or a salt thereof, maleic acid or a salt thereof, or maleic anhydride.

<14>
As the component (c), a structural unit derived from acrylic acid or a salt thereof [hereinafter, referred to as a structural unit (c _AA )] and a structural unit derived from maleic acid or a salt thereof, or maleic anhydride [hereinafter, a structural unit (c _MA )] The liquid detergent composition for dishes according to any one of the above <9> to <13>, comprising:

<15>
The molar ratio of the structural unit (c _AA ) / the structural unit (c _MA ) is 0.6 or more, preferably 1 or more, more preferably 1.5 or more, and 9 or less, preferably 4 or less, more preferably 3 or more. The liquid detergent composition for dishes according to <14>, which is as follows.

<16>
Component (c) is one selected from a constituent unit derived from component (c1), an olefin having 2 to 12 carbon atoms, an alkyl (meth) acrylate having 1 to 12 carbon atoms in an alkyl group, and styrene. Or the liquid detergent composition for tableware according to any one of the above <9> to <15>, which is a copolymer containing a structural unit derived from two or more kinds of monomers [hereinafter, referred to as a component (c2)]. object.

<17>
(C2) The olefin having 2 or more and 12 or less carbon atoms of the component is one or more selected from ethylene, propylene, butylene, isobutylene, diisobutylene, pentene, and hexene, preferably butylene, isobutylene, diisobutylene. <1> The dishwashing liquid cleaning composition according to <16>, wherein the composition is at least one selected from pentene, hexene, and hexene, more preferably diisobutylene.

<18>
(C2) The liquid detergent composition for dishes according to <16> or <17>, wherein the olefin of the component has 4 or more and 6 or less carbon atoms.

<19>
The molar ratio of the component (c1) to the component (c2) is such that the component (c1) / component (c2) is 0.1 or more, preferably 0.2 or more, more preferably 0.3 or more, and 10 or less, and preferably 10 or less. The dishwashing liquid cleaning composition according to any one of <16> to <18>, wherein the composition is 5 or less, more preferably 3 or less.

<20>
(C) Component is polyacrylic acid or its salt, polymethacrylic acid or its salt, acrylic acid-maleic acid copolymer or its salt, methacrylic acid-maleic acid copolymer or its salt, and diisobutylene-maleic acid One or more polymers selected from copolymers or salts thereof, preferably polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, acrylic acid-maleic acid copolymer or a salt thereof, and methacrylic acid- Any one of the above <1> to <8>, which is at least one polymer selected from a maleic acid copolymer or a salt thereof, and more preferably an acrylic acid-maleic acid copolymer or a salt thereof. Liquid detergent composition for dishes.

<21>
Component (c) has a weight average molecular weight of 5,000 or more, preferably 10,000 or more, more preferably 20,000 or more, still more preferably 40,000 or more, even more preferably 55,000 or more, and 250,000 or less, preferably 200,000 or less, more preferably The dishwashing liquid cleaning composition according to any one of <1> to <20>, wherein the composition is 150,000 or less, more preferably 100,000 or less, still more preferably 80,000 or less, and still more preferably 65,000 or less.

<22>
Component (a) is 2% by mass or more, preferably 3% by mass or more, more preferably 4% by mass or more, and 15% by mass or less, preferably 12% by mass or less, more preferably 10% by mass or less, further more preferably The liquid detergent composition for dishes according to any one of <1> to <21>, wherein the composition contains 8% by mass or less, more preferably 6% by mass or less.

<23>
Any of the above <1> to <22>, which contains the component (b) in an amount of 1.5% by mass or less, preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0% by mass. 6. The liquid detergent composition for dishes according to 4.

<24>
Component (c) is 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 4% by mass or more, still more preferably 6% by mass or more, and still more preferably 8% by mass. Above, more preferably 8.5% by mass or more, and 20% by mass or less, preferably 15% by mass or less, more preferably 12% by mass or less, even more preferably 11% by mass or less. The liquid detergent composition for dishes according to any one of <23>.

<25>
The mass ratio of the component (a) to the component (c) is such that the component (a) / component (c) is 0.05 or more, preferably 0.1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. , Even more preferably 0.4 or more, even more preferably 0.5 or more, and 10 or less, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, even more preferably 2 or less, and even more. The liquid detergent composition for dishes according to any one of <1> to <24>, which is preferably 1 or less.

<26>
The dishwashing liquid cleaning composition according to any one of <1> to <25>, further comprising (d) a nonionic surfactant (hereinafter, referred to as a (d) component).

<27>
The component (d) is (1) polyoxyalkylene monoalkyl or alkenyl ether, (2) alkyl polyglycoside, (3) aliphatic alkanolamide, (4) sorbitan nonionic surfactant, (5) alkylmono One or more nonionic surfactants selected from the group consisting of glyceryl ether, (6) fatty acid monoglyceride, and (7) sucrose fatty acid ester, preferably (1) polyoxyalkylene monoalkyl or alkenyl ether And (2) the liquid detergent composition for dishes according to <26>, wherein the composition is one or more nonionic surfactants selected from the group consisting of alkyl polyglycosides.

<28>
The dishwashing liquid composition according to <27>, wherein the component (d) is (1) a polyoxyalkylene monoalkyl or alkenyl ether.

<29>
The carbon number of the alkyl group or alkenyl group of the polyoxyalkylene monoalkyl or alkenyl ether is 6 or more, preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and 22 or less, preferably 18 or less, The dishwashing liquid cleaning composition according to <27> or <28>, wherein the composition is preferably 16 or less, more preferably 14 or less.

<30>
The average addition mole number of the alkylene oxide of the polyoxyalkylene monoalkyl or alkenyl ether is more than 0, preferably 1 or more, more preferably 3 or more, and 50 or less, preferably 30 or less, more preferably 20 or less, and still more preferably. The liquid detergent composition for dishes according to any one of <27> to <29>, wherein is less than or equal to 10.

<31>
The liquid detergent composition for dishes according to <27> or <28>, wherein the polyoxyalkylene monoalkyl or alkenyl ether is a nonionic surfactant represented by the following general formula (d1).
^{_{R 11 O [(C 2 H}} 4 O) l / (C 3 H 6 O) n] H (d1)
[In the formula, R ¹¹ represents a hydrocarbon group having 6 to 22 carbon atoms. l and n represent the average number of moles added, l represents a number of 0 or more and 30 or less, n represents a number of 0 or more and 30 or less, and 1 and n do not become 0 at the same time. “/” Indicates that the oxyethylene group and the oxypropylene group may be added to either random or block regardless of order. ]

<32>
The HLB value of the polyoxyalkylene monoalkyl or alkenyl ether defined by the following formula of Griffin is 5 or more, preferably 7 or more, and 19 or less, preferably 15 or less, more preferably 13 or less. The liquid detergent composition for dishes according to any one of <27> to <31>.
HLB value = 20 × Mw / M
(Where M is the molecular weight of the nonionic surfactant and Mw is the molecular weight of the hydrophilic portion of the nonionic surfactant.)

<33>
The liquid detergent composition for dishes according to <27>, wherein the component (d) is (2) an alkyl polyglycoside.

<34>
The liquid detergent composition for dishes according to <27> or <33>, wherein the alkyl polyglycoside is a nonionic surfactant represented by the following general formula (d2).
R ²¹ (OR ²² ) _x G _y (d2)
Wherein, R ²¹ represents a linear or branched carbon atoms chains 8 to 18, preferably 12 to 14 alkyl, alkenyl or alkylphenyl group, preferably an alkyl group, R ²² is the number of carbon atoms It represents an alkylene group of 2 or more and 4 or less, and G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. x represents the average number of moles added, and is a number from 0 to 5 inclusive. y represents a number whose average value is 1 or more and 5 or less. ]

<34>
Component (d) is 0.03% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, and 8% by mass or less, preferably The tableware according to any one of the above <26> to <33>, which contains 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and still more preferably 0.7% by mass or less. Liquid detergent composition for use.

<35>
The water content of 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and 98% by mass or less, preferably 95% by mass or less, more preferably 93% by mass or less. > The liquid detergent composition for dishes according to any one of <34>.

<36>
Any of the above <1> to <35>, wherein the pH of the 0.2% by mass aqueous solution at 20 ° C. is 6 or more, preferably 7 or more, and 11 or less, preferably 10 or less, more preferably 9 or less. A liquid detergent composition for tableware according to any one of the above items.

<37>
The dishwashing liquid cleaning composition according to any one of <1> to <36>, wherein the pH is 7 or more and 11 or less, preferably 10 or less, more preferably 9 or less at 20 ° C.

  The liquid detergent composition for dishes shown in Table 1 was prepared, and the following items were evaluated. Table 1 shows the results. The dishwashing liquid detergent composition in Table 1 was prepared by a conventional method. That is, the components (a), (b) and (d) were added to an appropriate amount of ion-exchanged water, dissolved at 60 ° C., and then cooled to room temperature (20 ° C.). Thereafter, the component (c) was added, and after the component (c) was dissolved, citric acid or sodium hydroxide was added to adjust the pH (20 ° C.).

<Evaluation method>
(1) Detergency of protein / lipid composite soil 0.1 g (dry weight) of soft-boiled egg yolk heated to 70 ° C. was applied to a slide glass of 5 cm × 2.5 cm, dried for 1 day, and protein / lipid composite soil adhered. A slide glass was prepared. A plurality of the stained slide glasses were prepared. The dishwashing liquid detergent composition shown in Table 1 was diluted with 5 ° DH hard water so as to be a 0.2% by mass aqueous solution to obtain a washing liquid. Using this cleaning solution and the three glass slides on which the dirt was adhered, a cleaning test was performed by a leanut test method. The washing time was 7 minutes, and the washing temperature was 40 ° C. After washing, the washing rate was calculated for each slide glass by the following formula, and the average value is shown in Table 1.
Washing rate (%) = [(weight of slide glass before washing−weight of slide glass after washing) /0.1] × 100
The higher the value of the cleaning rate (%), the better the cleaning power. In this evaluation, 50% or more is preferable, 70% or more is more preferable, 80% or more is more preferable, and 90% or more is used. More preferred.

(2) Foaming property After introducing 6 g of the dishwashing liquid detergent composition shown in Table 1 into a tabletop dishwasher (NP-TR3 manufactured by Panasonic Corporation), washing was started in a standard course using tap water. The height of the foam after 20 minutes was measured. The height of the foam was determined by measuring the height of the foam generated with reference to the drain port inside the washing machine. The lower the numerical value of the foam height, the more excellent the foam suppressing property. In this evaluation, the height of the foam is preferably 7 cm or less, more preferably 6 cm or less, still more preferably 5 cm or less, still more preferably 4 cm or less, and even more preferably 3 cm or less.

(3) Storage stability 30 g of the dishwashing liquid detergent composition shown in Table 1 was used in PS-No. The sample was placed in a 6-standard glass bottle, allowed to stand at 5 ° C., and observed for 20 days. The number of days until the appearance of the composition, such as translucent or partially turbid, changed visually, was recorded, and is shown in Table 1. 20 days or more in the table means that there was no change in the appearance during the storage stability test and the composition was stable.

The components in the table are as follows.
(A) Ingredient: sodium decyl sulfate: manufactured by Fluorochem Ltd., an anionic surfactant in which R ¹ is a linear alkyl group having 10 carbon atoms, m 1 is 0, and M ¹ is sodium ion in the general formula (a1). C10 (PO) 0.6AS: An anionic surfactant produced in the same manner as in Example 3 of JP-A-2009-035714 except that the raw material alcohol was changed to carbon number 10 [general formula (a1) ) in a linear alkyl group of 10 carbon atoms, m1 is 0.6, the anionic surfactant ^{M 1} is sodium]. That is, after adding an average of 0.6 mol of a propyleneoxy group to 1 mol of a natural alcohol having an alkyl chain of 10 carbon atoms, sulfating with sulfur trioxide and neutralizing with an aqueous sodium hydroxide solution, An activator was obtained.

Component (b), sodium dodecyl sulfate: manufactured by Wako Pure Chemical Industries, Ltd., in the general formula (b1), a straight-chain alkyl group ^{R 2} is 12 carbon atoms, m2 is 0, anionic ^{M 2} is a sodium ion Surfactant

Component (c) Salt of maleic acrylic acid copolymer (1): Poise 520, manufactured by Kao Corporation, Na acrylate / Na maleate = 2.3 (molar ratio), weight average molecular weight 21000
Salt of acrylic acid-maleic acid copolymer (2): manufactured by Nippon Shokubai Co., Ltd., Aqualic TL-400, Na acrylate / Na maleate = 1 (molar ratio), weight average molecular weight 50,000
-Salt of acrylic acid-maleic acid copolymer (3): manufactured by Nippon Shokubai Co., Ltd., Aqualic TL-500, Na acrylate / Na maleate = 2.3 (molar ratio), weight average molecular weight 60000
-Salt of acrylic acid / maleic acid copolymer (4): manufactured by BASF, Sokalan CP-45, Na acrylate / Na maleate = 2.3 (molar ratio), weight average molecular weight 70000
Salt of acrylic acid-maleic acid copolymer (5): manufactured by Kao Corporation, oligomer KDS, Na acrylate / Na maleate = 0.25, weight average molecular weight 10,000
-Na polyacrylate (1): manufactured by Wako Pure Chemical Industries, Ltd., sodium polyacrylate, weight average molecular weight 25,000
-Na polyacrylate (2): manufactured by Wako Pure Chemical Industries, Ltd., sodium polyacrylate, weight average molecular weight 250,000

The weight average molecular weight of the component (c) was measured by gel permeation chromatography (GPC) under the following conditions.
Column: Tosoh Corporation G4000PWXL + G2500PWXL (two connected),
Detector: Differential refractometer,
Eluent: 0.2 M phosphate buffer (KH ₂ PO ₄ , Na ₂ HPO ₄ , pH = 7) / acetonitrile = 9/1 (volume ratio)
Standard: polyethylene glycol Conditions: column temperature: 40 ° C., flow rate: 0.5 mL / min, concentration: 0.05 mg / mL

Component (d) Nonionic surfactant (1): higher alcohol ethoxylate (average addition mole number 3.3, alkyl group: branched chain alkyl group having 12 to 14 carbon atoms) [in the general formula (d1), R ¹¹ is a branched alkyl group having 12 to 14 carbon atoms, l is 3.3, and m is 0, a nonionic surfactant], manufactured by Nippon Shokubai Co., Ltd., sophthanol 33, HLB 8.4

(Discussion)
Comparing Examples 1, 8, and 9, it can be seen that Example 1 containing 5% by mass of sodium decyl sulfate as the component (a) in the detergent composition is more excellent in the balance between detergency and foam control. .
Comparing Examples 1 and 12, it can be seen that Example 1 in which the component (a) is sodium decyl sulfate is superior in detergency and foam control.
Comparing Example 1 with Comparative Example 3, it can be seen that Example 1 in which the component (a) is 5% by mass and the component (b) is 0% by mass has excellent detergency and defoaming properties.
Comparing Examples 1 to 7, it is understood that Example 3 using the maleic acid acrylate copolymer salt (3) having a weight average molecular weight of 60000 as the component (c) has higher detergency.
Comparing Examples 1 and 13 and Comparative Example 1, it can be seen that Example 1 in which the content of the component (c) is 10% by mass in the detergent composition is more excellent in detergency.
The results of Examples 6 and 7 show that Example 6 using sodium polyacrylate having a weight average molecular weight of 25,000 as the component (c) is more excellent in storage stability.
When Examples 1 and 8 to 11 are compared, it is understood that Example 1 in which the mass ratio of the component (a) / the component (c) is 0.5 is more excellent in the balance between detergency, foam control, and storage stability. .

Claims (5)

(A) 1.5% by mass or more of an anionic surfactant represented by the following general formula (a1) [hereinafter, referred to as "component (a)"]; and (b) an anionic surfactant represented by the following general formula (b1). A structural unit derived from a carboxylic acid or a salt thereof having an ionic surfactant [hereinafter referred to as a component (b)] in an amount of from 0% by mass to 2% by mass and (c) a reactive unsaturated group having 3 to 6 carbon atoms. only contains the polymer weight average molecular weight of 5,000 or more to 150,000 [hereinafter, (c) referred to as component, and contains water, pH (20 ° C.) Ri der 6 or more, (a) component and (c A liquid detergent composition for dishes, wherein the mass ratio of component (a) / component (c) is 0.3 or more and 10 or less .
R ¹ -O- (PO) _m1 -SO ₃ -M ¹ (a1)
[In the formula, R ¹ represents an alkyl group or an alkenyl group having 10 carbon atoms, PO represents a propyleneoxy group, m1 represents an average number of moles of PO added, and is a number from 0 to 1.5. M ¹ represents a hydrogen atom or a cation. ]
_{^{R 2 -O- (PO) m2 -SO}} 3 -M 2 (b1)
[Wherein, R ² represents an alkyl group or alkenyl group having 12 to 14 carbon atoms, PO represents a propyleneoxy group, m2 represents an average addition mole number of PO, and a number of 0 to 1.5. It is. M ² represents a hydrogen atom or a cation. ]   The liquid detergent composition for dishes according to claim 1, wherein the component (c) contains 1% by mass or more and 20% by mass or less.   The component (c) is selected from the group consisting of polyacrylic acid or a salt thereof, polymethacrylic acid or a salt thereof, an acrylic acid-maleic acid copolymer or a salt thereof, and a methacrylic acid-maleic acid copolymer or a salt thereof. The liquid detergent composition for dishes according to claim 1, which is at least one kind. The liquid detergent composition for dishes according to any one of claims 1 to 3, further comprising (d) a nonionic surfactant. The liquid detergent composition for dishes according to any one of claims 1 to 4 , wherein the pH is 6 or more and 11 or less at 20 ° C.