JP5642533B2 - Cleaning composition for automatic dishwasher - Google Patents

Description

  The present invention relates to a detergent composition for an automatic dishwasher, and more particularly to a detergent composition for an automatic dishwasher that has a low foaming property and a high detergency against solid fat and can shorten the drying time.

  Examples of detergents combined with a high molecular weight polycarboxylic acid or a salt thereof, a specific quaternary ammonium compound, and a specific surfactant include, for example, a water-soluble polymer, a specific quaternary ammonium compound, and a surfactant. A liquid detergent composition for hard bodies (for example, Patent Document 1) and a hand-washing laundry detergent (for example, a combination of a small amount of a polymer builder, a bis-alkoxylated quaternary ammonium cationic surfactant and a surfactant) Although there is a patent document 2), it improves the cleaning power against tea astringent stains and the finish of glass tableware, and further improves the cleaning power against solid fat that is strong dirt such as beef tallow, and shortens the drying time. The purpose provided by the liquid detergent composition is not achieved.

On the other hand, with the widespread use of automatic dishwashers, cleaning compositions for automatic dishwashers are also known.
As a detergent composition dedicated to automatic dishwashers, for example, to maintain performance and stability, it does not contain alkali agents such as alkyl hydroxide metal salts, sequestering agents, nonionic surfactants, cations It contains a surfactant, an organic electrolyte polymer, an alkyl aliphatic dicarboxylate, water, and the like, and has a pH of 7.0-9. A liquid detergent composition for an automatic dishwasher having a range of 5 (Patent Document 3) is known.
In addition to containing a polymer polycarboxylic acid or a salt thereof and a dispersant at the same time, and containing a specific surfactant, the synergistic effect of these components improves the cleaning power against tea astringent stains, A cleaning composition for an automatic dishwasher with improved finish (Patent Document 4) is known.

  However, in the above Patent Documents 3 to 4, there are those that partially describe the configuration of the present invention, but by combining two specific compounds at a specific ratio, it has low foaming properties and strong dirt such as beef tallow. There is no description or suggestion about a liquid detergent composition for an automatic dishwasher that satisfies the detergency of a certain solid fat and that can shorten the drying time when the automatic dishwasher is used.

2. Description of the Related Art In recent years, due to an increase in awareness of environmental problems, a technique for shortening the drying time after washing has been required for dishwashing by a dishwasher in order to reduce energy as well as convenience during use.
In addition, the conventional dishwasher detergent represented by Cited Document 4 has good cleaning power for tea astringents and liquid oil, and cloudy cleaning power for glasses, but it has good cleaning power for solid fat that is strong dirt such as beef tallow. Further improvement is required.
Therefore, there is a high demand for a detergent composition for a low-foam automatic dishwasher that can shorten the drying time and improve the detergency of solid fat.

JP-A-11-286699 (Claims, Examples, etc.) JP-T-11-510554 (Claims, Examples, etc.) JP 2002-146400 A (Claims, Examples, etc.) JP 2007-23268 (Claims, Examples, etc.)

  The present invention has been made in view of the above-mentioned problems, and realizes shortening of the drying time, which is a concern of the user who uses the detergent for dishwashers, while also having a low-foaming property with good detergency for solid fat. An object is to provide a detergent composition for a dishwasher.

In order to solve the above problems, the present invention employs the following configuration.
That is, (A) a compound represented by the following general formula (I) (where m + n is 10 to 50) and a compound represented by the following general formula (II) (where m + n is 10 to 50) At least one compound selected from the group consisting of: (B) a compound represented by the following general formula (I) (wherein m + n is 1 to 3) and the following general formula (II): A liquid detergent composition for an automatic dishwasher, comprising at least one compound selected from the group consisting of compounds represented by the formula (wherein m + n is 1 to 3): The content of the component is 0.4 to 5.0 mass%, the content of the component (B) is 0.3 to 5.0 mass%, and the mass ratio of (A) / (B) Is a liquid detergent composition for an automatic dishwasher, characterized by being 0.3 to 5.0.

(R ₁ and R ₂ are each independently a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having a linear or branched alkyl group having 1 to 20 carbon atoms, or a tolyl group. R ₃ represents a straight chain or branched chain alkyl group or alkenyl group having 8 to 20 carbon atoms, or a hydroxy group having a straight chain or branched chain alkyl group having 8 to 20 carbon atoms. Any one of an alkyl group, a tolyl group, a phenyl group, and a benzyl group, EO represents an ethylene oxide group, X ⁻ represents an anion, and m and n are average added moles of EO.)

  ADVANTAGE OF THE INVENTION According to this invention, while realizing the shortening of the drying time which is a user's concern which uses the washing | cleaning agent for dishwashers, it is a low-foaming automatic dishwasher washing agent excellent also in the cleaning power with respect to solid fat A composition can be obtained. Furthermore, according to the preferable aspect of this invention, the cleaning composition for automatic dishwashers excellent also in tea astringency washing | cleaning power and cloudy washing power can be obtained.

<< (A) Compound represented by General Formula (I) and / or (II) (m + n = 10-50) and (B) Compound represented by General Formula (I) and / or (II) (m + n) = 1 to 3) >>
As the component (A) and the component (B) used in the present invention, compounds represented by the following general formula (I) and / or the following general formula (II) are used. The component (A) is represented by the following general formula (I) (wherein the total value m + n of average addition moles of ethylene oxide is 10 to 50) and general formula (II) (wherein the average addition mole number of ethylene oxide) In which the total value m + n is 10 to 50) is selected from the group consisting of compounds represented by formula (I) (wherein the average of ethylene oxide) Selected from the group consisting of compounds represented by the total number of added moles m + n is 1 to 3) and (II) (wherein the total number m + n of average added moles of ethylene oxide is 1 to 3). At least one compound.

In the above formula (I), R ₁ and R ₂ are each independently a linear or branched alkyl or alkenyl group having 1 to 20 carbon atoms, preferably 10 to 18 carbon atoms, preferably 1 to 20 carbon atoms (preferably Represents a hydroxyalkyl group having a linear or branched alkyl group having 10 to 18 carbon atoms, a tolyl group, a phenyl group, or a benzyl group. Particularly preferably, _one of R ₁ and R ₂ is a combination of a linear or branched alkyl or alkenyl group having 10 to 18 carbon atoms, and the other is a combination of a methyl group or a tolyl group.
EO represents an ethylene oxide group.
X ⁻ is an anion, a halogen atom ion such as chlorine ion, bromine ion, iodine ion, or the general formula R ₅ O ⁻ (where R ₅ is an alkyl group having 1 to 3 carbon atoms, and is particularly preferable. Is a methyl group)).

In the above formula (II), R ₃ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms, or 8 to 20 carbon atoms (preferably 10 to 18 carbon atoms). ) Is a hydroxyalkyl group having a linear or branched alkyl group, a tolyl group, a phenyl group, or a benzyl group, and particularly preferably a linear or branched alkyl group or alkenyl having 10 to 18 carbon atoms. It is a group.
EO represents an ethylene oxide group.

<< (A) Compound Represented by General Formula (I) and / or (II) (m + n = 10-50) >>
The compound of component (A) has the above general formula (I) (wherein the total value m + n of average added moles of ethylene oxide is 10 to 50, preferably 10 to 40, more preferably 15 to 30) and Selected from the group consisting of compounds represented by the general formula (II) (wherein the total value m + n of average added moles of ethylene oxide is 10-50, preferably 10-30, more preferably 10-20) At least one compound is used. m and n each independently represents a number of 0 or more.
m + n is in the above range, and the mass ratio with the component (B) is 0.3 to 5.0, preferably 0.7 to 3.0 ((A) / (B)). The effect of detergency and drying on solid fat can be enhanced.

As the compound represented by the general formula (I) of the component (A), for example, a trade name “Bisnol UP-10” (R ₁ : beef tallow-derived alkyl group, R ₂ : Tolyl, manufactured by Yushi Kogyo Co., Ltd.) Group, m + n = 30, X ⁻ : Cl ⁻ ), trade name “Esocard C / 25” manufactured by Lion Akzo Co., Ltd. (R ₁ : alkyl group derived from palm, R ₂ : methyl group, m + n = 15, X ⁻ : Cl ⁻ ) and the like are commercially available.
In addition, as the compound represented by the general formula (II) of the component (A), for example, “Esomine C / 25” (R ₃ : Alkyl group derived from palm, m + n = 15) manufactured by Lion Akzo Co., Ltd. ), Trade name “ETHOMEEN SA2Y-103” manufactured by Lion Akzo Co., Ltd. (R ₃ : alkyl group derived from cured beef tallow, m + n = 50), trade name “Esomin SAJ-103 manufactured by Lion Akzo Co., Ltd.” (R ₃ : Alkyl group derived from cured beef tallow, m + n = 10) and the like are commercially available.
Among the components (A), an ethylene oxide adduct of alkylamine represented by the general formula (II) is particularly preferable from the viewpoint of low foaming properties.
(A) As a component, the compound represented by general formula (I) or general formula (II) may be used independently, and may be used in combination of 2 or more type.

(A) Total content of a component is 0.4-5.0 mass% with respect to cleaning composition whole quantity, Preferably it is 0.7-3.5 mass%.
If the content of component (A) is less than 0.4% by mass, the solid fat cleaning power will be insufficient. On the other hand, if it exceeds 5% by mass, bubbles will form too much during cleaning and the machine will not operate normally. There is.

<< (B) Compound represented by General Formula (I) and / or (II) (m + n = 1 to 3) >>
The compound of the component (B) has the above general formula (I) (wherein the total value m + n of average added moles of ethylene oxide is 1 to 3, preferably 2) and the general formula (II) (wherein The total value m + n of the average added mole number of ethylene oxide is 1 to 3, preferably 2. At least one compound selected from the group consisting of compounds represented by: m and n each independently represents a number of 0 or more.
m + n is in the above range, and the mass ratio with the component (A) is 0.3 to 5.0, preferably 0.7 to 3.0 ((A) / (B)). The effect of detergency and drying on solid fat can be enhanced.

As the compound represented by the general formula (I) of the component (B), a product name “Esocard C / 12” manufactured by Lion Akzo Co., Ltd. (R ₁ : alkyl group derived from palm, R ₂ : methyl group, m + n) = 2, X ⁻ : Cl ⁻ ) and the like are commercially available.
The compound represented by (B) the general formula of component (II), for example, Lion Akzo Co., Ltd., trade name "ETHOMEEN C / 12" (R _3: an alkyl group derived from coconut, m + n = 2 ), Manufactured by Clariant Japan Co., Ltd., trade name “Genamin C020” (R ₃ : alkyl group derived from palm, m + n = 2) and the like are commercially available.
Among the components (B), an ethylene oxide adduct of alkylamine represented by the general formula (II) is particularly preferable from the viewpoint of low foamability.
(B) As a component, the compound represented by general formula (I) or general formula (II) may be used independently, and may be used in combination of 2 or more type.

(B) Total content of a component is 0.3-5.0 mass% with respect to the cleaning composition whole quantity, Preferably it is 0.5-3.0 mass%.
If the content of the component (B) is less than 0.3% by mass, the solid fat detergency will be insufficient. On the other hand, if it exceeds 5% by mass, bubbles will be generated during cleaning and the machine will not operate normally. There is.

In the present invention, the mass ratio of the component (A) and the component (B) is (A) / (B) = 0.3 to 5.0, preferably 0.7 to 3.0. When it is within the above range, when used in a dishwasher, the drying time can be greatly shortened, and the detergency of solid fat, which has been difficult in the past, can be improved.
These effects cannot be achieved by component (A) and component (B) alone, and (A) / (B) must be in the above range.

Although not being bound by any theory, the reason why the detergency of the solid fat is improved by using the component (A) and the component (B) at a specific mass ratio is estimated as follows.
Since the component (B) has a small average added mole number of ethylene oxide, it has a relatively high hydrophobicity and is easily adsorbed on solid fat which is a soil component. On the other hand, the component (A) has a large ethylene oxide average addition mole number and high hydrophilicity. Therefore, by using the component (B) in combination with the component (A) at a specific ratio, the component (B) is adsorbed to the solid fat and peels off the fat from the tableware, and the component (A) wraps it to remove the dirt. Detergency improves because it can be dispersed efficiently in water. For this reason, it is presumed that the effect of improving the detergency of solid fat can be obtained.

Although not bound by any theory, the reason why the drying property is improved by using the component (A) and the component (B) at a specific mass ratio is estimated as follows.
The component (A) and the component (B) are weakly cationic, and are electrostatically adsorbed in the tableware or dishwasher cabinet, and slightly remain on the surface of the tableware or dishwasher cabinet after the final rinse. Thereby, the surface in tableware and a dishwasher cabinet is moderately hydrophobized by the specific ratio of the component (A) / (B), and the water slidability (the effect of sliding water off the surface: not water repellency) is improved. Can result in reduced drying time. For these reasons, it is presumed that the effect of improving the drying property can be obtained.

<< Arbitrary ingredient >>
<< (C) Non-crosslinked polymer polycarboxylic acid or salt thereof >>
The detergent composition for an automatic dishwasher of the present invention preferably contains (C) a non-crosslinked polymer polycarboxylic acid or a salt thereof in addition to the above components (A) and (B).
By including a non-crosslinked polymer polycarboxylic acid or a salt thereof, the detergent composition for an automatic dishwasher of the present invention exhibits excellent effects in terms of cleaning power against tea astringent stains and finish of glass tableware. I can do it. In addition, although the crosslinking type polymer represented by the carboxy vinyl polymer is useful as a thickener, the said effect cannot fully be confirmed.

The (C) non-crosslinked polymer polycarboxylic acid or salt thereof used in the present invention may be a homopolymer of a monomer having a carboxyl group or a copolymer of monomers having two or more kinds of carboxyl groups. A copolymer of a monomer having a carboxyl group and a monomer having no carboxyl group may be used. Examples of the homopolymer include poly (meth) acrylic acid or a salt thereof, polycrotonic acid or a salt thereof, polyitaconic acid or a salt thereof, and the like. Examples of the copolymer of monomers having two or more kinds of carboxyl groups include (meth) acrylic acid-maleic acid copolymers or salts thereof, and acrylic acid-crotonic acid copolymers or salts thereof. Examples of the copolymer of a monomer having a carboxyl group and a monomer having no carboxyl group include an ethylene-maleic acid copolymer or a salt thereof, a methacrylic acid-ethyl acrylate copolymer or a salt thereof.
Among these, a copolymer of a monomer having two or more kinds of carboxyl groups is preferable, and an acrylic acid / maleic acid copolymer is more preferable.
In the case of a copolymer of monomers having two kinds of carboxyl groups, the copolymerization ratio (molar ratio) is preferably 75/25 to 50/50.

  (C) The non-crosslinked polymer polycarboxylic acid or salt thereof preferably has a weight average molecular weight of 10,000 to 100,000 as measured by gel permeation chromatography, more preferably 30,000 to 80,000. preferable.

Examples of the salt of the non-crosslinked polymer polycarboxylic acid include sodium salt and potassium salt. Sodium salt is preferred.
Particularly preferred is an acrylic acid / maleic acid copolymer or a sodium salt thereof having a weight average molecular weight of 30,000 to 80,000 and a copolymerization ratio (molar ratio) of 75/25 to 50/50.
Moreover, the non-crosslinked polymer polycarboxylic acid or the salt thereof as the component (C) can be used alone or in combination.

  The content of the (C) component non-crosslinked polymer polycarboxylic acid or a salt thereof is preferably 4 to 50% by mass, more preferably 7 to 50% by mass, and more preferably 15 to 50% with respect to the total amount of the cleaning composition. Even more preferred is mass%. Within this range, the drying time is further shortened and the detergency against solid fat is further improved. Moreover, since it is excellent also in tea astringency cleaning power and cloudy cleaning power, it is preferable.

  The composition of the present invention can be produced as a cleaning composition by mixing the above-mentioned components by a conventional method. For example, it can be liquid, gel or paste.

The composition of the present invention may further contain other components other than those usually used in a detergent composition for an automatic dishwasher as long as the effects of the present invention are not impaired.
Specific examples of other ingredients include solvents such as ethanol, propylene glycol and purified water, inorganic metal salts, plant extracts, antiseptic / antibacterial / antibacterial agents, deodorants, stabilizers, thickeners And polymers other than (C) component, ionic surfactants other than (A) component and (B) component, and nonionic surfactants, fragrances, inorganic salts, enzymes, dyes and the like.

Specific examples of nonionic surfactants include alkyl glycosides, sucrose fatty acid esters, polyglycerin fatty acid esters, etc., but alkyl glycosides are particularly preferred, and 2-ethylhexyl glucoside is particularly preferred, and the blending amount thereof is not particularly limited. However, 0.1 to 10% of the total amount of the cleaning composition is preferable.
Specific examples of disinfecting / antibacterial / bactericidal agents include monoalkyltrimethylammonium chloride, dialkyldimethylammonium chloride, quaternary ammonium salts such as benzalkonium chloride, basic polypeptides such as polylysine, 2-methyl-4-isothiazoline- 3-one, 5-chloro-2-methyl-4-isothiazolin-3-one or a mixture of the two, 2-bromo-2-nitro-1,3-propanediol, benzoic acid and / or its salt, paraoxybenzoate Methyl acid, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and the like can be mentioned, and quaternary ammonium salts are particularly preferable, and the amount of the compound is not particularly limited, but is 0. 001 to 1% is preferable.
Specific examples of the thickener include carboxyvinyl polymer, polyacrylic acid, carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carrageenan, xanthan gum and the like. Although not performed, 0.01 to 5% is preferable with respect to the total amount of the cleaning composition.
Specific examples of the deodorant component include water-soluble and oil-soluble extracts extracted from lavender, rosemary, mulberry, sage, chamomile, jasmine and the like, but water-soluble and oil-soluble extracts of lavender and rosemary are particularly preferable. Is preferably a water-soluble extract, and its blending amount is not particularly limited, but is preferably 0.001 to 1%.
Specific examples of the enzyme include amylase, protease, lipase, cellulase and the like, and amylase and protease are particularly preferable. Although the compounding quantity is not specifically limited, 0.1-10 mass% is preferable with respect to cleaning composition whole quantity.

In the liquid detergent composition for an automatic dishwasher of the present invention, the pH is arbitrary within a range not impairing the effects of the present invention, but the pH of a 0.2 wt% aqueous solution of the composition at 25 ° C. is 6.0. Adjustment to ˜8.0 is preferable because improvement in finish of aluminum tableware can be realized at the same time.
As a pH adjuster, an organic acid, an inorganic acid, an organic alkali agent, and an inorganic alkali agent that are usually used in a liquid composition can be used. Examples of organic acids include citric acid, hydroxyethane diphosphonic acid and the like. Examples of inorganic acids include hydrochloric acid and sulfuric acid. Examples of the organic alkali agent include monoethanolamine, diethanolamine, triethanolamine and the like. Examples of the inorganic alkaline agent include sodium hydroxide and potassium hydroxide.

<< Examples 1-22 and Comparative Examples 1-10 >>
Each component was mix | blended with the compounding composition shown to the following Tables 1-3 using a three-one motor and a stirring blade, and the liquid detergent composition for automatic dishwashers was prepared.
In addition, each abbreviation in Tables 1-3 shows the following. Moreover, unless otherwise indicated,% in a table | surface represents the mass% of each component with respect to the whole composition.
Examples 19 to 22 are reference examples.

<Compound of (A) General Formulas (I) and (II) where m + n is 10 to 50>
A-1: Compound represented by the general formula (I) (where R ₁ : alkyl group derived from coconut oil, R ₂ : methyl group, m + n = 15, X ⁻ = Cl ⁻ ); Lion Akzo Co., Ltd. Product name "Eso Card C / 25"
A-2: Compound represented by general formula (I) (where R ₁ : alkyl group derived from coconut oil, R ₂ : tolyl group, m + n = 30, X ⁻ = Cl ⁻ ); ) Product name "Bisnol UP-10"
A-3: Compound represented by the general formula (II) (where R _{3 is} an alkyl group derived from palm, m + n = 15); manufactured by Lion Akzo Co., Ltd., trade name “Esomine C / 25”

<Compound of (B) component of general formulas (I) and (II) where m + n is 1 to 3>
B-1: Compound represented by general formula (I) (where R _{1 is} an alkyl group derived from palm, R _{2 is a} methyl group, m + n = 2, X ⁻ = Cl ⁻ ); manufactured by Lion Akzo Co., Ltd. , Product name "Esocard C / 12"
B-2: Compound represented by the general formula (II) (where R _{3 is} an alkyl group derived from palm, m + n = 2); trade name “Esomine C / 12” manufactured by Lion Akzo Co., Ltd.
B-3 (comparative product): C _n H 2 _{n + 1} O (EO) ₃ (PO) ₃ H (n = 12/13 mixture (mass ratio 65/35)), manufactured by Shell, average EO of trade name Neodol alcohol : 3, average PO: 3 mol adduct. EO represents an ethylene oxide group, and PO represents a propylene oxide group.

(Synthesis method of B-3)
As solution a, 47.69 g of aluminum nitrate nonahydrate and 24.43 g of manganese nitrate hexahydrate were dissolved in 68.03 g of magnesium nitrate hexahydrate with 450 g of deionized water. As solution b, 13.47 g of sodium carbonate was dissolved in 450 g of deionized water.
Solution a and solution b were added dropwise to a catalyst preparation tank in which 1800 g of deionized water had been previously charged, with an aqueous NaOH solution at pH = 9 and a temperature of 45 ° C. in 45 minutes. After aging for 1 hour, the mother liquor was filtered off, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain 30 g of a composite metal hydroxide.
This was calcined at 800 ° C. in a nitrogen atmosphere to obtain 19 g of a composite metal oxide catalyst mainly composed of magnesium oxide.
Next, 120 g of Neodol 23 (C12,13, branching rate 20%: manufactured by Shell) and 0.3 g of the above-mentioned catalyst were charged in the autoclave as raw alcohol, and the inside of the autoclave was replaced with nitrogen, followed by ascending with stirring. Warm up. Subsequently, 82 g of ethylene oxide was introduced and reacted while maintaining the temperature at 180 ° C. and the pressure at 0.5 MPa or less. The obtained polyoxyalkylene ether had an average ethylene oxide addition mole number of 3.
Furthermore, 108 g of propylene oxide was introduced and reacted while maintaining the temperature of the autoclave at 180 ° C. and the pressure at 0.5 MPa or less. The average polypropylene oxide addition mole number of the obtained polyoxyalkylene ether was 3. After cooling the reaction solution to 80 ° C., 11 g of water and 3 g of Hyflo Supercell (Celite) as a filter aid are added, stirred and mixed, and then the catalyst is filtered through a cellulose filter (quantitative filter paper 5C: Advantech). Separated. In this way, a nonionic surfactant 1 was obtained.

<(C) Component Non-Crosslinked Polymer Polycarboxylic Acid>
C-1: Acrylic acid / maleic acid copolymer soda salt, manufactured by Nippon Shokubai Co., Ltd., trade name Aqualic TL-400 (mass average molecular weight Mw = 50,000)
C-2: Acrylic acid / maleic acid copolymer soda salt, manufactured by BASF, trade name Socaran CP7 (mass average molecular weight Mw = 50,000)
C-3 (Comparative product of A): Polyvinyl alcohol, manufactured by Kuraray Co., Ltd., trade name “Kuraray Poval PVA-103”

<Common ingredients (Mixed amount is mass% as it is)>
Z: 1% amylase (trade name “Termamyl Mill 300L” manufactured by Novozymes Japan), 1% protease (trade name “Sabinase Ultra 16XL” manufactured by Novozymes Japan).
<PH adjuster>
In all examples and comparative examples, after mixing the components (A), (B), (C), and the common components in the blending ratios shown in Tables 1 to 3, ion-exchanged water was added to adjust the pH, 100% by mass. In addition, pH adjustment added the appropriate quantity so that it might become pH 7 using a sodium hydroxide solution, and adjusted pH of the composition.

About each obtained composition, based on the following evaluation method, drying property, the cleaning power of solid fat, foaming, tea astringency cleaning power, and the cloudy cleaning power of glass were evaluated.
The results are shown in Tables 1-3.

[Dryability evaluation method]
Three white ceramic dishes (diameter 20 mm) were loaded into an automatic dishwasher “Model NP-TS1 manufactured by Panasonic Corporation”, and low-temperature course washing (without heater drying) was performed using 6 g of the prepared composition. Then, it was set as ventilation mode (60 minutes), and the dry state of the white earthenware dish was determined visually every 10 minutes, and evaluated according to the following evaluation criteria.
In terms of product value, the evaluations of 〜 to ○ were regarded as acceptable.
Evaluation criteria:
A: Dried in less than 30 minutes.
○: Dried for 30 minutes to less than 40 minutes.
Δ: Dried in 40 minutes to less than 50 minutes.
X: It dried in 50 minutes or more.

[Evaluation method of detergency of solid fat]
Polypropylene lunch box (inner dimensions: freshly 113mm, width 174mm, depth 35mm, open top) coated with 2g of beef tallow (Wako Pure Chemical Industries, Ltd.), automatic dishwasher "Matsushita Electric Standard model washing using 6g of the prepared composition NP-40SX2 made by Sangyo Co., Ltd., and sensory evaluation of residual fat in polypropylene lunch box based on the following evaluation criteria did.
Evaluation criteria (In terms of product value, ◎ to ○ are considered acceptable)
A: No oil droplets remain and no stickiness is felt.
○: Residual oil droplets are not observed, but a slight sliminess is felt.
Δ: Slight residual oil droplets are observed.
X: Residual oil droplets are remarkably observed.

[Bubbling evaluation method]
6 g of the prepared composition was added to an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., model NP-40SX2”, and washing was started on a standard course. One minute after the start of washing, the lid of the dryer was opened, and foaming was subjected to sensory evaluation based on the following evaluation criteria.
Evaluation criteria (In terms of product value, ◎ to ○ are considered acceptable)
A: A little bubbling.
○: Slightly bubbling.
(Triangle | delta): It is quite foamy.
X: Very foamy.

[Evaluation method of tea astringency cleaning power]
Three cups of coffee with tea stains (inner diameter 70 mm, height 70 mm) left for 5 days at 25 ° C and 50% RH after drinking and drinking tea are automatically washed by the dishwasher “Matsushita Electric Industrial Co., Ltd. The model NP-40SX2 "was loaded, 6 g of the prepared composition was used for standard course cleaning, and the finished condition was sensory evaluated based on the following evaluation criteria.
Evaluation criteria (In terms of product value, ◎ to ○ are considered acceptable)
(Double-circle): A stain | pollution | contamination does not remain | survive at all and the discomfort, such as roughness, is not felt.
○: Residue of dirt is not visually recognized, but feels slightly rough when touched.
Δ: Residue of dirt is slightly recognized visually.
X: Dirt is not removed.

[Evaluation method for cloudy detergency of glass]
A glass cup (upper diameter 63 mm, lower diameter 53 mm, height 100 mm) is filled into an automatic dishwasher, 1.2 g of sodium carbonate is put into the machine, and the entire process of washing to rinsing is performed with 30 degrees (German hardness) hard water. The cup was whitened. The cup is loaded into an automatic dishwasher “Matsushita Electric Industrial Co., Ltd., Model NP-40SX2”, and 6 g of the prepared composition is used for standard course washing, and the finish is determined based on the following evaluation criteria. Sensory evaluation was performed.
Evaluation criteria (In terms of product value, ◎ to ○ are considered acceptable)
A: No whitened material remains and no discomfort such as roughness is felt.
○: A slight whitening residue is observed partially.
Δ: A slight amount of whitened product was visually observed, and the overall transparency was lost.
X: The whitened material has not fallen.

From the result of the said Tables 1-3, Examples 1-22 of this invention are compared with Comparative Examples 1-9, drying time is shortened, ensuring low foaming property, and also the detergency of solid fat It became clear that it was excellent. Moreover, it turned out that Examples 1-20 of this invention can obtain a favorable result also in the point of tea astringency cleaning power and cloudy cleaning power.
Since the comparative example 1 does not contain the component (A), the dryness and the detergency of the solid fat are inferior, and further, sufficient results were not obtained in terms of the detergency of tea astringency.
Since Comparative Examples 2 and 3 did not contain the component (B) (Comparative Example 2) or were different from the component (B) used in the present invention (Comparative Example 3), The result was inferior to the detergency of solid fat.
In Comparative Examples 4 to 7, the content ratio of the component (A) to the component (B) is outside the scope of the present invention, and for Comparative Examples 4 and 6, the amounts of the component (A) and the component (B) are also present. Since it was outside the scope of the invention, the results were inferior in dryness and detergency of solid fat.
In Comparative Example 8, since the amount of the component (A) and the component (B) was larger than the upper limit in the present invention, foaming could not be suppressed.
Since the amount of (A) component and (B) component was smaller than the lower limit in this invention, the comparative example 9 was a result inferior to the cleaning power of solid fat.

Claims (9)

(A) at least one compound selected from the group consisting of compounds represented by the following general formula (II) (wherein m + n is 10 to 50);
(B) the following general formula (II) compounds represented by (wherein, m + n is 1 to 3) at least one compound selected from the group consisting of, and
(C) a non-crosslinked polymer polycarboxylic acid or a salt thereof ,
Content of the said (A) component is 0.4-5 mass%,
The content of the component (B) is 0.3 to 5% by mass, and
(A) / (B) mass ratio is 0.3-5, The liquid detergent composition for automatic dishwashers characterized by the above-mentioned.

(R ₃ is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, a hydroxyalkyl group having a linear or branched alkyl group having 8 to 20 carbon atoms, a tolyl group, a phenyl group, or a benzyl group. Indicates one of them.
EO represents an ethylene oxide group. m and n are the average added moles of EO. )   The cleaning composition for an automatic dishwasher according to claim 1, wherein the mass ratio of (A) / (B) is 0.7 to 3.0.   (B) Cleaning composition for automatic dishwashers of Claim 1 or 2 whose content of a component is 0.5-3 mass%.   The cleaning composition for an automatic dishwasher according to any one of claims 1 to 3, wherein the content of the component (A) is 0.7 to 3.5% by mass. Wherein in component (B), R ₃ is an alkyl or alkenyl group of a straight-chain or branched-chain having 10 to 18 carbon atoms, an automatic dishwasher detergent according to any one of claims 1-4 Composition. The washing | cleaning agent for automatic dishwashers as described in any one of Claims 1-5 whose R < ₃ > is a C10-C18 linear or branched alkyl group or alkenyl group in said (A) component. Composition. The cleaning composition for an automatic dishwasher according to any one of claims 1 to 6 , wherein the component (B) is polyoxyethylene (2) alkylamine. The cleaning composition for an automatic dishwasher according to any one of claims 1 to 7 , wherein the component (A) is polyoxyethylene (15) alkylamine. (C) The cleaning composition for automatic dishwashers as described in any one of Claims 1-8 whose component is a (meth) acrylic acid / maleic acid copolymer or its salt.