JP7285765B2 - Dishwasher Liquid Detergent Composition - Google Patents

Description

The present invention relates to liquid dishwashing detergent compositions.

2. Description of the Related Art In recent years, dishwashers for washing tableware, cooking utensils, etc. (objects to be washed) have become popular not only in the kitchens of hotels, restaurants, food service centers, etc., but also in general households. Dedicated detergents (dishwasher detergents) are generally used for washing in dishwashers.
Liquid detergent compositions used for dishwashers are required to have high detergency against complex stains such as a mixture of oil stains, starch stains, tea stains, and the like.

For example, Patent Literature 1 proposes a strongly alkaline dishwasher detergent. According to the detergent composition of Patent Document 1, detergency is enhanced.

Japanese Patent Application Laid-Open No. 2001-316700

However, with the liquid detergent of Patent Document 1, problems derived from strong alkalinity (for example, deterioration of tableware, generation of scale, fogging of glass tableware, etc.) tend to occur.
In order to solve this problem, when the liquid detergent is made weakly alkaline, when the container is filled with the liquid detergent and stored at a high temperature, there is a problem that gas is generated in the container, causing the container to swell.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition for dishwashers which is excellent in detergency and can suppress the generation of gas.

The liquid detergent composition for dishwashers of the present invention includes the following aspects.
[1] including components (a), (b), (c) and (d),
The component (a) is a surfactant,
The component (b) is at least one selected from the group consisting of carbonates and hydrogencarbonates,
The component (c) is at least one selected from the group consisting of sulfites and hydrogen sulfites,
The component (d) is water,
The mass ratio represented by component (b)/component (c) is 50 to 50000,
A liquid dishwashing detergent composition having a pH of 7.5 to 10.5 at 25°C.
[2] The liquid detergent composition for dishwashers according to [1], wherein the mass ratio represented by component (a)/component (b) is 0.02 to 1.
[3] a container;
and the liquid detergent composition for dishwashers according to [1],
A container-packed liquid detergent article for a dishwasher, wherein the liquid detergent composition for a dishwasher is housed in the container.

The liquid detergent composition for dishwashers of the present invention is superior in detergency and can suppress the generation of gas.

<<Liquid detergent composition for dishwasher>>
The liquid detergent composition for dishwashers of the present invention comprises components (a), (b), (c) and (d).

<(a) component>
(a) Component is a surfactant. Containing the component (a), the liquid detergent composition for dishwashers of the present invention can easily improve its detergency.
Component (a) includes anionic surfactants, nonionic surfactants, amphoteric surfactants, semipolar surfactants, and the like.
[Anionic surfactant]
Anionic surfactants are roughly classified into sulfonate type, sulfate type, carboxylate type and phosphate type.
Sulfonate types are anionic surfactants with -SO ₃ ^- X ⁺ (where X ⁺ represents a metal ion) in the molecule. Sulfonate types include alkylbenzenesulfonates, alkylsulfates, alkanesulfonates, α-olefinsulfonates, α-sulfo fatty acid salts, α-sulfo fatty acid alkyl ester salts, alkylsulfosuccinates, and dialkylsulfosuccinates. etc.
The sulfate salt type is an anionic surfactant having —O—SO ₃ ⁻ X ⁺ (where X ⁺ represents a metal ion) in the molecule. Sulfuric acid ester salt types include alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, and the like.
Carboxylate types are anionic surfactants with —CO ₂ ⁻ X ⁺ (where X ⁺ represents a metal ion) in the molecule. Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid-based anionic surfactants, and the like. The carboxylate type preferably does not contain soap (higher fatty acid salt).
The anionic surfactant preferably has an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and an alkyl group having 8 to 18 carbon atoms is preferable. The alkyl group or alkenyl group may be linear or branched.
Among them, the sulfonate type is preferable from the viewpoint of the detergency against complex stains, the straight-chain alkylbenzenesulfonate is more preferable, and the straight-chain alkylbenzenesulfonate having an alkyl group of 8 to 18 carbon atoms is even more preferable.
Salts constituting the anionic surfactant include salts of metals such as sodium, potassium, magnesium and calcium.

[Nonionic surfactant]
Examples of nonionic surfactants include polyoxyalkylene type nonionic surfactants, alkyl polyglycoside type nonionic surfactants, aliphatic alkanolamide type nonionic surfactants, sorbitan fatty acid ester type nonionic surfactants, and alkyl monoglyceryl ether type nonionic surfactants. Surfactants, fatty acid monoglyceride type nonionic surfactants, sucrose fatty acid ester type nonionic surfactants and the like can be mentioned. Specifically, polyoxyalkylene-type nonionic surfactants, alkylphenols, alkylene oxide adducts such as higher amines, polyoxyethylene polyoxypropylene block copolymers, fatty acid alkanolamines, fatty acid alkanolamides, polyhydric alcohol fatty acid esters, or alkylene oxides thereof. Oxide adducts, polyhydric alcohol fatty acid ethers, alkyl (or alkenyl) amine oxides, alkylene oxide adducts of hydrogenated castor oil, sugar fatty acid esters such as sorbitan fatty acid esters, N-alkyl polyhydroxy fatty acid amides, alkyl glycosides, etc. .

As the polyoxyalkylene-type nonionic surfactant, a compound represented by the following formula (a21) (hereinafter also referred to as "compound (a21)") is preferable.
R ²¹ -X-[(EO) _s /(PO) _t ]-R ²² (a21)

In formula (a21), R ²¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, R ²² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 2 to 2 carbon atoms. 6 alkenyl groups, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents the average number of repetitions of EO, a number from 1 to 20, and t represents the average number of repetitions of PO. , is a number from 0 to 10.

In formula (a21), the number of carbon atoms in the hydrocarbon group of R ²¹ is 6 to 22, preferably 8 to 22, more preferably 10 to 18. The hydrocarbon group of R ²¹ may be linear or branched, and may or may not have an unsaturated bond.
-X- includes -O-, -COO-, -CONH- and the like.
The number of carbon atoms in the alkyl group for R ²² is 1-6, preferably 1-3.
The alkenyl group for R ²² has 2 to 6 carbon atoms, preferably 2 to 3 carbon atoms.

The compound (a21) wherein -X- is -O-, -COO- or -CONH- is a primary or secondary higher alcohol (R ^-OH ), a higher fatty acid (R ^-COOH ) or a higher It is obtained using a fatty acid amide (R ²¹ -CONH) as a starting material. R ²¹ in these raw materials is the same as R ²¹ in formula (a21).

s is a number from 1 to 20, preferably from 3 to 10.
t is a number from 0 to 10, preferably from 0 to 8.
When t is 1 or more, that is, when compound (a21) has EO and PO, the addition method of ethylene oxide and propylene oxide is not particularly limited, and may be, for example, random addition method or block addition method. Examples of the block addition method include a method of adding ethylene oxide and then adding propylene oxide, a method of adding propylene oxide and then adding ethylene oxide, a method of adding ethylene oxide and then adding propylene oxide, and then adding ethylene oxide. and methods to do so.

As the compound (a21), in particular, a compound in which -X- is -O- (alcohol-type nonionic surfactant), or a compound in which -X- is -COO- and R ²² is an alkyl having 1 to 6 carbon atoms or a compound having an alkenyl group having 2 to 6 carbon atoms (fatty acid alkyl (alkenyl) ester).

When -X- is -O-, R ²¹ preferably has 10 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and still more preferably 10 to 18 carbon atoms. When -X- is -O-, R ²² is preferably a hydrogen atom.

When -X- is -COO-, R ²¹ preferably has 9 to 21 carbon atoms, more preferably 11 to 21 carbon atoms. When -X- is -COO-, R ²² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
Specifically, NNAEP manufactured by Lion Specialty Chemicals, Sannonic series and Narrow Acty series manufactured by Sanyo Chemical, Neugen series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Plurafac manufactured by BASF, Lutensol series manufactured by ADEKA. and the Emulgen series manufactured by Kao Corporation.

As the alkylpolyglycoside nonionic surfactant, a nonionic surfactant represented by the following formula (a22) is preferable.
^R25 ( ^OR26 ) _{xGy (} a22)
In formula (a22), R ²⁵ represents a linear or branched alkyl group, alkenyl group or alkylphenyl group having 8 to 18, preferably 12 to 14 carbon atoms, preferably an alkyl group, and R ²⁶ represents It represents an alkylene group having 2 or more and 4 or less carbon atoms, and _Gy represents a residue derived from a reducing sugar having 5 or 6 carbon atoms. x represents the average number of added moles and is a number of 0 or more and 5 or less. y indicates a number whose average value is 1 or more and 5 or less.
In formula (a22), R ²⁵ 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 from the viewpoint of storage stability.
In formula (a22), x is preferably 0 or more and 2 or less, more preferably 0, from the viewpoint of storage stability. From the viewpoint of storage stability, y is preferably 1.1 or more, preferably 1.5 or less, and more preferably 1.4 or less. Note that y is a value measured by the proton NMR method.
In formula (a22), G includes residues derived from one or more monosaccharides selected from glucose and fructose in terms of their availability and cost. G also includes residues derived from one or more polysaccharides selected from maltose and sucrose. G is preferably a residue derived from a monosaccharide of glucose.

As the fatty alkanolamide type nonionic surfactant, a nonionic surfactant selected from the group consisting of fatty acid alkanolamides and polyoxyethylene fatty acid alkanolamides and having an HLB of 9.5 or more and less than 12 is preferable.
In the present invention, "fatty acid alkanolamide" means, for example, fatty acid, fatty acid alkyl ester, fatty acid chloride, fat, or the like, and alkanolamine (monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, etc.) produced by reaction. ie fatty acid monoalkanolamides and/or fatty acid dialkanolamides.
"Polyoxyethylene fatty acid alkanolamide" refers to the aforementioned fatty acid alkanolamide into which an oxyethylene group has been introduced.

“HLB” is indicated by IOB×10 in the organic conceptual diagram.
The IOB in the organic conceptual diagram means the ratio of the inorganic value (IV) to the organic value (OV) in the organic conceptual diagram, that is, "inorganic value (IV)/organic value (OV)".
The organic conceptual diagram was proposed by Mu Fujita, and its details are described in "Pharmaceutical Bulletin", 1954, vol. 2, 2, pp. 163-173; "The Area of Chemistry", 1957, vol. 11, 10, pp. 719-725; "Fragrance Journal", 1981, vol. 50, pp. 79-82 and others. That is, the source of all organic compounds is methane (CH ₄ ), and all other compounds are regarded as derivatives of methane, and the number of carbon atoms, substituents, modified moieties, rings, etc. are set to constant values. Add the scores to determine the organic and inorganic values. Then, these values are plotted on a diagram with the organic values on the X axis and the inorganic values on the Y axis. This organic conceptual diagram is also shown in "Organic Conceptual Diagram - Fundamentals and Applications" (Yoshio Koda, Sankyo Publishing, 1984).

Specific examples of aliphatic alkanolamide-type nonionic surfactants include coconut oil fatty acid monoethanolamide, lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, and isostearic acid monoethanolamide. fatty acid monoalkanolamides such as amides and lauric acid monoisopropanolamide; polyoxyethylene coconut oil fatty acid monoethanolamide, polyoxyethylene lauric acid monoethanolamide, polyoxyethylene myristic acid monoethanolamide, polyoxyethylene palmitic acid monoethanolamide , polyoxyethylene stearic acid monoethanolamide, polyoxyethylene isostearic acid monoethanolamide, and polyoxyethylene lauric acid monoisopropanolamide.

[Amphoteric Surfactant]
Examples of amphoteric surfactants include carboxylate type, sulfate type, sulfonate type, and phosphate type, and carboxylate type amphoteric surfactants are preferred.
Specific examples of carboxylate type amphoteric surfactants include betaine lauryldimethylaminoacetate, betaine coconutalkyldimethylaminoacetate, betaine coconut fatty acid amidopropyl betaine, betaine lauramidopropyldimethylaminoacetate, and coconutalkylamidopropyldimethylamino Examples include betaine-type amphoteric surfactants such as betaine acetate.

[Semi-polar surfactant]
Amine oxides include alkyldimethylamine oxides such as lauryldimethylamine oxide, palm alkyldimethylamine oxide and n-dodecyldimethylamine oxide; alkyldiethylamine oxides such as lauryldiethylamine oxide; and alkanoylamide alkyls such as lauramidopropyldimethylamine oxide. dimethylamine oxide and the like. Among them, alkyldimethylamine oxides are more preferred.

Component (a) is preferably an anionic surfactant from the viewpoint of detergency against complex stains.
(a) component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

The content of component (a) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, more preferably 0.3 to 2.0% by mass, relative to the total mass of the liquid detergent composition for dishwashers. 5% by mass is more preferred.
When the content of the component (a) is at least the above lower limit, the cleaning power for multiple stains increases.
When the content of component (a) is equal to or less than the above upper limit, foaming tends to be reduced.
If too much foam is generated in the dishwasher, the foam may reduce mechanical power and detergency. Also, washing may stop depending on the type of dishwasher.

<(b) component>
Component (b) is at least one selected from the group consisting of carbonates and hydrogencarbonates. Containing the component (b), the liquid detergent composition for dishwashers of the present invention can easily improve the detergency against complex stains.
Carbonates refer to compounds in general containing carbonate ions (CO ₃ ²⁻ ). Bicarbonate refers to all compounds containing bicarbonate ions (HCO ₃ ⁻ ). Among them, alkali metal salts such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate are preferable. Sodium hydrogencarbonate and potassium hydrogencarbonate are particularly preferred from the viewpoint of detergency against complex stains due to pH buffering capacity.
(b) component may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.

The content of component (b) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, and even more preferably 3 to 7% by mass, relative to the total mass of the liquid detergent composition for dishwashers.
When the content of component (b) is at least the above lower limit, the detergency against complex stains increases.
(b) When the content of the component is equal to or less than the above upper limit, it becomes easier to suppress the generation of gas.

The mass ratio represented by component (a)/component (b) (hereinafter also referred to as a/b ratio) is preferably 0.02 to 1, more preferably 0.04 to 1, and 0.06 to 1. More preferred.
When the a/b ratio is equal to or higher than the above lower limit, it becomes easier to suppress the generation of gas.
When the a/b ratio is equal to or less than the above upper limit, foaming tends to be reduced.

<(c) component>
Component (c) is at least one selected from the group consisting of sulfites and hydrogen sulfites. The liquid detergent composition for dishwashers of the present invention can suppress generation of gas by containing the component (c).
Sulfites refer to all compounds containing sulfite ions (SO ₃ ²⁻ ). Bisulfite refers to all compounds containing bisulfite ions (HSO ₃ ⁻ ). Among them, alkali metal salts such as sodium sulfite, sodium hydrogen sulfite and potassium sulfite are preferred. In particular, sodium sulfite is preferable from the viewpoint of suppression of gas generation.
Component (c) may be used singly or in combination of two or more.

The content of component (c) is preferably 0.0001 to 0.1% by mass, more preferably 0.0005 to 0.07% by mass, and 0.0005 to 0.07% by mass, based on the total mass of the liquid detergent composition for dishwashers. 007 to 0.025% by mass is more preferred.
When the content of component (c) is within the above range, it becomes easier to suppress the generation of gas.

The mass ratio represented by component (b)/component (c) (hereinafter also referred to as b/c ratio) is preferably from 50 to 50,000, more preferably from 70 to 10,000, and even more preferably from 200 to 800.
When the b/c ratio is within the above range, it becomes easier to suppress the generation of gas.

<(d) component>
(d) Component is water.
The content of component (d) is preferably 70 to 99% by mass, more preferably 80 to 95% by mass, based on the total mass of the liquid detergent composition for dishwashers.
(d) It becomes easy to adjust the liquid detergent composition for dishwashers that content of a component is in the said range.

<pH>
The pH (25° C.) of the liquid detergent composition for dishwashers is 7.5 to 10.5, more preferably 8.5 to 10.5, even more preferably 9 to 10.5.
When the pH of the liquid detergent composition for dishwashers is at least the above lower limit, the detergency is enhanced and the generation of gas is easily suppressed.
When the pH of the liquid detergent composition for dishwashers is equal to or less than the above upper limit, deterioration of tableware, generation of scale, fogging of glass tableware, and the like are less likely to occur.
In the present invention, the pH (25°C) of the liquid detergent composition for dishwashers indicates a value measured by a method conforming to JIS Z 8802:1984 "pH measurement method".

<Optional component>
The liquid detergent composition for dishwashers of the present invention contains a sequestering agent, a solvent other than the component (d), a hydrotrope agent, a dispersant, a thickener, and a viscosity adjuster, as long as the objects of the present invention are not impaired. Ingredients such as agents, enzymes, fragrances, colorants, preservatives, disinfectants, bleaches, and bleach activators can be incorporated.
The sequestering agent is not particularly limited, and includes conventional sequestering agents commonly used in dishwashing liquid detergent compositions, and either low-molecular sequestering agents or polymeric sequestering agents are used. be able to.

Examples of low-molecular-weight sequestering agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminedisuccinic acid, L-aspartic acid-N,N-diacetic acid, dihydroxyethylethylenediaminediacetic acid, and hydroxyethylimino. Diacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamic diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, dihydroxyethylglycine , 3-hydroxy-2,2′-iminodisuccinic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphoric acid, or salts thereof.

As the polymer sequestering agent, those having a weight average molecular weight of 1000 or more are suitable. Polymer sequestering agents include, for example, polyacrylic acid or salts thereof, polymethacrylic acid or salts thereof, acrylic acid-maleic acid copolymers or salts thereof, methacrylic acid-maleic acid copolymers or salts thereof, ethylene- A maleic acid copolymer or a salt thereof may be used. Among them, the polymer sequestering agent is preferably an acrylic acid-maleic acid copolymer or a salt thereof. The copolymerization ratio (molar ratio) of acrylic acid and maleic acid is preferably acrylic acid/maleic acid=75/25 to 50/50, and the weight average molecular weight is preferably 10,000 or more and 100,000 or less. The weight average molecular weight of the polymer sequestering agent is the value measured by gel permeation chromatography using sodium polyacrylate as a standard substance. The salt constituting the sequestering agent is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt. Among these, citric acid, an acrylic acid-maleic acid copolymer, or salts thereof are preferred, and citric acid or a salt thereof is particularly preferred, from the viewpoint of cleaning performance against complex stains.

The sequestering agent may be used singly or in combination of two or more. The content of the sequestering agent is preferably 6 to 15% by mass, more preferably 8 to 15% by mass as an acid form, relative to the total mass of the liquid detergent composition for dishwashers. When the content of the sequestering agent is at least the above lower limit, the cleaning performance for complex stains is enhanced. When the content of the sequestering agent is equal to or less than the above upper limit, foaming tends to be reduced.

Thickeners include acidic thickening polysaccharides.
Acidic thickening polysaccharides are polysaccharides in which monosaccharide oxides such as glucuronic acid, which is an oxide of glucose, galacturonic acid, which is an oxide of galactose, and mannuronic acid, which is an oxide of mannose, are combined. good.
Acidic thickening polysaccharides include: xanthan gum, gellan gum, carrageenan, pectin, soybean polysaccharides, alginic acid, gum arabic, gum karaya, gum tragacanth, hyaluronic acid and the like.
Xanthan gum, gellan gum and carrageenan are preferred, and xanthan gum and gellan gum are more preferred.
The content of the acidic thickening polysaccharide is preferably 0.05 to 1.5% by mass, more preferably 0.1 to 1% by mass, more preferably 0.2% by mass, relative to the total mass of the liquid detergent composition for dishwashers. ~1% by mass is more preferred.

<<Method for producing liquid detergent composition for dishwasher>>
The liquid detergent composition for dishwashers of the present invention is not particularly limited, and conventionally known production methods can be used.
As a method for producing a liquid detergent composition for dishwashers, component (d) (water), component (a), component (b), component (c), optional components as necessary, and pH adjustment It is prepared by adding and dissolving the agent.

<<Method of using liquid detergent composition for dishwasher>>
The liquid detergent composition for dishwashers of the present invention can be used for dishwashers, and may be used according to the model of the dishwasher and the degree of soiling of dishes and the like.
Examples of methods for washing an object to be washed with a dishwasher using a liquid detergent composition for dishwashers include methods having both washing and rinsing steps.
As a washing method, for example, a washing liquid prepared by introducing normal temperature (preferably about 5 to 30 ° C.) tap water into a dishwasher is heated to a predetermined washing temperature (the temperature of the washing liquid circulating during washing). A step of washing the object to be washed while warming it (hereinafter referred to as the “washing step”), a step of rinsing the washed object with normal temperature tap water (hereinafter referred to as the “rinsing (1) step”), A step of further rinsing the object to be cleaned after the rinsing (1) step (hereinafter referred to as the “rinsing (2) step” while raising the temperature of tap water at room temperature to preferably 70 to 75° C. at a rate of 2 to 3° C./minute). .). The washing time in the washing step is preferably 10 to 40 minutes.
In the case of a general standard course, the washing temperature in the washing process is about 55-65° C., and the heating rate is about 2-3° C./min. In the low-temperature course, for example, the washing temperature is about 35 to 45° C. and the heating rate is about 1° C./min. The liquid detergent composition for dishwashers of the present invention exhibits excellent detergency against oil stains even in low-temperature washing, and exhibits excellent detergency even at a washing temperature of 35°C, for example.
In any course, the amount of liquid detergent used at one time is preferably 2 to 9 g per about 3 liters of tap water.

≪Dishwasher Liquid Detergent Products in Containers≫
The containerized liquid detergent article for dishwashers of the present invention comprises a container and the liquid detergent composition for dishwashers of the present invention, wherein the liquid detergent composition for dishwashers is housed in the container. Become.
The container is manufactured by using, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, and synthetic resins in which these are mixed as a raw material resin, and blow molding or injection molding the raw material resin.
The shape of the container is not particularly limited, and may be a round bottle, a rectangular bottle, or a pouch.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

The unit of the compounding amount in the table is "% by mass", and all the components show the amount in terms of pure content.
Blanks in the table indicate that the component was not included.
"Balanced" means that water is blended so that the total amount (% by mass) of all compounding components contained in the composition of each example is 100% by mass.
The components shown in the table are described below.

≪Raw materials used≫
<(a) Component: Surfactant>
a-1: LAS, linear alkyl (C 12-14) sodium benzenesulfonate (trade name Lipon LS-250, Lion Specialty Chemicals Co., Ltd.).
· a-2: SAS, sodium secondary alkanesulfonate (trade name "HOSTAPUR SAS 30A", manufactured by Clariant Japan KK).
a-3: AS, linear alkyl (C12) sodium sulfate ester (trade name Sunol LM-1130, Lion Specialty Chemicals Co., Ltd.).
・ a-4: AE (15), BRE (15) Polyoxyethylene (average repetition number 15) alkyl (linear C12/14 = 75/25) ether (trade name LMAO-90, Lion Specialty Chemicals Co., Ltd. ).
· a-5: APG, alkyl (C8-10) polyglucoside (trade name: GLUCOPON 215UP, Cognis Japan Co., Ltd.).
a-6: AX, n-dodecyldimethylamine oxide (Cadenax DM12D-W, Lion Specialty Chemicals Co., Ltd.).

<(b) component: at least one selected from the group consisting of carbonates and hydrogencarbonates>
· b-1: Sodium hydrogen carbonate (Wako Pure Chemical Industries, reagent).
· b-2: Sodium carbonate (Wako Pure Chemical Industries, reagent).
· b-3: Potassium hydrogen carbonate (Wako Pure Chemical Industries, reagent).
· b-4: potassium carbonate (Wako Pure Chemical Industries, reagent).

<(c) component: at least one selected from the group consisting of sulfites and hydrogen sulfites>
· c-1: sodium sulfite (Wako Pure Chemical Industries, reagent).
· c-2: sodium hydrogen sulfite (Wako Pure Chemical Industries, reagent).
· c-3: Potassium sulfite (Wako Pure Chemical Industries, reagent).
· c'-1: ascorbic acid (Wako Pure Chemical Industries, reagent).
· c'-2: uric acid (Wako Pure Chemical Industries, reagent).

<(d) component: water>
・Ion-exchanged water

<Optional component>
- Sequestering agent: citric acid (trade name "purified citric acid (anhydrous)", Fuso Chemical Industry Co., Ltd.).
- Sequestering agent: Tetrasodium glutamate diacetate (GLDA-Na): manufactured by Cherest.
- Sequestering agent: ethylenediaminetetraacetic acid (Tokyo Chemical Industry Co., Ltd., reagent).
Sequestering agent: sodium salt of maleic acid/acrylic acid copolymer (trade name “Aqualic TL400”, Nippon Shokubai Co., Ltd., molar ratio of acrylic acid/maleic acid = 60/40, weight average molecular weight 50000, active ingredient 40% by mass).
- pH adjuster: Sulfuric acid (Kanto Kagaku Co., Ltd.).
- pH adjuster: sodium hydroxide (48% potassium hydroxide, AGC Inc.).
- pH adjuster: potassium hydroxide (48% sodium hydroxide, AGC Inc.).

<Examples 1 to 42, Comparative Examples 1 to 8>
According to the compositions of Examples 1 to 42 in Tables 1 to 5 and Comparative Examples 1 to 8 in Table 6, the component (d) includes the component (a), the component (b), the component (c), and an optional component. 0.8 kg of each liquid detergent of each example was prepared by dissolving the pH adjuster.
Specifically, water was put into a 1 L beaker (12 cm in diameter) so as to be 50% by mass of the entire composition. A HEIDON FBL1200 three-one motor (manufactured by Shinto Kagaku Co., Ltd.) stirrer is equipped with a 4-blade paddle with a diameter of 7.5 cm, a width of 1.5 cm, and an angle of 45 degrees, and then rotates at 400 to prevent the contents from scattering. Stirred at ~900 rpm. Next, components (a), (b), (c) and a pH adjuster (sodium hydroxide or potassium hydroxide) were added to obtain a mixture. The pH of the liquid detergent of each example was adjusted with a pH adjuster so as to achieve the pH values shown in the table. The rest of the water was added so that the total composition was 100% by mass, and the mixture was stirred for 1 minute at 650 rpm with the stirrer to obtain a liquid detergent composition for dishwashers.
The pH (25° C.) of the composition was measured using a glass electrode pH meter (HM-30G, manufactured by Toa DKK Co., Ltd.) with a liquid detergent adjusted to 25° C. The measurement method was performed in accordance with JIS Z 8802:1984 "pH measurement method".

Evaluation of Liquid Dishwasher Cleaning Compositions:
Each cleaning agent of each example and comparative example was evaluated by the following evaluation methods, and the results are also shown in the table.
As a dishwasher, an automatic dishwasher (manufactured by Panasonic Corporation, model NP-TM2) was used. In each evaluation, the washing treatment was performed by operating the automatic dish washer/dryer in the standard course (normal mode).

Standard Course (Normal Mode):
After putting 6 g of liquid detergent (for 3 L of tap water) into the automatic dish washer/dryer, tap water of about 5°C was introduced into the chamber, and the washing liquid prepared was increased to 55°C at a rate of 2 to 3°C/min. Washing is performed for 20 minutes while the temperature is raised, and the washing solution is drained. Then, fresh tap water is introduced, and 2 repetitions of rinsing (2 minutes/time) and draining are performed. After draining water, introduce new tap water and rinse once (final rinse) for 20 minutes while raising the temperature to 70°C at a rate of 2-3°C/min. do.

<Evaluation method for combined stain detergency>
Contaminants include beef tallow/lard/butter/salad oil = 3/3/3/1 (mass ratio) mixed oil, retort curry (Bon Curry Gold 21 dry), raw egg (L size), rice (self-distribution rice class 1 Koshihikari equivalent) , the ratio of the amount of rice and water is the standard of the rice cooker, and rice should be used within 12 hours after cooking), and black tea (Nitto Tea DAY & DAY TEA BAG) was used. Dirt is attached to a small ceramic plate (radius 60 mm, height 20 mm), a melamine plate (radius 100 mm, height 15 mm) and a glass cup (top diameter 63 mm, bottom diameter 53 mm, height 100 mm). evaluated.
Specifically, 2 g of the mixed oil was attached to a small dish, and three plates were prepared. Next, 200 g of the retort curry, 1 raw egg, and 150 g of rice were mixed. 30 g of the mixture was placed on a large plate, and after the surface of the large plate was uniformly contaminated, the mixture was discarded leaving about 10 rice grains, and the rice grains were crushed with a spoon and attached to the large plate. A total of 6 platters contaminated in this way were prepared. A total of four glass cups containing 10 g of the black tea were prepared. The contaminated tableware (total of 13 items) prepared as described above was loaded into the automatic dishwashing/drying machine, and 6 g of detergent was added to wash the tableware in a standard course.
After the washing treatment, the tableware was visually observed, and the composite soil detergency was evaluated based on the following evaluation criteria. The scores of Examples and Comparative Examples are the average values of 3 washing treatments, and 3 points or more were accepted. The evaluation results are shown in Tables 1-6.

(Evaluation criteria)
5 points: Stain was completely removed from all 6 large plates.
4 points: There were 5 plates from which stains were completely removed.
3 points: Four large plates were completely cleaned of stains.
2 points: 2 to 3 platters were completely cleaned of stains.
1 point: One or less large plates were completely cleaned of stains.

<Evaluation method for container swelling (gas generation)>
360 g of the liquid detergent composition for dishwashers is filled in a measuring cap type container (Charmy Crysta Clear Gel, manufactured by Lion Corporation), and a torque of 100 (cN m) is measured using a torque meter (TOHNICHI torque meter, 2TME900CN). ), and lightly shaken to mix. It was left in a temperature-controlled room at 50°C for one month, and the swelling of the container was evaluated based on the following evaluation criteria. The scores of Examples and Comparative Examples are the average values of visual judgment by five panelists, and 3 or more points were accepted. The evaluation results are shown in Tables 1-6.

(Evaluation criteria)
5 points: Swelling of the container was observed.
4 points: The trunk portion of the container swelled very slightly.
3 points: The body of the container was slightly swollen.
2 points: The body of the container was clearly swollen and wobbly when touched.
1 point: The bottom of the container protruded, or the contents spouted out.

Examples 1 to 43, to which the present invention was applied, were excellent in detergency against stains and gas generation suppression effect.
Comparative Example 1, which did not contain the component (a), was inferior in both the detergency against stains and the effect of suppressing gas generation.
Comparative Example 2 containing no component (b) was inferior in detergency against stains.
Comparative Example 3, which did not contain the component (c), was inferior in the effect of suppressing gas generation.
Comparative Examples 4 and 5 using antioxidants other than the component (c) were inferior in the effect of suppressing gas generation.
Comparative Example 6, in which the b/c ratio exceeded the upper limit, was inferior in the effect of suppressing gas generation.
Comparative Example 7, in which the b/c ratio was less than the lower limit, was inferior in the effect of suppressing gas generation.
Comparative Example 8, in which the pH was less than the lower limit, was inferior in the effect of suppressing gas generation.

Claims (3)

(a) component, (b) component, (c) component, and (d) component,
The component (a) is a surfactant,
The component (b) is at least one selected from the group consisting of carbonates and hydrogencarbonates,
The component (c) is at least one selected from the group consisting of sulfites and hydrogen sulfites,
The component (d) is water,
The mass ratio represented by component (b)/component (c) is 50 to 50000,
A liquid dishwashing detergent composition having a pH of 7.5 to 10.5 at 25°C. 2. The liquid detergent composition for dishwashers according to claim 1, wherein the mass ratio represented by component (a)/component (b) is 0.02 to 1. a container;
and the liquid detergent composition for dishwashers according to claim 1,
A container-packed liquid detergent article for a dishwasher, wherein the liquid detergent composition for a dishwasher is housed in the container.