JP6956671B2 - Dishwasher detergent composition - Google Patents

Description

The present invention relates to a dishwasher detergent composition.

In recent years, dishwashers for washing tableware, cooking utensils, etc. (objects to be washed) have become widespread not only in kitchens such as hotels, restaurants, and food service centers, but also in ordinary households. For washing with a dishwasher, a special detergent (dishwasher detergent) is generally used.
Microorganisms can easily grow in a humid environment such as in a dishwasher. Therefore, the dishwasher detergent is required to have sterilizing power.
In addition, the dishwasher detergent is required to have high detergency against oil stains.

For example, Patent Document 1 proposes a detergent composition containing an amine compound, an alkaline compound, and water. According to the cleaning agent composition of Patent Document 1, a biofilm suppressing effect and a cleaning power against oil stains can be obtained.

Japanese Unexamined Patent Publication No. 2016-183242

However, the liquid cleaning agent of Patent Document 1 does not have sufficient sterilizing power and cleaning power against oil stains.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a dishwasher detergent composition having excellent sterilizing power and cleaning power against oil stains.

The liquid detergent composition of the present invention includes the following aspects.
[1] Containing (A) component, (B) component, (C) component, and (D) component.
The component (A) is an anionic surfactant, and the component (A) is an anionic surfactant.
The component (B) is a compound represented by the following formula (b-1).
The component (C) is a chelating agent.
The component (D) is an amine-type surfactant (d1) (excluding the component (B)), an amphoteric surfactant (d2), an amine oxide-type surfactant (d3), and a quaternary ammonium salt type. At least one selected from the group consisting of surfactant (d4),
A dishwasher detergent composition having a mass ratio of the component (D) / the component (B) of 0.05 to 400.
R ¹ −N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
(In the formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group of the branched chain of the number 8-18; n is an integer of 2-6.)
[2] The component (D) contains the amine-type surfactant (d1).
The dishwasher detergent composition according to [1], wherein the amine-type surfactant (d1) is a compound represented by the following formula (d-1).
R ² R ³ R ⁴ N ... (d-1)
(In formula (d-1), R ² , R ³ , and R ⁴ are substituents on N, and R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms. A group, an alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or a carbon number of carbon atoms. It is an aminoalkyl group of 1 to 4; R ⁴ is an alkyl group having 8 to 21 carbon atoms, an alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or R ⁵ -X- (CH _2). ) _m - it is a group represented by; ^{R 5} is a linear alkyl group of 8 to 21 carbon atoms, linear alkenyl group having 8 to 21 carbon atoms, branched chain alkyl group of 8 to 21 carbon atoms, Alternatively, it is an alkenyl group of a branched chain having 8 to 21 carbon atoms; X is -O-, -C (O) NR ^6- , or -NH-; R ⁶ is a hydrogen atom, an alkyl having 1 to 4 carbon atoms. A group or a hydroxyalkyl group having 1 to 4 carbon atoms; m is an integer of 1 to 5).
[3] The dishwasher according to [1] or [2], wherein the mass ratio represented by the component (A) / [component (B) + component (D)] is 0.01 to 20. Detergent composition for.
[4] The dishwasher according to any one of [1] to [3], wherein the total amount of the surfactant is 0.1 to 10% by mass with respect to the total mass of the dishwasher detergent composition. Detergent composition for.
[5] The item according to any one of [1] to [4], wherein the content of the component (C) is 8% by mass or more in terms of acid with respect to the total mass of the dishwasher detergent composition. Dishwasher detergent composition.

The detergent composition for a dishwasher of the present invention is excellent in sterilizing power and cleaning power against oil stains.

≪Dishwasher detergent composition≫
The dishwasher detergent composition of the present invention contains (A) component, (B) component, (C) component, and (D) component.

<Ingredient (A)>
The component (A) is an anionic surfactant. Examples of the component (A) include a sulfonate type, a sulfate ester type, a carboxylate type, and a phosphate ester type.
Examples of the sulfonate type include alkylbenzene sulfonate, alkane sulfonate, α-olefin sulfonate, α-sulfo fatty acid salt, α-sulfo fatty acid alkyl ester salt, alkyl sulfosuccinate, dialkyl sulfosuccinic acid and the like. ..
Examples of the sulfate ester salt type include alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, and polyoxyalkylene alkenyl ether sulfate ester salts.
Examples of the carboxylate type include alkyl ether carboxylates, amide ether carboxylates, sulfosuccinates, amino acid-based anionic surfactants and the like.
The component (A) 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 the alkenyl group may be linear or branched.
Among them, the sulfonate type is preferable in terms of suppressing oil recontamination, tea astringency detergency, and low foaming property, and among them, alkane sulfonate and dialkyl sulfosuccinate are preferable, and alkane sulfonate is more preferable. ..
Examples of the salt constituting the anionic surfactant include metal salts such as sodium, potassium, magnesium and calcium.
Specific examples of the alkane sulfonate include sodium tetradecane sulfonate, sodium hexadecane sulfonate, sodium octadecane sulfonate and the like.
Among these, a mixture of secondary sodium alkanesulfonate having 14 or more carbon atoms and 17 or less carbon atoms is preferable.
Examples of commercially available products include HOSTAPUR SAS30A manufactured by Clariant Japan, MERSOLATE H-95 manufactured by Bayer, and Ramtel PS manufactured by Kao Corporation.

The component (A) may be used alone or in combination of two or more.
The content of the component (A) is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and 0.1 to 3% by mass with respect to the total mass of the dishwasher detergent composition. % Is more preferable.
When the content of the component (A) is not more than the above upper limit value, foaming is easily suppressed.
When the content of the component (A) is at least the above lower limit value, the detergency against oil stains is likely to be improved.

<Ingredient (B)>
The component (B) is a compound represented by the following formula (b-1).
R ¹ −N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
(In the formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group of the branched chain of the number 8-18; n is an integer of 2-6.)

Examples of the component (B) include N- (3-aminopropyl) -N-decylpropane-1,3-diamine, N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine, and N. -(3-Aminoethyl) -N-dodecylpropane-1,3-diamine, N- (3-aminopropyl) -N-tetradecylpropane-1,3-diamine and the like can be mentioned. N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine is preferable from the viewpoint of detergency and sterilizing power against oil stains.

The component (B) may be used alone or in combination of two or more.
The content of the component (B) is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.5% by mass, and 0.01 to 0, based on the total mass of the dishwasher detergent composition. .1% by mass is more preferable.
When the content of the component (B) is not more than the above upper limit value, the detergency against oil stains is likely to be improved.
When the content of the component (B) is at least the above lower limit value, the sterilizing power is likely to be improved.

<Ingredient (C)>
The component (C) is a chelating agent.
The component (C) is not particularly limited, and any of the general chelating agents that have been used in dishwasher detergents can be used.
A small molecule chelating agent is preferably mentioned as the component (C) because the sterilizing power is further enhanced. Examples of the low molecular weight chelating agent include ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N, N-diacetic acid, dihydroxyethyl ethylenediamine diacetic acid, and hydroxyethyl iminoni. Acetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamate diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexacetic acid, dihydroxyethylglycine, Examples thereof include 3-hydroxy-2,2'-iminodicohactic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, hydroxyethanediphosphonic acid, aminotrimethylenephosphonic acid, tripolyphosphoric acid, and salts thereof. As the salt constituting the low molecular weight chelating agent, an alkali metal salt is preferable, and a sodium salt and a potassium salt are more preferable.
Among them, low molecular weight chelating agents tend to increase the sterilizing power, so ethylenediaminetetraacetic acid, nitrilotriacetic acid, β-alanine diacetic acid, ethylenediamine disuccinic acid, L-aspartic acid-N, N-diacetic acid, and dihydroxy. Ethylenediaminediamine diacetic acid, hydroxyethyliminodiacetic acid, citric acid, hydroxyethylethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, L-glutamate diacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, diethylenetriaminetetraacetic acid, tri One or more chelating agents selected from the group consisting of ethylenediaminetetraacetic acid, dihydroxyethylglycine, 3-hydroxy-2,2'-iminodicohactic acid, serine diacetic acid, asparagine diacetic acid, methylglycine diacetic acid, and salts thereof. Is preferably used.
Further, citric acid, L-glutamate diacetic acid, methylglycine diacetic acid, diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid or salts thereof are preferable, and citric acid, ethylenediamine tetraacetic acid or salts thereof are particularly preferable.

The component (C) may be used alone or in combination of two or more.
The content of the component (C) is preferably 8% by mass or more in terms of acid, more preferably 10 to 25% by mass in terms of acid, and 10 to 10% in terms of acid with respect to the total mass of the dishwasher cleaning agent composition. 18% by mass is more preferable, and 12 to 18% by mass in terms of acid is particularly preferable.
When the content of the component (C) is within the above range, it is easy to improve the sterilizing power and the detergency against oil stains.

<Ingredient (D)>
The component (D) is an amine-type surfactant (d1) (excluding the component (B)) (hereinafter, also referred to as "(d1) component"), an amphoteric surfactant (d2) (hereinafter, "(d2)". ) Component), amine oxide-type surfactant (d3) (hereinafter, also referred to as “(d3) component”), and quaternary ammonium salt-type surfactant (d4) (hereinafter, “(d4) component”). It is at least one selected from the group consisting of (also referred to as).

[(D1) component]
The component (d1) is a primary amine, a secondary amine, or a tertiary amine that functions as a surfactant (however, the component (B) is not included).
As the component (d1), a compound represented by the following formula (d-1) is preferable.
R ² R ³ R ⁴ N ... (d-1)
(In formula (d-1), R ² , R ³ , and R ⁴ are substituents on N, and R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms. , An alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or 1 carbon group. be ~ 4 aminoalkyl group; ^{R 4} is an alkyl group having 8 to 21 carbon atoms, an alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or ^R 5 -X- _(CH 2) _m - be a group represented by; ^{R 5} is a linear alkyl group of 8 to 21 carbon atoms, linear alkenyl group having 8 to 21 carbon atoms, branched chain alkyl group of 8 to 21 carbon atoms, or It is an alkenyl group of a branched chain having 8 to 21 carbon atoms; X is -O-, -C (O) NR ^6- , or -NH-; R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. , Or a hydroxyalkyl group having 1 to 4 carbon atoms; m is an integer of 1 to 5).
The compound represented by the formula (d-1) preferably contains at least one or more, preferably 1 to 2 alkyl groups or alkenyl groups having 8 to 21 carbon atoms in the molecule.

Of these, a compound represented by the following formula (d-1-1) is preferable.

(In the formula (d-1-1), R ⁷ is a linear alkyl group having 13 to 21 carbon atoms, a branched alkyl group having 13 to 21 carbon atoms, a linear alkenyl group having 13 to 21 carbon atoms, and the like. Alternatively, it is an alkenyl group of a branched chain having 13 to 21 carbon atoms; R ⁸ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms; R ⁹ is an alkyl group having 1 to 4 carbon atoms. It is an alkylene group of 1 to 4; R ¹⁰ and R ¹¹ are independently hydrogen atoms or alkyl groups having 1 to 4 carbon atoms.)

In the formula (d-1-1), R ⁷ is preferably a linear or branched alkyl group having 13 to 21 carbon atoms. The number of carbon atoms of the alkyl group and alkenyl group for R ⁷ are each 13 to 21, since the anti-foaming effect is enhanced more, preferably 15 to 21, more preferably from 15 to 19.
The number of hydroxy groups in the hydroxyalkyl group in R ^{8 may be one or two or more.} Among these, as R ^8, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms is preferable, a hydrogen atom, more preferably a methyl group, a hydrogen atom is particularly preferred.
The carbon number of the alkylene group in R ⁹ is 1 to 4, preferably 1 to 3, more preferably 2 or 3, and particularly preferably 3. The ^{number of carbon atoms of the alkyl group in R 10} and R ¹¹ is 1 to 4, preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. Among them, R ¹⁰ and R ¹¹ are preferably alkyl groups having 1 to 4 carbon atoms, respectively, and are preferably the same as each other.
Specific examples of the compound represented by the formula (d-1-1) include dimethylaminopropyl amide myristate, dimethyl aminopropyl palmitate, and dimethyl aminopropyl amide stearate because the foam-suppressing effect can be more easily obtained. , Bechenic acid dimethylaminopropylamide is preferable, palmitic acid dimethylaminopropylamide, stearate dimethylaminopropylamide and behenic acid dimethylaminopropylamide are more preferable, palmitic acid dimethylaminopropylamide and stearate dimethylaminopropylamide are particularly preferable. ..

Examples of the component (d1) other than the compound represented by the formula (d-1-1) include coconut alkylamine, beef alkylamine, oleylamine, octylamine, dodecylamine, octadecylamine, di-cured beef alkylamine, and coconut. Alkyldimethylamine, beef alkyldimethylamine, dodecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, behenyldimethylamine, diorailmethylamine, didecylmethylamine, N-palmalkyl-1,3-diaminopropane, N-beef alkyl Examples thereof include -1,3-diaminopropane, N-hardened beef fat alkyl-1,3-diaminopropane, and 3,3'-diamino-N-methyldipropylamine.

[(D2) component]
The component (d2) is an amphoteric surfactant.
Of these, the compound represented by the following formula (d-2) is preferable.
_{^{R 12 - (A) p -N}} + (-R 13) (- R 14) -R 15 -R 16 ··· (d-2)
(In formula (d-2), R ¹² is a linear or branched alkyl group having 8 to 18 carbon atoms; R ¹³ and R ¹⁴ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl. Group; A is -C = O (-NH-X)-; X is an alkylene group having 1 to 4 carbon atoms; p is a number of 0 or 1; R ¹⁵ is 1 to 4 carbon atoms. is 2 alkylene ^{group; R 16} is -CO ₂ ^- or -SO ₃ ^- and is).
Examples of the component (d2) include amidopropyl octanoate dimethylaminoacetic acid betaine, amidopropyl dimethylaminoacetic acid betaine decanoate, amidopropyl dimethylaminoacetic acid betaine laurate, amidopropyl dimethylaminoacetic acid betaine myristate, and amide propyl dimethyl stearate. Aminoacetate betaine, oleate amide propyl dimethylamino acetate betaine, coconut oil fatty acid amide propyl dimethylamino acetate betaine, palm oil fatty acid amide propyl dimethyl amino acetate betaine, palm kernel oil fatty acid amide propyl dimethyl amino acetate betaine, octyl dimethyl amino acetate betaine, Decyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, myristyldimethylaminoacetic acid betaine, stearyldimethylaminoacetic acid betaine, oleyldimethylaminoacetic acid betaine, octanoic acid amide propyl hydroxysulfobetaine, decanoate amide propyl hydroxysulfobetaine, laurate amide propyl Hydroxysulfobetaine, myristate amide propyl hydroxysulfobetaine, stearate amide propyl hydroxysulfobetaine, oleate amide propyl hydroxysulfobetaine, palm oil fatty acid amide propyl hydroxysulfobetaine, palm oil fatty acid amide propyl hydroxysulfobetaine, palm kernel oil fatty acid Examples thereof include amidopropyl hydroxysulfobetaine, octyl hydroxysulfobetaine, decyl hydroxy sulfobetaine, lauryl hydroxy sulfobetaine, myristyl hydroxy sulfobetaine, stearyl hydroxy sulfobetaine and oleyl hydroxy sulfobetaine.

[(D3) component]
The component (d3) is an amine oxide type surfactant.
Of these, the compound represented by the following formula (d-3) is preferable.

(In the formula (d-3), R ¹⁷ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or It is an alkenyl group of a branched chain having 8 to 18 carbon atoms; R ¹⁹ and R ²⁰ are independently alkyl groups having 1 to 3 carbon atoms or hydroxyalkyl groups having 1 to 3 carbon atoms; ¹⁸ is an alkylene group having 1 to 4 carbon atoms; B is -CONH -, - NHCO -, - COO -, - OCO- or -O- and is; r is a number of 0 or 1; Z ^- is It is a counter ion.)
Examples of the component (d3) include alkyldimethylamine oxides such as lauryldimethylamine oxide, coconut alkyldimethylamine oxide, and n-dodecyldimethylamine oxide; alkyldiethylamine oxides such as lauryldiethylamine oxide; lauric acid amidopropyldimethylamine oxide and the like. Arcanoylamide alkyldimethylamine oxide and the like.

[(D4) component]
The component (d4) is a quaternary ammonium salt type surfactant.
Examples of the component (d4) include tetra short-chain (alkyl having 1 to 4 carbon atoms) ammonium salts such as tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, and tetrabutylammonium salt; octyltrimethylammonium salt and decyltrimethylammonium salt. Ammonium salt, dodecyltrimethylammonium salt, tetradecyltrimethylammonium salt, lauryltrimethylammonium salt, cetyltrimethylammonium salt, palmityltrimethylammonium salt, stearyltrimethylammonium salt, octyldimethylethylammonium salt, decyldimethylethylammonium salt, dodecyldimethylethyl Ammonium salt, tetradecyldimethylethylammonium salt, lauryldimethylethylammonium salt, cetyldimethylethylammonium salt, stearyldimethylethylammonium salt, octyldiethylmethylammonium salt, decyldiethylmethylammonium salt, dodecyldiethylmethylammonium salt, tetradecyldiethylmethyl Long-chain (alkyl with 8 to 18 carbon atoms) tri-short chain (alkyl with 1 or 2 carbon atoms) ammonium salt such as ammonium salt, cetyldiethylmethylammonium salt, stearyldiethylmethylammonium salt; dioctyldimethylammonium salt, didecyldimethyl Ammonium salt, didodecyldimethylammonium salt, ditetradecyldimethylammonium salt, disetyldimethylammonium salt, distearyldimethylammonium salt, dioctylmethylethylammonium salt, didecylmethylethylammonium salt, didecylmethylethylammonium salt, ditetra Dilong (alkyl with 8 to 18 carbon atoms) dishort chain (alkyl with 1 or 2 carbon atoms) ammonium salt such as decylmethylethylammonium salt, disetylmethylethylammonium salt, distearylmethylethylammonium salt; stearyldimethyl Long chain (alkyl with 8 to 18 carbon atoms) such as hydroxyethylammonium, dishort chain (alkyl with 1 or 2 carbon atoms) Hydroxyalkyl (1 or 2 carbon atoms) ammonium salt; [3 (trimethoxysilyl)] propyl ( Dishort chain (alkyl with 1 or 2 carbon atoms) long chain (alkyl with 8 to 18 carbon atoms) ammonium salt having a trialkoxysilylalkyl group (4 to 10 carbon atoms) such as dimethyl) octadecyl ammonium salt; amine nitrate Benzyltrimethyl Ammonium salt; benzalkonium salt; benzethonium salt and the like can be mentioned.
Among these, long-chain (alkyl with 8 to 18 carbon atoms) tri-short chain (alkyl with 1 or 2 carbon atoms) ammonium salt, di-long chain (alkyl with 8 to 18 carbon atoms) di-short chain (alkyl with 1 or 2 carbon atoms) Alkyl) ammonium salt, benzyltrimethylammonium salt, benzalconium salt, benzethonium salt and the like are preferable, and long-chain (alkyl having 8 to 18 carbon atoms) tri-short chain (alkyl having 1 or 2 carbon atoms) ammonium salt, di-long Chain (alkyl with 8 to 12 carbon atoms) di-short chain (alkyl with 1 or 2 carbon atoms) ammonium salt is more preferred.

Examples of the salt include halides such as chlorine, bromine and iodine; hydroxides; sulfonic acid esters having 1 to 5 carbon atoms, sulfate esters, nitrate esters and the like.

The component (D) may be used alone or in combination of two or more.
The content of the component (D) is preferably 0.01 to 5% by mass, more preferably 0.1 to 5% by mass, and 0.1 to 3% by mass with respect to the total mass of the dishwasher detergent composition. % Is more preferable.
When the content of the component (D) is not more than the above upper limit value, the detergency against oil stains is likely to be improved.
When the content of the component (D) is at least the above lower limit value, the sterilizing power is likely to be improved.

The mass ratio represented by the component (D) / component (B) (hereinafter, also referred to as “D / B ratio”) is 0.05 to 400, more preferably 4 to 55.
When the D / B ratio is not more than the above upper limit value, the sterilizing power is likely to be improved.
When the D / B ratio is at least the above lower limit value, it is easy to improve the detergency against oil stains.

The mass ratio represented by the component (A) / [component (B) + component (D)] (hereinafter, also referred to as “A / (B + D) ratio”) is preferably 0.01 to 20, preferably 0.1 to 0. 5 is more preferable, and 0.5 to 2 is even more preferable.
When the A / (B + D) ratio is not more than the above upper limit value, the sterilizing power is likely to be improved.
When the A / (B + D) ratio is at least the above lower limit value, the detergency against oil stains can be easily improved.

<Arbitrary ingredient>
The dishwasher detergent composition of the present invention may contain any component normally contained in a dishwasher detergent, as long as it does not contradict the object of the present invention. For example, acidic thickening polysaccharides, water, organic solvents, enzymes, plant extracts, oil absorbents, defoamers, tableware protectants, thickeners, colorants, nonionic surfactants, hydrotropes, antioxidants. , PH adjusters, colorants, fragrances, bleaches and other substances commonly used in dishwasher cleaners can be used.

Examples of the acidic thickening polysaccharide include a polysaccharide 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 bound. By containing the acidic thickening polysaccharide, it becomes easy to increase the viscosity of the composition.
Examples of the acidic thickening polysaccharide include xanthan gum, gellan gum, carrageenan, pectin, soybean polysaccharide, alginic acid, arabic gum, karaya gum, tragant gum, hyaluronic acid and the like.
Among them, xanthan gum, gellan gum and carrageenan are preferable, and xanthan gum and gellan gum are more preferable.
When the dishwasher detergent composition of the present invention contains an acidic thickening polysaccharide, the content of the acidic thickening polysaccharide is 0.05 to 1. 5% by mass is preferable, 0.1 to 1% by mass is more preferable, and 0.2 to 1% by mass is further preferable.

The total amount of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.2 to 6% by mass, and 1.0 to 3.5% by mass with respect to the total mass of the dishwasher detergent composition. % Is more preferable.
When the total amount of the surfactant is not more than the above upper limit value, it is easy to suppress foaming during washing.
When the total amount of the surfactant is not more than the above lower limit value, the detergency against oil stains can be easily improved.

The pH of the dishwasher detergent composition of the present invention at 25 ° C. is preferably 5 or more from the viewpoint of corrosiveness to the dishwasher. Further, from the viewpoint of low foaming property, 11 or less is preferable. More preferably, it is 6 to 10.
In the present invention, the pH of the dishwasher detergent composition indicates a value measured by adjusting the dishwasher detergent composition to 25 ° C. and using a pH meter or the like.

≪Manufacturing method of detergent composition for dishwasher≫
The detergent composition for a dishwasher of the present invention is not particularly limited, and a conventionally known production method can be used.
As a method for producing a liquid dishwasher detergent composition, a component (A), a component (B), a component (C), a component (D), and an optional component are mixed as needed. Is prepared by

≪How to use the detergent composition for dishwasher≫
The detergent composition for a dishwasher of the present invention may be used according to the model of the dishwasher and the degree of stain on the dishes and the like.
Examples of the method of washing the object to be washed by the dishwasher using the dishwasher detergent composition include a method having both washing and rinsing steps.
As a washing method, for example, the washing liquid prepared by introducing tap water at room temperature (preferably about 5 to 30 ° C.) into the dishwasher chamber is raised to a predetermined washing temperature (the temperature of the washing liquid circulated during washing). A process of cleaning the object to be cleaned while warming (hereinafter referred to as "cleaning process"), a process of rinsing the object to be cleaned after cleaning with tap water at room temperature (hereinafter referred to as "rinsing (1) process"), and While warming tap water at room temperature to 70 to 75 ° C. at 2 to 3 ° C./min, the cleaning object after the rinsing (1) step is further rinsed (hereinafter referred to as "rinsing (2) step"). ) Is mentioned. The cleaning time in the cleaning step is preferably 10 to 40 minutes.
In the case of a general standard course, the cleaning temperature in the cleaning step is about 55 to 65 ° C., and the heating rate is about 2 to 3 ° C./min. In the low temperature course, for example, the cleaning temperature is about 35 to 45 ° C. and the heating rate is about 1 ° C./min. The detergent composition for a dishwasher of the present invention has excellent detergency against oil stains even in low-temperature cleaning, and exhibits excellent detergency even when the cleaning temperature is 35 ° C., for example.
In any course, the amount of the cleaning agent used at one time is preferably 2 to 9 g with respect to about 3 liters of tap water in the case of a liquid cleaning agent.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

The unit of the blending amount in the table is "mass%", and all the components indicate the net conversion amount.
Blanks in the table indicate that the ingredient is not blended.
"Balance" means that water is blended so that the total blending amount (mass%) of all the blending components contained in the composition of each example is 100% by mass. The content of the component (C) is the content as an anhydrous acid type.
The components shown in the table will be described below.

<Ingredient (A)>
-A-1: Secondary sodium alkane sulfonate (secondary sodium alkane sulfonate having 14 to 17 carbon atoms, manufactured by Clariant Japan, trade name "HOSTAPUR SAS 30A").
-A-2: Polyoxyethylene (3 mol on average) sodium lauryl ether sulfate (manufactured by Lion Specialty Chemicals, trade name: "Sannol LMT-1430").
-A-3: Di (2-ethylhexyl) sodium sulfosuccinate (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Repearl 870P").

<Ingredient (B)>
B-1: (N- (3-aminopropyl) -N-dodecylpropane-1,3-diamine) (manufactured by Lonza, trade name "Lonzabac 12.100", in formula (b-1), R ¹ is A compound that is an alkyl group having 12 carbon atoms and has n of 3.

<Ingredient (C)>
-C-1: Citric acid (manufactured by Fuso Chemical Industry Co., Ltd., trade name "purified citric acid (anhydrous)").
-C-2: Methylglycine diacetic acid (manufactured by BASF, trade name "Torillon M").
C-3: L-glutamic acid diacetate (manufactured by AkzoNobel, trade name "GL-47- · S").
-C-4: Ethylenediaminetetraacetic acid (manufactured by Tokyo Chemical Industry Co., Ltd., reagent).

<Ingredient (D)>
· D1-1: C18 dimethylaminopropylamide (Toho Chemical Co., Ltd., trade name "Catinal MPAS"); wherein (d1-1), molecular ^{R 7} is a straight chain alkyl group having 15 carbon atoms ( A mixture of C16) and a molecule (C18) which is a linear alkyl group having R ^{7 = 17 carbon atoms and C16: C18 = 3: 7 in terms of mass ratio.} A ^{compound in which R 8} is a hydrogen atom, R ⁹ is a propylene group ((CH ₂ ) ₃ ), R ¹⁰ is a methyl group, and R ¹¹ is a methyl group.
-D1-2: 3,3'-diamino-N-methyldipropylamine (Tokyo Kasei Kogyo Co., Ltd., reagent), in formula (d-1), R ² is a methyl group and R ³ is 3-amino. propyl group, compounds wherein R ⁴ is 3-aminopropyl group.
D1-3: N-Yashialkyl-1,3-diaminopropane (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Lipomin DA-CD"), in formula (d-1), R ² is a hydrogen atom and R ^A compound in which 3 is a 3-aminopropyl group and R ⁴ is a linear alkyl group having 12 to 16 carbon atoms.
-D2-1: Betaine lauryldimethylaminoacetate, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name "Amigen S"), in formula (d-2), R ¹² is a linear alkyl group having 11 carbon atoms, and R ¹³ and R ¹⁴ are methyl groups, A is -C = O (-NH-X)-, X is a propylene group ((CH ₂ ) ₃ ), p is 1, and R ¹⁵ is methylene. a ^{group, R 16} is -CO ₂ ^-, compound.
D3-1: n-dodecyldimethylamine oxide (manufactured by Lion Specialty Chemicals Co., Ltd., trade name "Cadenax DM12D-W (C)").
-D4-1: Didecyldimethylammonium chloride (manufactured by Lonza, trade name "Bardac2280G").
-D4-2: Dioctyldimethylammonium chloride (manufactured by Lonza, trade name "BardacLF-80").

<Arbitrary ingredient>
-Xanthan gum (manufactured by Sansho Co., Ltd., product name KELZANT).
-PH adjuster: sulfuric acid (manufactured by Kanto Chemical Co., Ltd.), sodium hydroxide: 48% sodium hydroxide (manufactured by Asahi Glass Co., Ltd.), granular sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.), potassium hydroxide: 48% Potassium hydroxide (manufactured by Asahi Glass Co., Ltd.), Granular potassium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.).

<Preparation of detergent composition for dishwasher>
In accordance with the compositions of Tables 1 to 4, each example was prepared by dissolving the component (A), the component (B), the component (C), the component (D), the optional component, and the pH adjuster in water as a solvent. 0.8 kg of a dishwasher detergent composition was prepared respectively.
Specifically, it was put into a 1 L beaker (diameter 12 cm) so that the total amount of xanthan gum and water was 50% by mass of the whole composition. The stirrer of HEIDON FBL1200 Three-One Motor (manufactured by Shinto Kagaku Co., Ltd.) 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. The mixture was stirred at ~ 900 rpm, and stirring was continued until there were no undissolved components (lumps) to obtain a polymer aqueous solution. Then, the component (A), the component (B), and a pH adjuster (sodium hydroxide or sulfuric acid) were added to obtain a mixed solution A.
Separately from this, water adjusted to 75 ° C. and component (D) were added to a beaker having a capacity of 1 L (diameter 12 cm) to obtain a mixed solution B.
The mixture B was added to the mixture A while stirring the stirrer at a rotation speed of 650 rpm. After completion of the addition, the mixture was stirred for 5 minutes to obtain a mixed solution C. After cooling this mixed solution C to 25 ° C., the component (C) was added. Further, a pH adjuster was added to adjust the pH to 7.0 so that the pH value shown in the table was obtained. The remaining water was added so that the total amount of the composition was 100% by mass, and the mixture was stirred at the rotation speed of the stirrer at 650 rpm for 1 minute to obtain a dishwasher detergent composition.
The pH (25 ° C.) of the composition was measured by measuring the composition adjusted to 25 ° C. using a glass electrode type pH meter (HM-30G, manufactured by DKK-TOA CORPORATION). The measuring method was carried out in accordance with JIS Z 8802: 1984 "pH measuring method".

<Evaluation of dishwasher detergent>
The compositions of each Example and Comparative Example were evaluated by the evaluation methods shown below, and the results are shown in the table.
As a dishwasher, an automatic dishwasher (manufactured by Panasonic Corporation, model NP-40SX2) was used. In each evaluation, the washing process was performed by operating in the standard course (power saving mode or normal mode) set in the automatic dishwasher. In the power saving mode, the water temperature in the washing step is set to be 15 ° C. lower than that in the normal mode. The contents of the standard course (power saving mode) are shown below.
・ Standard course (power saving mode):
After 2 to 6 g of the composition (for 3 L of tap water) is put into the automatic dishwasher, tap water of about 5 ° C. is introduced into the refrigerator to prepare a cleaning solution up to 40 ° C. at 2 to 3 ° C./min. Wash for 20 minutes while raising the temperature with, and drain the washing liquid. Next, fresh tap water is introduced, and rinsing (2 minutes / time) and drainage are repeated 3 times. After draining, introduce new tap water, rinse once (final rinse) for 20 minutes while raising the temperature to 70 ° C at 2-3 ° C / min, and after draining, dry the dishes etc. while circulating warm air. do.
-The standard course (normal mode) is the standard course (power saving mode), and the other operations of washing for 20 minutes while raising the cleaning liquid to 55 ° C at 2 to 3 ° C / min are the standard course (power saving mode). ).

<Evaluation of detergency against oil stains>
As oil stains, a mixed oil of beef tallow / lard / butter / salad oil = 3/3/3/1 (mass ratio) and retort curry (Bon Curry Gold 21 dry) were used.
A polypropylene lunch box (length 110 mm, width 170 mm, height 35 mm) contaminated by adhering 3 g of the mixed oil and 6 g of the retort curry to the entire surface is loaded into the automatic dishwasher, and 6 g of the composition is charged. The cleaning process was performed in the standard course (power saving mode).
After the cleaning treatment, the finished condition of the polypropylene lunch box was observed, and the detergency against oil stains was evaluated based on the following evaluation criteria. As the evaluation points shown in the table, the average value of three cleaning treatments was described, and if the value was 3 points or more, it was regarded as acceptable.
(Evaluation criteria)
4 points: Oil stains were completely removed.
3 points: Some oil stains remained, but it was at a level that did not need to be washed again.
2 points: Oil stains remained and it was a level that needed to be washed again.
1 point: Oil stains remained sticky.

<Evaluation of sterilizing power>
Before the evaluation, the inside of the automatic dishwasher was washed with a chlorine-based mold remover.
Based on the Better Living Association certified standard performance test method (enforced on November 6, 1995: dishwasher), tonkatsu for tableware such as chopsticks, glass cups, teacups, dishes (large, medium, small), soup bowls, etc. Dirty tableware was prepared by attaching juice, milk, miso soup, green tea, rice, raw eggs, curry, commercially available pork cutlet sauce, ham egg, and the like.
Next, the dirty tableware was stored in an automatic dishwasher after being washed with a chlorine-based mold remover, 2 to 6 g of the composition was added, and the washing treatment was performed in a standard course (power saving mode). When the washing water in the refrigerator reached about 60 ° C. after the start of washing, the door of the automatic dishwasher was opened and the water remaining in the refrigerator was collected to prepare a 10-fold dilution series diluted solution.
1.0 mL of each diluted solution was dispensed into a sterile petri dish, 15 to 20 mL of SCD agar medium at 45 to 48 ° C. was added, and the mixture was stirred well. The petri dish was covered and left at room temperature, and after the medium had solidified, the petri dish was inverted and cultured at a temperature of 37 ± 1 ° C. for 40 to 48 hours. After culturing, the number of colonies in the diluted petri dish in which 30 to 300 colonies appeared was measured, and the viable cell count (N) was determined from the following formula (I).
Viable cell count (cfu / mL) = colony count x 10 M x 10 ... (I)
In formula (I), "M" is the number of dilutions of the dilution series diluent dispensed into the adopted petri dish.
Separately, a sterilized 0.05 mass / volume% (w / v%) Tween 80 aqueous solution (manufactured by Kanto Chemical Co., Ltd., "Polysorbate 80") was used as a control detergent, and the same cleaning treatment was performed to extract bacteria. Then, a 10-fold dilution series diluted solution was prepared, and the number of colonies was measured to determine the viable cell count (N).
From the measured values of the viable cell count when treated with the dishwasher detergent composition and the viable cell count when treated with the control detergent, the activity value was calculated from the following formula (II) and used as the following evaluation criteria. Evaluated based on. An activity value of 2 or more was regarded as acceptable.
Activity value = log10N (number of viable bacteria when treated with a control detergent) -log10N (number of viable bacteria when treated with a dishwasher detergent composition) ... (II)

Examples 1 to 30 to which the present invention was applied were excellent in detergency and sterilizing power against oil stains.
Comparative Example 1 having a D / B ratio of more than 400 was inferior in detergency and sterilizing power against oil stains.
Comparative Example 2 having a D / B ratio of less than 0.05 was inferior in detergency and sterilizing power against oil stains.
Comparative Example 3 containing no component (B) was inferior in sterilizing power.
^{Comparative Example 4 in which R 1 in} the formula (b-1) of the component (B) is a methyl group having 1 carbon atom (does not contain the component (B)) was inferior in sterilizing power.
Comparative Example 5 containing no component (C) was inferior in sterilizing power.
Comparative Example 6 containing the quaternary ammonium salt-type surfactant of the component (d4) instead of the component (B) was inferior in sterilizing power.

Claims (5)

It contains (A) component, (B) component, (C) component, and (D) component.
The component (A) is an anionic surfactant, and the component (A) is an anionic surfactant.
The component (B) is a compound represented by the following formula (b-1).
The component (C) is a chelating agent.
The component (D) is an amine-type surfactant (d1) (excluding the component (B)), an amphoteric surfactant (d2), an amine oxide-type surfactant (d3), and a quaternary ammonium salt type. At least one selected from the group consisting of surfactant (d4),
A dishwasher detergent composition having a mass ratio of the component (D) / the component (B) of 0.05 to 400.
R ¹ −N ((CH ₂ ) _n NH ₂ ) ₂ ... (b-1)
(In the formula (b-1), R ¹ is a linear alkyl group having 8 to 18 carbon atoms, an alkyl group having a branched chain having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or carbon. It is an alkenyl group of the branched chain of the number 8-18; n is an integer of 2-6.) The component (D) contains the amine-type surfactant (d1), and the component (D) contains the amine-type surfactant (d1).
The detergent composition for a dishwasher according to claim 1, wherein the amine-type surfactant (d1) is a compound represented by the following formula (d-1).
R ² R ³ R ⁴ N ... (d-1)
(In formula (d-1), R ² , R ³ , and R ⁴ are substituents on N, and R ² is hydrogen, an alkyl group having 1 to 4 carbon atoms, and a hydroxyalkyl group having 1 to 4 carbon atoms. , An alkyl group having 8 to 21 carbon atoms, or an alkenyl group having 8 to 21 carbon atoms; R ³ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 4 carbon atoms, or 1 carbon group. be ~ 4 aminoalkyl group; ^{R 4} is an alkyl group having 8 to 21 carbon atoms, an alkenyl group having 8 to 21 carbon atoms, an aminoalkyl group having 1 to 4 carbon atoms, or ^R 5 -X- _(CH 2) _m - be a group represented by; ^{R 5} is a linear alkyl group of 8 to 21 carbon atoms, linear alkenyl group having 8 to 21 carbon atoms, branched chain alkyl group of 8 to 21 carbon atoms, or It is an alkenyl group of a branched chain having 8 to 21 carbon atoms; X is -O-, -C (O) NR ^6- , or -NH-; R ⁶ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms. , Or a hydroxyalkyl group having 1 to 4 carbon atoms; m is an integer of 1 to 5). The dishwasher detergent composition according to claim 1 or 2, wherein the mass ratio represented by the component (A) / [component (B) + component (D)] is 0.01 to 20. .. The dishwasher detergent composition according to any one of claims 1 to 3, wherein the total amount of the surfactant is 0.1 to 10% by mass with respect to the total mass of the dishwasher detergent composition. .. The dishwasher washing according to any one of claims 1 to 4, wherein the content of the component (C) is 8% by mass or more in terms of acid with respect to the total mass of the dishwasher cleaning agent composition. Agent composition.