JP2019172819A - Dishwashing detergent composition - Google Patents

Abstract

An object of the present invention is to provide a dishwashing detergent composition which is excellent in detergency and excellent in drainage even when diluted. A component (A): an anionic surfactant containing an alkylbenzene sulfonate (A1); a component (B): at least one selected from the group consisting of an amphoteric surfactant and an amine oxide surfactant. , (C) component: cationized cellulose, and (D) component: nonionic surfactant, wherein the content of component (A) is 10% by mass or more based on the total mass of the dishwashing detergent composition. The content of the component (A1) is 50% by mass or more based on the total mass of the component (A), and the content of magnesium ions is 0% based on the total mass of the dishwashing detergent composition. 0.02 to 0.60% by mass, and the (A + B) / D ratio is 1 to 10; [Selection diagram] None

Description

  The present invention relates to a dishwashing detergent composition.

As a method of washing dishes such as tableware and cooking utensils (hereinafter collectively referred to as “tableware”), the dishwashing detergent is directly applied to a washing tool such as a sponge, and the objects to be washed are rubbed with the washing tool. Examples thereof include a method, a method of diluting a dishwashing detergent with water, preparing a diluted solution, taking the diluted solution in a cleaning tool such as a sponge, and rubbing an object to be washed with the cleaning tool.
However, when cleaning is performed using a diluting solution, it is difficult to exert sufficient cleaning power because the concentration of the cleaning agent at the time of cleaning is low.
Moreover, the washing | cleaning agent for dishwashing requires the performance (water drainability) that the water adhering to a to-be-washed object cuts quickly, and to-be-washed object dries quickly.

  Patent Document 1 proposes a liquid detergent containing an α-sulfo fatty acid alkyl ester salt, an anionic surfactant other than the α-sulfo fatty acid alkyl ester salt, and an amphoteric surfactant. The liquid detergent of patent document 1 is excellent in detergency and is excellent in dilution dispersibility.

International Publication No. 2017/069017

  However, the liquid detergent disclosed in Patent Document 1 has not been studied for water drainage.

  This invention is made | formed in view of the said situation, Even if it is a case where it is diluted, it aims at providing the washing | cleaning composition for dishwashing which is excellent in detergency and is also excellent in drainage.

The dishwashing detergent composition of the present invention includes the following aspects.
[1] Including (A) component, (B) component, (C) component, and (D) component,
The component (A) is an anionic surfactant,
The component (B) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants,
The component (C) is cationized cellulose,
The component (D) is a nonionic surfactant;
The content of the component (A) is 10% by mass or more based on the total mass of the dishwashing detergent composition,
The component (A) contains an alkylbenzene sulfonate (A1),
The content of the component (A1) is 50% by mass or more based on the total mass of the component (A),
The magnesium ion content is 0.02 to 0.60% by mass relative to the total mass of the dishwashing detergent composition,
The dishwashing detergent composition whose mass ratio represented by [the said (A) component + said (B) component] / (D) component is 1-10.
[2] The dishwashing detergent composition according to [1], wherein the component (B) is the amphoteric surfactant.
[3] The dishwashing detergent composition according to [1] or [2], wherein the mass ratio represented by the component (A) / the component (B) is 2 to 80.
[4] The component (D) contains a polyoxyalkylene type nonionic surfactant having a polyoxyalkylene group, and the content of the polyoxyalkylene group is an average per molecule of the polyoxyalkylene type nonionic surfactant. The dishwashing detergent composition according to any one of [1] to [3], which is 50 to 99% by mass.
[5] For dishwashing according to any one of [1] to [4], wherein a mass ratio represented by [the component (A) + the component (B)] / the magnesium ion is 20 to 800. Cleaning composition.
[6] As described in any one of [1] to [5], the component (A) contains an ether sulfate type anionic surfactant (A2) represented by the following formula (AI). A dishwashing detergent composition.
^{_{R 1 -O - [(PO)}} m / (EO) n] -SO 3 - 1 / X · M + ··· (A-I)
(In the formula (AI), R ¹ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; Represents the number of repetitions, 0 ≦ m ≦ 1, n represents the average number of repetitions of EO, 0 ≦ n ≦ 5; in [(PO) _m / (EO) _n ], EO and PO are randomly added And may be a block addition; M ⁺ is a counter ion; X is the valence of M ⁺ .)
[7] The component (A2) includes an alkyl sulfate ester type anionic surfactant (A3) in which m is 0 and n is 0 in the formula (AI),
The dishwashing detergent composition according to [6], wherein the content of the component (A3) is 30% by mass or more based on the total mass of the component (A2).

  The dishwashing detergent composition of the present invention is excellent in detergency and drainage even when diluted.

≪Dishwashing detergent composition≫
The dishwashing detergent composition of the present invention is a liquid containing a component (A), a component (B), a component (C), a component (D), and magnesium ions.

<(A) component>
The component (A) is an anionic surfactant. (A) As a component, the well-known anionic surfactant used for the dishwashing detergent can be used.
(A) A component contains the alkylbenzene sulfonate (A1). The alkyl group of component (A1) may be linear or branched. (A1) As for carbon number of the alkyl group of a component, 8-18 are preferable and 12-14 are more preferable. Examples of the salt form of the component (A1) include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as magnesium; alkanolamine salts such as monoethanolammonium and diethanolammonium.

The component (A) preferably contains an ether sulfate type anionic surfactant (A2) represented by the following formula (AI).
^{_{R 1 -O - [(PO)}} m / (EO) n] -SO 3 - 1 / X · M + ··· (A-I)
(In the formula (AI), R ¹ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; Represents the number of repetitions, 0 ≦ m ≦ 1, n represents the average number of repetitions of EO, 0 ≦ n ≦ 5; in [(PO) _m / (EO) _n ], EO and PO are randomly added And may be a block addition; M ⁺ is a counter ion; X is the valence of M ⁺ .)

  The component (A2) preferably contains an alkyl sulfate anionic surfactant (A3) in which m is 0 and n is 0 in the formula (AI). Examples of the component (A3) include linear alkyl (C12) sulfate ester salts, linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate ester salts, and the like.

  In the formula (AI), at least one of m and n is 1 or more, and the ether sulfate type anionic surfactant is polyoxyethylene (average number of repetitions 1) linear alkyl (C12) sodium ether sulfate. Salt, polyoxyethylene (average number of repetitions 2) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (average number of repetitions 4) linear alkyl (C12) ether sulfate sodium salt, polyoxypropylene (average number of repetitions 0) .4) Polyoxyethylene (average repetition number 1.5) linear alkyl (C12) ether sulfate sodium salt, polyoxyethylene (average repetition number 1) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Sodium ether sulfate, polyoxyethylene (average number of repetitions 2) linear alkyl ( 12/14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt, polyoxyethylene (average number of repetitions 4) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt, polyoxypropylene (Average 0.4) polyoxyethylene (average number of repetitions 1.5) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ether sulfate sodium salt and the like.

Moreover, the (A2) component generally used is manufactured and used as a mixture containing the (A3) component.
For example, in the case of polyoxyethylene (average number of repetitions 1) linear alkyl (C12) ether sulfate sodium salt, a compound having an average number of repetitions of oxyethylene groups of 0 (corresponding to the component (A3)) is about 35 to 55. It is preferably used as a compound containing mass%. In the case of polyoxyethylene (average number of repetitions 2) linear alkyl (C12) ether sulfate sodium salt, about 20 to 40% by mass of a compound having an average number of oxyethylene group repetitions of 0 (corresponding to component (A3)) It is preferably used as a compound containing.

M ⁺ is a counter ion. For example, any ion that is an alkali metal, alkaline earth metal, ammonium, or alkanolamine ion that can form a water-soluble salt may be used. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium, magnesium, and zinc. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
X is the valence of M ⁺ and is preferably 1 to 2.

(A) A component may be used individually by 1 type and may use 2 or more types together.
(A) Content of a component is 10 mass% or more with respect to the total mass of the detergent composition for dishwashing, 11-20 mass% is preferable, 12-18 mass% is more preferable, 13-16 mass % Is more preferable.
When the content of the component (A) is equal to or less than the above upper limit value, it becomes easy to improve drainage.
When the content of the component (A) is equal to or higher than the lower limit, it is easy to improve the cleaning power.

Content of (A1) component is 50 mass% or more with respect to the total mass of (A) component, 60-100 mass% is preferable and 70-90 mass% is more preferable.
When the content of the component (A1) is equal to or less than the above upper limit value, it becomes easy to improve drainage.
When the content of the component (A1) is equal to or higher than the lower limit, it is easy to improve the cleaning power.

0-50 mass% is preferable with respect to the total mass of (A) component, and, as for content of (A2) component, 20-60 mass% is more preferable.
When the content of the component (A2) is equal to or lower than the above upper limit value, the cleaning power is easily improved.
When the content of the component (A2) is equal to or more than the lower limit value, it becomes easy to improve drainage.

1-20 are preferable and, as for mass ratio (henceforth "A1 / A2 ratio") represented by (A1) component / (A2) component, 3-18 are more preferable.
When the A1 / A2 ratio is less than or equal to the above upper limit value, it becomes easy to improve water drainage.
When the A1 / A2 ratio is equal to or higher than the lower limit, it is easy to improve the cleaning power.

  The content of the component (A3) is preferably 30% by mass or more, more preferably 50 to 95% by mass, and particularly preferably 65 to 90% by mass with respect to the total mass of the component (A2). Within the above range, it is easy to improve detergency and drainage.

<(B) component>
The component (B) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants.
Examples of the amphoteric surfactant include a carboxylate salt type, a sulfate ester salt type, a sulfonate salt type, and a phosphate ester salt type, and a carboxylate salt type amphoteric surfactant is preferable.
Specific examples of the carboxylate type amphoteric surfactant include lauryl dimethylaminoacetic acid betaine, coconut alkyldimethylaminoacetic acid betaine, coconut oil fatty acid amidepropylbetaine, lauric acid amidepropyldimethylaminoacetic acid betaine, coconut alkylamidopropyldimethylamino Examples include betaine-type amphoteric surfactants such as betaine acetate.
As the amphoteric surfactant, a compound represented by the following general formula (BI) is preferably used.
_{^{R 2 - (A) p -N}} + (-R 3) (- R 4) -R 5 -R 6 ... (B-I)
(In formula (BI), R ² represents a linear or branched alkyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group or hydroxyalkyl having 1 to 3 carbon atoms. Represents a group, A represents —C═O (—NH—X) —, X represents an alkylene group having 1 to 4 carbon atoms, p is a number of 0 or 1, and R ⁵ represents 1 to C 1 carbon atoms. 2 represents an alkylene group, and R ⁶ represents —CO ₂ ^— or —SO ₃ ^— .)

  Examples of amine oxide surfactants include alkylamine oxide and alkanoylamide alkylamine oxide. Of these, preferred are compounds represented by the following formula (B-II).

In the formula (B-II), R ¹⁰ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or A branched alkenyl group having 8 to 18 carbon atoms, and R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; ⁹ is an alkylene group having 1 to 4 carbon atoms, B is —CONH—, —NHCO—, —COO—, —OCO— or —O—, and r is a number of 0 or 1.

In the alkyl group and alkenyl group of R ¹⁰ , the carbon number is 8 to 18, and preferably 10 to 14.
R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. . R ⁷ and R ⁸ are more preferably both methyl groups.
r is a number of 0 or 1, and 0 is preferable.

Specific examples of the amine oxide surfactant include lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide, lauryl diethyl amine oxide, and alkyl dimethyl amine oxides such as n-dodecyl dimethyl amine oxide; lauric acid amide propyl amine oxide, etc. And alkanoylamidoalkyldimethylamine oxides. Of these, alkyldimethylamine oxides are more preferable.
Component (B) is preferably an amphoteric surfactant from the viewpoint of drainage and detergency.

(B) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (B) is preferably 0.1 to 10% by mass, more preferably 0.2 to 8% by mass, and 0.3 to 6% by mass with respect to the total mass of the dishwashing detergent composition. Is more preferable.
When the content of the component (B) is within the above range, it is easy to improve the cleaning power and drainage.

2-80 are preferable and, as for mass ratio (henceforth "A / B ratio") represented by (A) component / (B) component, 10-50 are more preferable.
When the A / B ratio is within the above range, it becomes easy to improve drainage and detergency.

<(C) component>
Component (C) is cationized cellulose.
As the component (C), a compound represented by the following general formula (CI), a compound represented by the following general formula (C-II), a compound represented by the following general formula (C-III), etc. Is mentioned.

In the general formula (CI), n represents the average number of repetitions, and the average molecular weight of the compound is preferably 10,000 to several million.
In the general formula (C-II), v and w represent the average number of repetitions, and the average molecular weight of the compound is preferably 10,000 to several hundred thousand.
In general formula (C-III), u represents the average number of repetitions, and the average molecular weight of the compound is preferably 10,000 to several hundred thousand.

  The cationization degree of the component (C) is preferably 0.5 to 3.5% by mass, and more preferably 0.8 to 1.3% by mass. If the degree of cationization is within the above range, the water drainage property is further increased. Here, “cationization degree” means the content (% by mass) of nitrogen atoms derived from the cationizing agent in the cationized cellulose molecule, that is, the content of nitrogen atoms relative to the total mass of the cationized cellulose. Means. The degree of cationization of the cationized cellulose is calculated based on the identified chemical structure. When the chemical structure of cationized cellulose is not specified, such as when the ratio of any monomer in cationized cellulose is unknown, the degree of cationization is calculated from the nitrogen content determined experimentally. Examples of the method for measuring the nitrogen content in cationized cellulose include the Kjeldahl method.

1000-5000 mPa * s is preferable, as for the viscosity of the 1 mass% aqueous solution of (C) component in 25 degreeC, 2000-3000 mPa * s is more preferable, 2500-3000 mPa * s is further more preferable. If the viscosity of the 1% by weight aqueous solution of the component (C) is within the above range, it is more excellent in water drainability at the time of washing at a low concentration. The viscosity is a value obtained by measuring a 1% by mass aqueous solution of cationized cellulose at 25 ° C. with a B-type viscometer. Viscosity measurement conditions are as follows.
Measurement condition:
[rotor]
The rotor number and rotor rotation speed corresponding to the viscosity of the measurement object are as follows.
・ Viscosity is less than 500 mPa · s: Rotor No. 2. Rotation speed 60rpm.
・ Viscosity of 500 mPa · s or more and less than 2000 mPa · s: Rotor No. 3. Rotation speed 60rpm.
・ Viscosity is 2000 mPa · s or more and less than 10000 mPa · s: Rotor No. 4, 60 rpm.
・ Viscosity is 10000 mPa · s or more and less than 50000 mPa · s: Rotor No. 4, rotation speed 12rpm.
[Read numerical values]
60 seconds after the rotor starts rotating.

  Examples of the component (C) include a trade name “Leogard GP (quaternary nitrogen content 1.8% by mass, manufactured by Lion Specialty Chemicals)”, and a trade name “Leogard MGP (quaternary nitrogen content). 1.8% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.), product name “Leoguard MLP (quaternary nitrogen content 0.6% by mass, manufactured by Lion Specialty Chemicals Co., Ltd.)”, product name “UCARE JR125 (quaternary nitrogen content 1.9% by mass, hydrophobic substitution index 0, manufactured by Dow Chemical Co., Ltd.), trade name “UCARE JR400 (quaternary nitrogen content 1.9% by mass, hydrophobic substitution index 0, Dow Chemical Co., Ltd.), trade name “UCARE LR30M (quaternary nitrogen content 1.0 mass%, hydrophobic substitution index 0, Dow Chemical Co., Ltd.)”, trade name “SO TCAT SL-5 (quaternary nitrogen content 0.95 mass%, hydrophobic substitution index 5, manufactured by Dow Chemical Co., Ltd.), trade name “SOFT CAT SL-30 (quaternary nitrogen content 0.95 mass) %, Hydrophobic substitution index 30, manufactured by Dow Chemical Co., Ltd.), trade name “SOFT CAT SL-60 (quaternary nitrogen content 0.95 mass%, hydrophobic substitution index 60, manufactured by Dow Chemical Co., Ltd.)”, product Name “SOFT CAT SL-100 (quaternary nitrogen content 0.95 mass%, hydrophobic substitution index 100, manufactured by Dow Chemical Co.)”, trade name “SOFT CAT SX-400H (quaternary nitrogen content 2. 5% by mass, hydrophobic substitution index 30, manufactured by Dow Chemical Co., Ltd.) ”, trade name“ SOFT CAT SX-1300H (quaternary nitrogen content 2.5% by mass, hydrophobic substitution index 45, manufactured by Dow Chemical Company) ” ,Product name" OFC CAT SX-400X (quaternary nitrogen content 2.1 mass%, hydrophobic substitution index 30, manufactured by Dow Chemical Co., Ltd.), trade name “SOFT CAT SX-1300X (quaternary nitrogen content 2.1 mass) %, Hydrophobic substitution index 45, manufactured by Dow Chemical Co., Ltd.). Among these, “SOFT CAT SL-5”, “SOFT CAT SL-30”, “SOFT CAT SL-60”, “SOFT CAT SL-100”, “SOFT CAT SX-” having a high hydrophobic substitution index from the viewpoint of drainage performance. 400H "," SOFT CAT SX-1300H "," SOFT CAT SX-400X ", and" SOFT CAT SX-1300X "are more preferable.

(C) A component may be used individually by 1 type and may use 2 or more types together.
(C) 0.05-1.5 mass% is preferable with respect to the total mass of the detergent composition for dishwashing, and, as for content of a component, 0.1-1.0 mass% is more preferable.
(C) It is easy to improve usability as content of a component is below the above-mentioned upper limit.
When the content of the component (C) is equal to or higher than the lower limit, it is easy to improve water drainage.

<(D) component>
Component (D) is a nonionic surfactant.
As the component (D), polyoxyalkylene type nonionic surfactant, alkylphenol, alkylene oxide adduct such as higher amine, polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or The alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester such as sorbitan fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, etc. Can be mentioned.

Among the above, the nonionic surfactant is preferably a polyoxyalkylene type nonionic surfactant in terms of drainage.
Examples of the polyoxyalkylene-type nonionic surfactant include a compound represented by the following general formula (DI) (hereinafter sometimes referred to as “compound (DI)”).
^{_{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (D-I)

In the formula (DI), R ¹¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 2 to 6 alkenyl groups, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average number of repetitions of EO, is a number of 3 to 100, and t is an average number of repetitions of PO Represents a number from 0 to 6.

In formula (DI), the carbon number of the hydrocarbon group for R ¹¹ is 6 to 22, preferably 8 to 22, and more preferably 10 to 18. The hydrocarbon group for R ¹¹ may be linear or branched, and may or may not have an unsaturated bond.
Examples of —X— include —O—, —COO—, —CONH— and the like.
The number of carbon atoms of the alkyl group in R ¹² is 1 to 6, 1 to 3 are preferred.
The number of carbon atoms of the alkenyl group for R ¹² is 2-6, preferably 2-3.

The compound (DI) in which —X— is —O—, —COO— or —CONH— is a primary or secondary higher alcohol (R ¹¹ —OH) or higher fatty acid (R ¹¹ —COOH). Alternatively, a higher fatty acid amide (R ¹¹ —CONH) is obtained as a raw material. ^{R 11} in these raw materials is the same as ^{R 11} in formula (D-I).

s is the number of 3-100 showing the average repeating number (namely, average addition mole number of ethylene oxide) of EO, and 5-50 are preferable. If the value exceeds the upper limit, the HLB value becomes too high, and the cleaning power against oil stains may be reduced. If it is less than the said lower limit, there exists a possibility of producing deterioration of the raw material odor of (D) component itself.
t is a number from 0 to 6 that represents the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), preferably 0 to 3, and more preferably 0 to 1. If it exceeds the above upper limit, the liquid stability of the cleaning composition at a high temperature tends to decrease.

  When t is 1 or more, that is, when the compound (DI) has EO and PO, the addition method of ethylene oxide and propylene oxide is not particularly limited, and for example, a random addition method or a block addition method may be used. Block addition methods include, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding propylene oxide after adding propylene oxide, a method of adding ethylene oxide, adding propylene oxide, and then adding ethylene oxide. The method of doing is mentioned.

Examples of the compound (D-I), in particular, compounds -X- is -O- (alcohol type nonionic surface active agents), or a -X- is ^{-COO-, R 12} is 1 to 6 carbon atoms And a compound (fatty acid alkyl (alkenyl) ester) which is an alkyl group or an alkenyl group having 2 to 6 carbon atoms is preferred.

If -X- is ^-O-, and the carbon number of ^{R 11} is preferably 10 to 22, more preferably from 10 to 20, more preferably 10 to 18. When -X- is -O-, R ¹² is preferably a hydrogen atom.

If -X- is ^-COO-, the carbon number of ^{R 11} is preferably 9 to 21, 11 to 21 is more preferable. When -X- is -COO-, R ¹² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

  As the compound (DI) in which -X- is -O- or -COO-, for example, Diadol (trade name, C13 (C represents the number of carbon atoms; hereinafter the same)) manufactured by Mitsubishi Chemical Corporation. 12 mol equivalent or 15 mol equivalent of ethylene oxide with respect to alcohol such as Neodol (trade name, mixture of C12 and C13) manufactured by Shell, Safol 23 (trade name, mixture of C12 and C13) manufactured by Sasol Added: Protter & Gamble CO-1214 or CO-1270 (trade name) or other natural alcohol added with 12 mol equivalent or 15 mol equivalent ethylene oxide; Butene trimerized 7 mol equivalent of ethylene oxide was added to C13 alcohol obtained by subjecting the C12 alkene obtained in this way to the oxo process. (Trade name: Lutensol TO7, manufactured by BASF); 9 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mole equivalent ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XL70, manufactured by BASF); C10 alcohol obtained by subjecting pentanol to garvet reaction In contrast, 6 mole equivalent of ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 5 mole equivalent, 7 mole equivalent or 9 mole equivalent or a secondary alcohol having 12 to 14 carbon atoms Ethyleneoxy equivalent to 15 moles (Product names: Softanol 50, Softanol 70, Softanol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.); Palm fatty acid methyl (lauric acid / myristic acid = 8/2), alkoxyl And the like (polyoxyethylene coconut fatty acid methyl ester (EO 15 mol)) to which 15 mol of ethylene oxide has been added using an oxidization catalyst.

Especially, as (D) component, the compound represented by the following general formula (D-II) is preferable.
R ¹³ —O— (EO) _n —H (D-II)
In Formula (D-II), R ¹³ represents a linear or branched alkyl group having 8 to 18 carbon atoms, EO represents an oxyethylene group, n represents an average number of repeating EO, and 5 ≦ n ≦ 100.
In the formula (D-II), n is 5 ≦ n ≦ 100, and preferably 10 ≦ n ≦ 25.
When n is within the above range, it is easy to improve detergency and drainage.

When the component (D) includes a polyoxyalkylene type nonionic surfactant, the content of the polyoxyalkylene group is preferably 50 to 99% by mass per molecule of the polyoxyalkylene type nonionic surfactant. -98 mass% is more preferable, and 70-90 mass% is further more preferable.
When the average content of the polyoxyalkylene group per molecule of the polyoxyalkylene type nonionic surfactant is within the above range, the detergency and water drainage can be easily improved.

(D) A component may be used individually by 1 type and may use 2 or more types together.
(D) As for content of a component, 1-10 mass% is preferable with respect to the total mass of the detergent composition for dishwashing, and 2-9 mass% is more preferable.
(D) It is easy to improve detergency that content of a component is below the said upper limit.
When the content of the component (D) is equal to or more than the above lower limit value, it is easy to improve drainage.

The mass ratio represented by [(A) component + (B) component] / (D) component (hereinafter also referred to as “(A + B) / D ratio”) is 1 to 10, preferably 1.5 to 7. 3 to 7 are more preferable.
When the (A + B) / D ratio is less than or equal to the above upper limit value, it is easy to improve drainage.
When the (A + B) / D ratio is equal to or higher than the above lower limit value, it is easy to improve the cleaning power.

The total of the component (A), the component (B), and the component (D) (hereinafter also referred to as “A + B + D”) is preferably 10 to 30% by mass relative to the total mass of the dishwashing detergent composition. 25 mass% is more preferable, and 18-21 mass% is further more preferable.
When A + B + D is within the above range, it is easy to improve the cleaning power.

<Magnesium ion>
The dishwashing detergent composition of the present invention contains magnesium ions.
Magnesium ions may be included in the dishwashing detergent composition by using a magnesium salt as the component (A) or adding a magnesium inorganic salt (hereinafter also referred to as the component (E)). it can.
Examples of the magnesium salt of component (A) include alkylbenzene sulfonic acid 1/2 magnesium salt, polyoxyethylene alkyl ether sulfate 1/2 magnesium salt, alkyl ether magnesium sulfate, and the like.
Examples of the component (E) include magnesium chloride, magnesium sulfate, magnesium nitrate, and magnesium phosphate. Of these, magnesium sulfate is preferable.

In addition, content of the magnesium ion contained in the cleaning composition for dishwashing of this invention can be calculated | required as follows. For example, when using magnesium sulfate 7 hydrate (MgSO ₄ .7H ₂ O), the content (mass%) of magnesium ion (Mg) is {[Mg atomic weight: 24] / [magnesium sulfate 7 water]. Molecular weight of Japanese product: 246]} × 100 = 9.8% by mass, and can be easily calculated from the amount of magnesium sulfate heptahydrate blended in the dishwashing detergent composition. The content of the composition can also be measured using a conventional method such as high frequency inductively coupled plasma emission spectroscopy.

The content of magnesium ions is 0.02 to 0.60 mass%, preferably 0.10 to 0.40 mass%, based on the total mass of the dishwashing detergent composition.
When the magnesium ion content is not more than the above upper limit value, it becomes easy to improve drainage.
When the content of magnesium ions is not less than the above lower limit, the cleaning power is easily improved.

  When the detergent composition for dishwashing of this invention contains (E) component, 0.1-10 mass% is preferable, as for content of (E) component, 0.2-8 mass% is more preferable, and 0.2. 2-6 mass% is further more preferable.

The mass ratio represented by [(A) component + (B) component] / magnesium ions (hereinafter also referred to as “(A + B) / Mg ²⁺ ratio”) is preferably 20-800, more preferably 20-320, and 50 -150 is more preferable.
When the (A + B) / Mg ²⁺ ratio is within the above range, the cleaning power and water drainage are easily improved.

<Other ingredients>
The dishwashing detergent composition of the present invention may contain optional components other than the components (A) to (D). The type and amount of the optional component are not particularly limited as long as they do not impair the gist of the present invention, and components blended in known dishwashing detergents can be applied. Examples of such optional components include surfactants (arbitrary surfactants) other than the components (A) to (D), hydrotropes, preservatives, pH adjusters, disinfecting components, bleaching components, and metal capture agents. Ingredients, radical trapping agents, fragrances, water, pigments and the like can be mentioned.

[Hydrotrope]
The dishwashing detergent composition of the present invention comprises at least one hydrotrope selected from the group consisting of toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt, benzoic acid, benzoic acid salt and ethanol. Furthermore, it is preferable to contain. By containing a hydrotrope agent, the storage stability (especially low temperature stability) of the dishwashing detergent composition is mainly improved, and it becomes easier to ensure a more stable transparent appearance. In the hydrotrope, toluenesulfonic acid, toluenesulfonic acid salt, cumenesulfonic acid, cumenesulfonic acid salt may be any of the three isomers, o-form, m-form, and p-form, and these are easily available. The p-form is preferable because it is possible, and among them, p-toluenesulfonic acid and p-toluenesulfonate are more preferable.
A hydrotrope agent may be used individually by 1 type, and may use 2 or more types together.
When the dishwashing detergent composition of the present invention contains a hydrotrope agent, the content of the hydrotrope agent is preferably 0.1 to 10% by mass relative to the total mass of the dishwashing detergent composition, 0.2 -5 mass% is more preferable. When the content of the hydrotrope is within the above range, the blending effect can be obtained without deteriorating the cleaning power and drainage.

[Preservative]
The dishwashing detergent composition of the present invention preferably further contains an isothiazoline-based compound as a preservative. By containing the isothiazoline-based compound, even when microorganisms are mixed into the composition, the growth of the bacteria can be suppressed and the composition can be used safely.
Examples of the isothiazoline-based compounds include benzisothiazolinone, methylisothiazolinone, butylbenzisothiazolinone, chloromethylisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone and the like.
A preservative may be used individually by 1 type and may use 2 or more types together.
The content of the preservative is preferably 0.0002 to 0.05 mass% (2 to 500 ppm), preferably 0.001 to 0.03 mass% (10 to 300 ppm) with respect to the total mass of the dishwashing detergent composition. Is more preferable.

[PH adjuster]
Although it does not specifically limit as a pH adjuster, Organic acids, such as inorganic acids, such as hydrochloric acid and a sulfuric acid, acetic acid, a citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid, maleic acid, p-toluenesulfonic acid Acid agents selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and derivatives thereof, monoethanolamine, diethanolamine, triethanolamine, N-methylpropanol, 2-amino-2-methyl-1- It is preferable to use an alkali agent selected from propanol, N- (β-aminoethyl) ethanolamine, diethylenetriamine, morpholine, N-ethylmorpholine, etc., and an acid agent selected from hydrochloric acid, sulfuric acid, citric acid, sodium hydroxide, water It is more preferable to use an alkaline agent selected from potassium oxide. There.
A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

[Disinfecting ingredients]
Suitable examples of the disinfecting component include zinc compounds such as zinc sulfate, zinc oxide and zinc hydroxide. Of these, zinc sulfate and zinc oxide are more preferable, and zinc sulfate is particularly preferable.
The disinfecting component may be used alone or in combination of two or more.
The total amount of the components contained in the dishwashing detergent composition of the present invention does not exceed 100% by mass.

[PH]
The pH at 25 ° C. of the dishwashing detergent composition of the present invention is preferably from 4 to 8, more preferably from 4 to 5.5, from the viewpoint of improving the detergency and drainage.
In this invention, pH (25 degreeC) of the cleaning composition for dishwashing shows the value measured by the method based on JISZ8802: 1984 "pH measuring method".

[viscosity]
As a dishwashing detergent composition, a highly viscous dishwashing detergent composition may be preferred. This is because the high viscosity makes the image of the high cleaning power of the dishwashing detergent composition. However, when the viscosity is too high, the usability is deteriorated due to a decrease in dischargeability. Accordingly, the viscosity of the dishwashing detergent composition is preferably 500 to 10,000 mPa · s, and more preferably 1000 to 5000 mPa · s.
The viscosity is a value obtained by measuring a dishwashing detergent composition at 25 ° C. with a B-type viscometer. Viscosity measurement conditions are as follows.
Measurement condition:
[rotor]
The rotor number and rotor rotation speed corresponding to the viscosity of the measurement object are as follows.
・ Viscosity is less than 500 mPa · s: Rotor No. 2. Rotation speed 60rpm.
・ Viscosity of 500 mPa · s or more and less than 2000 mPa · s: Rotor No. 3. Rotation speed 60rpm.
・ Viscosity is 2000 mPa · s or more and less than 10000 mPa · s: Rotor No. 4, 60 rpm.
・ Viscosity is 10000 mPa · s or more and less than 50000 mPa · s: Rotor No. 4, rotation speed 12rpm.
[Read numerical values]
60 seconds after the rotor starts rotating.

≪Manufacturing method≫
It does not restrict | limit especially as a manufacturing method of the detergent composition for dishwashing. For example, it is manufactured by mixing the components (A) to (D), water as a solvent, and the component (E) and optional components as necessary.

≪How to use≫
When washing kitchen utensils using the dishwashing detergent composition of the present invention, the dishwashing detergent composition of the present invention may be diluted with water or used without being diluted with water. May be. The dishwashing detergent composition of the present invention is excellent in detergency and drainage even when diluted with water. Therefore, it is particularly suitably used as a dishwashing detergent diluted with water.
When the dishwashing detergent composition of the present invention is used after being diluted with water, it is preferable to use 5 to 15 g of the dishwashing detergent composition of the present invention dissolved in 1 L of water.
When the dishwashing detergent composition of the present invention is used without being diluted, it is preferably used by taking about 1 to 10 g in a cleaning tool such as a sponge.
The dishwashing detergent composition of the present invention can be used for washing dishes such as chopsticks, forks and dishes, and cooking utensils such as pans and kitchen knives.

  Hereinafter, the present invention will be described in more detail using 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 amount in terms of pure content.
A blank in the table indicates that the component is not blended.
“Balance” means that water is blended so that the total blending amount (mass%) of all blending components contained in the composition of each example is 100 mass%.
Below, the component shown in the table | surface is demonstrated.

<(A) component>
A-1: LAS, linear alkyl (carbon number 12-14) sodium benzenesulfonate (trade name Rypon LS-250, Lion Specialty Chemicals, Inc.), (A1) component.
A-2: AES (2), polyoxyethylene (average number of repetitions 2), linear alkyl (C12 / 14 = 75/25) sodium ether sulfate (trade name Sinoline SPE-1250, Shin Nippon Rika Co., Ltd.) (A2) component which contains 25 mass% of (A3) component of the repeating number 0 of polyoxyethylene.
A-3: SLS, sodium linear alkyl (C12) sulfate ester (trade name SANNOL LM-1130, Lion Specialty Chemicals Co., Ltd.), (A3) component.

<(B) component>
B-1: CAPB, coconut oil fatty acid amidopropyl betaine (trade name NIKKOL AM-313ON, Nikko Chemicals Corporation). In formula (BI), R ² is an alkyl group having 11 to 15 carbon atoms, A is —C═O (—NH—X —) —, and X is — (CH ₂ ) ₃ —. , R ³ is a methyl group, R ⁴ is a methyl group, p is 1, R ⁵ is —CH ₂ —, and R ⁶ is —CO ₂ ^— .
B-2: APAX, lauric acid amidopropyl dimethylamine oxide (trade name GENAMINOX AP, Clariant Japan Co., Ltd.). In Formula (B-II), R ¹⁰ is an alkyl group having 11 to 15 carbon atoms, B is —CONH—, R ⁹ is an alkylene group having 3 carbon atoms, and R ⁷ is a methyl group. A compound in which R ⁸ is a methyl group and r is 1.
B-3: AX, n-dodecyldimethylamine oxide (Cadenax DM12D-W, Lion Specialty Chemicals). In the formula (B-II), compounds wherein R ¹⁰ is a dodecyl group, r is 0, R ⁷ is a methyl group, and R ⁸ is a methyl group.

<(C) component>
C-1: SL-100, cationized cellulose (nitrogen content 0.8 to 1.1% by mass, hydrophobic substitution index 100) (trade name SOFT CAT SL-100, Dow Chemical Company).
-C-2: SL-30, cationized cellulose (nitrogen content 0.8-1.1 mass%, hydrophobic substitution index 30) (trade name SOFT CAT SL-30, Dow Chemical Company).
C-3: SX-400H, cationized cellulose (nitrogen content 2.4 to 2.6% by mass, hydrophobic substitution index 30) (trade name SOFT CAT SX-400H, Dow Chemical Company).

<(D) component>
D-1: BRE (100), polyoxyethylene (average number of repetitions 100) alkyl (straight chain C12) ether (trade name: Nonion K2100-W, NOF Corporation). The average content of polyoxyethylene is 96.4% by mass.
D-2, BRE (15) Polyoxyethylene (average number of repetitions 15) alkyl (linear C12 / 14 = 75/25) ether (trade name LMAO-90, Lion Specialty Chemicals Co., Ltd.) of polyoxyethylene Average content 79.3 mass%.
D-3: BRE (5), polyoxyethylene (average number of repetitions 5) alkyl ether (straight chain C12) (trade name EMALEX 705, Nippon Emulsion Co., Ltd.) Polyoxyethylene content 57 mass%.
D-4: APG, alkyl (C8-10) polyglucoside (trade name: GLUCOPON 215UP, Cognis Japan Co., Ltd.) Polyoxyethylene content 0 mass%.

<(E) component>
E-1: MgSO ₄ .7H ₂ O, magnesium sulfate heptahydrate (trade name magnesium sulfate heptahydrate, Kanto Chemical Co., Inc.).
E′-1: Zinc sulfate monohydrate (trade name: Zinc sulfate monohydrate, Kanto Chemical Co., Inc.).

<Optional component>
-Ethanol: Ethanol (trade name Ethyl Alcohol Fermentable Traceable 95 Grade 1 Nippon Alcohol Sangyo Co., Ltd.).
・ Trisodium citrate (trade name: Trisodium citrate, Kanto Chemical Co., Inc.)
-Zinc sulfate monohydrate (trade name: Zinc sulfate monohydrate, Kanto Chemical Co., Inc.).
-Water: Ion exchange water.
・ PH adjuster: 1N sulfuric acid (Pure Chemical Co., Ltd.), 1N sodium hydroxide aqueous solution (Pure Chemical Co., Ltd.)

<Preparation of dishwashing detergent composition>
1000 g of a dishwashing detergent composition having the composition shown in the table was prepared by the following procedure.
(A) component, (B) component, (D) component, (E) component and 300 g of ion-exchanged water were put into a 1 L beaker and sufficiently stirred with a three-one motor (product name: FBL600, manufactured by Shinto Scientific Co., Ltd.). . Next, the component (C) and an optional component were added and sufficiently stirred.
After adding an appropriate amount of pH adjuster so that the pH at 25 ° C. is 4.7, add ion-exchanged water so that the total amount becomes 1000 g, and stir until uniform to obtain a dishwashing detergent composition. Obtained.
The pH (25 ° C.) of the dishwashing detergent composition was adjusted to 25 ° C. using a glass electrode type pH meter (trade name “HM-30G” manufactured by Toa DKK Corporation). The glass electrode was directly immersed in the dishwashing detergent composition, and the pH indicated after 1 minute was measured. The measuring method was performed according to JIS Z 8802: 1984 “pH measuring method”.
About the obtained dishwashing detergent composition of each example, the drainage property and the cleaning power were evaluated as follows.

<Evaluation of drainability>
A ceramic dish having a diameter of 18.5 cm uniformly coated with 0.25 g of beef tallow (manufactured by Kanto Chemical Co., Ltd.) was used as the item to be washed.
The dishwashing detergent composition of each example was diluted with water to prepare 500 ml of a 1.25% by weight diluted solution.
A 11.5 cm × 7.5 cm × 3 cm dishwashing sponge (trade name: Scotch Bright, manufactured by Sumitomo 3M Limited) was immersed in 500 ml of the diluent, and 40 g of the diluent was attached to the sponge. After the sponge was rubbed by hand 5 times, the surface of one ceramic dish was rubbed 10 times, and the ceramic dish was thoroughly rinsed with running water (tap water). The same sponge was dipped again in the same pot, and another dish was washed in the same manner as described above. The above operation was repeated to wash a total of 5 dishes. A fifth plate was stood vertically, and the time for 100% of the water on the plate to flow down was evaluated. Evaluation was performed according to the following evaluation criteria. ○, ◎, ◎◎ are acceptable.
[Evaluation criteria]
A: 100% drainage time is 60 seconds or less.
A: 100% drainage time exceeds 60 seconds and is 120 seconds or less.
○: 100% drainage time exceeds 120 seconds and is 180 seconds or less.
X: 100% drainage time exceeds 180 seconds.

<Evaluation of cleaning power>
Margarine (trade name for VITA, manufactured by PT BINA KARYA PRIMA) and Sudan IV (manufactured by Kanto Chemical Co., Ltd.) were mixed as stains to prepare colored margarine (colored margarine). The Sudan IV concentration in the colored margarine was set to 0.1% by mass.
The colored margarine 0.5g was uniformly apply | coated to the plastic dish (product made from a polypropylene) with a diameter of 18.5 cm, and this was made into the wash object.
40g of cleaning solution obtained by diluting the detergent composition to 1.25% by mass with tap water on a dishwashing sponge (product name: Scotch Bright, manufactured by Sumitomo 3M Ltd.) measuring 11.5 cm long × 7.5 cm wide × 3 cm high I took it. After the sponge was rubbed by hand five times, the object to be washed was rubbed. Specifically, the surface of the object to be cleaned was rubbed 10 times and the edge 10 times with a sponge containing a cleaning solution, and then rinsed with tap water. Thereafter, the objects to be washed were evaluated according to the following evaluation criteria. ○ and ◎ are acceptable.
[Evaluation criteria]
(Double-circle): The stain | pollution | contamination remainder of coloring margarine is not recognized visually, and there is no nulliness by coloring margarine residue.
◯: The stain residue of the colored margarine is not visually recognized, but there is a slight amount of null due to the remaining colored margarine.
(Triangle | delta): The stain | pollution | contamination remainder of coloring margarine is recognized visually, and there exists a null with the coloring margarine residue.
X: A considerable amount of stain residue of the colored margarine is observed.

Examples 1 to 35 to which the present invention was applied were excellent both in drainage and detergency.
Comparative Example 1 in which the content of the component (A1) is less than 50% by mass with respect to the total mass of the component (A) was inferior in cleaning power.
Comparative Example 2 having an (A + B) / D ratio of less than 1 was inferior in both water drainage and detergency.
The comparative example 3 whose (A + B) / D ratio is more than 10 was inferior in water drainage.
The comparative example 4 which does not contain magnesium ion was inferior in any of water drainage and detergency.
Comparative Example 5 containing zinc ions instead of magnesium ions was inferior in both drainage and detergency.

Claims (7)

(A) component, (B) component, (C) component, and (D) component are included,
The component (A) is an anionic surfactant,
The component (B) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants,
The component (C) is cationized cellulose,
The component (D) is a nonionic surfactant;
The content of the component (A) is 10% by mass or more based on the total mass of the dishwashing detergent composition,
The component (A) contains an alkylbenzene sulfonate (A1),
The content of the component (A1) is 50% by mass or more based on the total mass of the component (A),
The magnesium ion content is 0.02 to 0.60% by mass relative to the total mass of the dishwashing detergent composition,
The dishwashing detergent composition whose mass ratio represented by [the said (A) component + said (B) component] / (D) component is 1-10.   The dishwashing detergent composition according to claim 1, wherein the component (B) is the amphoteric surfactant.   The detergent composition for dishwashing of Claim 1 or 2 whose mass ratio represented by said (A) component / said (B) component is 2-80.   The component (D) contains a polyoxyalkylene type nonionic surfactant having a polyoxyalkylene group, and the average content of the polyoxyalkylene group is 50 to 99 per molecule of the polyoxyalkylene type nonionic surfactant. The detergent composition for dishwashing as described in any one of Claims 1-3 which is the mass%.   The detergent composition for dishwashing as described in any one of Claims 1-4 whose mass ratio represented by [the said (A) component + said (B) component] / magnesium ion is 20-800. The washing | cleaning agent for dishwashing as described in any one of Claims 1-5 in which the said (A) component contains the ether sulfate type anionic surfactant (A2) represented by a following formula (AI). Composition.
^{_{R 1 -O - [(PO)}} m / (EO) n] -SO 3 - 1 / X · M + ··· (A-I)
(In the formula (AI), R ¹ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; Represents the number of repetitions, 0 ≦ m ≦ 1, n represents the average number of repetitions of EO, 0 ≦ n ≦ 5; in [(PO) _m / (EO) _n ], EO and PO are randomly added And may be a block addition; M ⁺ is a counter ion; X is the valence of M ⁺ .) The component (A2) includes an alkyl sulfate ester type anionic surfactant (A3) in which m is 0 and n is 0 in the formula (AI),
The detergent composition for dishwashing of Claim 6 whose content of the said (A3) component is 30 mass% or more with respect to the total mass of the said (A2) component.