JPH1112596A - Liquid cleaner composition for tableware - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition manifesting high detergency against the clinging dirt derived from a hardness component in water by formulating a specific quantity of a specific serine-N,N-diacetic acid and/or a specific glutamic acid-N,N-diacetic acid with the cleaner composition. SOLUTION: This composition consists essentially of (A) a serine-N,N-diacetic acid of formula I [M<1> to M<3> are each H, an alkali (alkaline earth) metal, ammonium or a (substituted) alkylammonium] or a salt thereof and/or glutamic acid- N,N-diacetic acid of formula II [M<4> -M<7> are each H, an alkali (alkaline earth) metal, ammonium or a (substituted) alkylammonium] or the salt thereof, of 0.1-30 wt.%, (B) a surfactant (preferably, one or more kinds chosen from an anionic surfactant, a nonionic surfactant and an ampholytic surfactant) of 0.1-60 wt.% and (C) a lower alcohol (preferably, a 2-4C alcohol) of 0.01-10 wt.%. The weight of component B is five or more times as heavy as the weight of component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a dishwashing detergent composition, and more particularly, to a method for effectively removing fixed dirt derived from the hardness component of water remaining on the surface of dishware, The present invention relates to a dishwashing liquid composition capable of restoring aesthetic appearance.

[0002]

2. Description of the Related Art Today, with increasing awareness of human safety, kitchen cleaners are cleaners that often come into contact with the human body.
Investigations have been made to increase detergency and to mildly affect the skin. As a well-known technique, there is a method in which polyoxyethylene alkyl ether sulfate, which is an anionic surfactant, and alkyldimethylamine oxide are used in combination. This technique can improve the mildness to the skin while increasing the oily dirt cleaning power. This is due to a synergistic effect due to ion pair formation. In other words, the alkyldimethylamine oxide is in equilibrium between the cationic structure and the nonionic structure in the solution, and the amine oxide having the cationic structure forms an ion pair with the anionic surfactant. By the action of the bonding force, the surfactant is densely arranged on the surface or the interface, and foaming and oily stain cleaning power increase.

[0003] However, this technique is based on the surfactant activity of a surfactant, and has no effect on fixed soil such as calcium salts and magnesium salts derived from water hardness components. Since tap water is used for washing water and rinsing water, fixed dirt derived from hardness components always exists on the tableware surface. There has been a demand for a detergent composition that can effectively remove such stains and that is gentle on the skin.

[0004]

Means for Solving the Problems Under such circumstances, the present inventors have developed a method in which a specific serine-N, N-diacetate or a salt thereof and / or a specific glutamic acid-N, N-diacetic acid or a salt thereof are used as a detergent. A liquid detergent composition for tableware which has a high mildness to the skin, a high foaming power and a high cleaning power for oily stains by adding a specific amount to the composition, and also has a cleaning power for fixed soils derived from the hardness component of water. It was found that a product was obtained, and the present invention was completed.

That is, the present invention relates to (a) serine-N, N-diacetate represented by the following general formula (1) or a salt thereof and / or glutamic acid represented by the following general formula (2): 0.1 to 30% by weight of N, N-diacetic acid or a salt thereof,

[0006]

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(Wherein, M ^{1 to} M ³ represent hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium)

[0008]

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Wherein M ^{4 to} M ⁷ represent hydrogen, alkali metal, alkaline earth metal, ammonium, alkyl ammonium or substituted alkyl ammonium. (B) 0.1 to 60% by weight of a surfactant; and (c) A liquid detergent composition for dishes which contains 0.01 to 10% by weight of a lower alcohol as an essential component, and wherein the weight of the component (b) is more than 5 times the weight of the component (c).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) of the present invention, serine-N, N-diacetic acid represented by the above general formula (1) or glutamic acid-N represented by the above general formula (2) , N
In diacetic acid, M ^{1 to} M ⁷ in the general formulas (1) and (2)
As the (counter ion), hydrogen, sodium, and potassium are generally used. Here, the partially neutralized one has the highest sequestering ability of metal ions and has a high effect of improving the detergency, but the completely neutralized one exhibits a sufficient effect of improving the detergency.

In the present invention, the content of the component (a) is 0.1
-30% by weight, preferably 0.1-10% by weight. When the content of the component (a) is less than 0.1% by weight, the detergency of the fixed soil derived from the hardness component is poor, and when the content is more than 30% by weight, the solution stability is impaired.

The component (b) in the present invention is preferably at least one selected from anionic surfactants, nonionic surfactants and amphoteric surfactants.

Examples of the anionic surfactant include linear alkyl benzene sulfonate, alkyl ether sulfate,
It is preferably at least one selected from polyoxyalkylene alkyl ether sulfates, fatty acid soaps, and carboxyl group-containing surfactants represented by the following general formulas (3) to (4). R ¹ -O- (R ² O) _m -COOM ⁸ (3) (wherein, R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, a linear or branched alkyl group having 8 to 18 carbon atoms) A branched alkenyl group or a linear or branched alkylphenyl group having 8 to 18 carbon atoms in the alkyl portion, and R ² has ² carbon atoms;
Represents an alkylene group of 1 to 4, m represents a number of 1 to 20, and M ⁸
Represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium. )

[0014]

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(Wherein R ³ is a straight-chain or branched-chain alkyl group having 8 to 18 carbon atoms, a straight-chain or branched-chain alkenyl group having 8 to 18 carbon atoms or an alkyl portion having 8 to 18 carbon atoms)
18 represents a linear or branched alkylphenyl group,
R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms, m represents a number of 1 to 20, M ⁹ represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, an alkyl ammonium or a substituted alkyl ammonium; Is hydrogen atom, carbon number 1
An alkyl group of 4 to-(R ⁴ O) _m CH ₂ COOM ⁹ or-(R ⁴ O) _n CH ₂ C
H ₂ OH (n is a number from 0 to 20) is shown. ).

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers, fatty acid monoalkanolamides, fatty acid dialkanolamides, alkyl glycosides represented by the following general formula (5) and the following general formula (6). It is preferably at least one selected from the amine oxides represented. R ⁵ (OR ⁶ ) _x G _y (5) (wherein, R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms, and a linear or branched alkenyl group having 8 to 18 carbon atoms) Or a linear or branched alkylphenyl group having 8 to 18 carbon atoms in the alkyl portion, and R ⁶ has 2 carbon atoms.
Represents an alkylene group of -4, x represents a number having an average value of 0 to 2, G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, and y represents a residue having an average value of 1 to 10 R ⁷ -NR ⁸ R ⁹ → O (6) (wherein, R ⁷ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, and R ⁸ and R ⁹ represents an alkyl group having 1 to 3 carbon atoms which may be the same or different.) In the above general formula (6), the carbon number of R ⁷ is 10
~ 14 is more preferred.

The amphoteric surfactant is preferably at least one selected from surfactants represented by the following general formulas (7) and (8).

[0018]

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[0019] (wherein, R ¹⁰ represents an alkyl or alkenyl group of straight or branched chain 8 to 18 carbon atoms, R ¹¹
Represents an alkylene group having 1 to 4 carbon atoms, and R ¹² and R ¹³
Represents an alkyl group having 1 to 3 carbon atoms which may be the same or different. ^{) R 14 -N + R 15 R} 16 -CH 2 CH (OH) CH 2 SO 3 - (8) ( wherein, R ¹⁴ represents an alkyl group or an alkenyl group of straight or branched chain 8 to 18 carbon atoms And R ¹⁵ and R ¹⁶
Represents an alkyl group having 1 to 3 carbon atoms which may be the same or different. In the above general formulas (7) and (8), R ¹⁰ and R
10 to 14 is more preferable as ¹⁴ carbon atoms.

In the present invention, the content of the component (b) is 0.1
6060% by weight, preferably 0.5-55% by weight. When the content of the component (b) is less than 0.1% by weight, the washing performance of oily soil is poor, and when the content is more than 60% by weight, the solution stability is impaired.

In the present invention, the lower alcohol as the component (c) is preferably an alcohol having 2 to 4 carbon atoms, particularly preferably ethyl alcohol having 2 carbon atoms.

In the present invention, the content of the component (c) is 0.01
-10% by weight, preferably 0.1-8% by weight. When the content of the component (c) is less than 0.01% by weight, the detergency is poor, and when it is more than 10% by weight, the mildness to the skin is poor.

In the present invention, the weight of the component (b) is
Desirably, it is more than 5 times the weight of the component (c). If it is less than 5 times, the oily dirt cleaning power will be poor.

The undiluted solution of the liquid detergent composition for dishes of the present invention
The pH is preferably from 4.0 to 12.0, particularly preferably from 5.0 to 8.0.

Further, other optional components can be added to the dishwashing liquid detergent composition of the present invention as long as the solution stability and washing performance of the composition are not impaired. For example, solubilizers such as urea, viscosity modifiers such as clay minerals and water-soluble polymer substances, calcite, silica, calcium phosphate, zeolite,
Water-insoluble abrasives such as polyethylene, nylon and polystyrene, humectants such as glycerin and sorbitol, other enzymes, fragrances, dyes, preservatives, fungicides and the like can be added and blended.

[0026]

EFFECT OF THE INVENTION The liquid detergent composition for dishes according to the present invention has a mild effect on the human body and is excellent not only in foaming power and oily dirt cleaning power but also in cleaning power of fixed dirt derived from water hardness components. As a result, the original aesthetic appearance can be restored to the surface of the tableware after washing.

[0027]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 16 and Comparative Examples 1 to 10 The compositions shown in Tables 1 and 2 below were prepared and evaluated according to the following test methods and evaluation criteria. The obtained results are shown in Tables 1 and 2.

<Test Method and Evaluation Criteria> (1) Foaming Power The foaming power of a solution obtained by adding 0.1% of commercially available butter to a detergent solution having a detergent concentration of 0.5% is measured. The measurement method is as follows. 40 ml of the above solution is placed in a glass cylinder having a diameter of 5 cm, and the mixture is rotated and stirred at 30 rpm for 15 minutes, and the foam height immediately after the stop is measured. The evaluation criteria were as follows: ○ when the foam height exceeded 90 mm, Δ when 70 to 90 mm, and × when less than 70 mm.

(2) Detergency of oily dirt / fixed dirt Ten test subjects were actually washed with an index detergent (detergent A) and a measurement detergent (detergent B), and compared with detergent A to obtain detergent B. Was evaluated for its detergency. Washing dishes used were a dish coated with 2 g of salad oil (for evaluation of oily soil cleaning power) and a dish in which the operation of immersing in tap water for 10 seconds and then drying was repeated 50 times (for evaluation of fixed soil cleaning power). . The evaluation criteria were as follows: the average score of the following evaluation values was 4 or more: 、 ２, 2 or more and less than 4, Δ: less than 2. Detergent B is good 5 points Detergent B is slightly good 4 points Both are the same 3 points Detergent A is slightly good 2 points Detergent A is good 1 point

[0031]

[Table 1]

[0032]

[Table 2]

(Note) * 1: Emar E-27C (Kao Corporation) * 2: ES-4.0K (100) L (Kao Corporation) * 3: Pure soap (Kao Corporation) * 4: AG-124 (manufactured by Kao Corporation) * 5: Softanol 33 (manufactured by Nippon Shokubai Co., Ltd.) * 6: Aminoen PK-025 (manufactured by Kao Corporation) * 7: Amphitol 20N (manufactured by Kao Corporation) * 8: Amphitol 20AB (Manufactured by Kao Corporation) * 9: Amphitol 20HD (manufactured by Kao Corporation) * 10: Obtained according to the following synthesis example. <Synthesis example> 134 g of nitrilotriacetonitrile and 402 g of ethanol were charged into a two-liter four-necked flask.
The temperature was raised to 75 ° C. 37% formaldehyde aqueous solution here 1
22 g were added dropwise at the same temperature in 3 hours. At that time, the pH of the reaction mixture was maintained at 10 using triethylamine. After completion of the dropwise addition, the mixture was aged at the same temperature for 5 hours to obtain a solution containing hydroxymethyl nitrilotriacetonitrile. Here, 600 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour.
At the same time, the temperature of the reaction mixture was raised to 100 ° C., and ethanol, triethylamine, generated ammonia and a part of water were distilled out of the reaction system. Keep at 100 ℃ for 5 hours,
Ethanol, triethylamine and ammonia were completely removed. As a result, 792 g of an aqueous solution containing 29% of serine-N, N-diacetate / 3Na salt represented by the general formula (I-1) was obtained. Compounds of other salts were synthesized in the same manner.

[0034] * 11: GBS-5 (Rhone-Poulenc, Inc., M ⁴
MM ⁷ = Na) or derived therefrom.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 1/29 C11D 1/29 1/52 1/52 1/68 1/68 1/72 1/72 1/75 1/75 1/90 1/90 1/92 1/92 3/20 3/20 9/26 9/26 9/30 9/30

Claims (6)

[Claims] (A) Serine-N, N-diacetate represented by the following general formula (1) or a salt thereof and / or glutamic acid-N, N- represented by the following general formula (2) 0.1 to 30% by weight of diacetic acid or a salt thereof (Wherein, M ^{1 to} M ³ represent hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium). (Wherein, M ^{4 to} M ⁷ represent hydrogen, alkali metal, alkaline earth metal, ammonium, alkyl ammonium or substituted alkyl ammonium.) (B) 0.1 to 60% by weight of a surfactant, and (c) lower alcohol A liquid detergent composition for dishes, comprising 0.01 to 10% by weight as an essential component, wherein the weight of the component (b) is more than 5 times the weight of the component (c). 2. The liquid detergent for dishes according to claim 1, wherein (b) the surfactant is at least one selected from anionic surfactants, nonionic surfactants and amphoteric surfactants. Composition. 3. The liquid detergent composition for dishes according to claim 1, wherein (b) the surfactant is an anionic surfactant or a nonionic surfactant. 4. An anionic surfactant comprising a linear alkylbenzene sulfonate, an alkyl ether sulfate, a polyoxyalkylene alkyl ether sulfate, a fatty acid soap, and a compound represented by the following general formulas (3) to (4): The liquid detergent composition for dishes according to claim 2 or 3, which is at least one selected from carboxyl group-containing surfactants. R ¹ -O- (R ² O) _m -COOM ⁸ (3) (wherein, R ¹ is a linear or branched alkyl group having 8 to 18 carbon atoms, a linear or branched alkyl group having 8 to 18 carbon atoms) A branched alkenyl group or a linear or branched alkylphenyl group having 8 to 18 carbon atoms in the alkyl portion, and R ² has ² carbon atoms;
Represents an alkylene group of 1 to 4, m represents a number of 1 to 20, and M ⁸
Represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium. ) (In the formula, R ³ is a straight-chain or branched-chain alkyl group having 8 to 18 carbon atoms, a straight-chain or branched-chain alkenyl group having 8 to 18 carbon atoms or a straight-chain or branched-chain alkyl group having 8 to 18 carbon atoms. Represents a chain or branched alkylphenyl group, and R ⁴ has 2 carbon atoms
Indicates to 4 alkylene group, m represents a number of 1 to 20, M ⁹
Is a hydrogen atom, an alkali shown metals, alkaline earth metals, ammonium, alkyl ammonium or substituted alkyl ammonium, A is a hydrogen atom, an alkyl group having 1 to 4 carbon _{^{atoms, - (R 4 O) m}} CH 2 COOM 9 or - (R ⁴ O) _n CH ₂ CH ₂ OH (n is 0
~ 20 numbers). ) 5. The nonionic surfactant is a polyoxyalkylene alkyl ether, a fatty acid monoalkanolamide, a fatty acid dialkanolamide, represented by the following general formula (5):
The liquid detergent composition for dishes according to claim 2 or 3, wherein the composition is at least one selected from the group consisting of an alkyl glycoside represented by the following formula and an amine oxide represented by the following general formula (6). R ⁵ (OR ⁶ ) _x G _y (5) (wherein, R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms, and a linear or branched alkenyl group having 8 to 18 carbon atoms) Or a linear or branched alkylphenyl group having 8 to 18 carbon atoms in the alkyl portion, and R ⁶ has 2 carbon atoms.
Represents an alkylene group of -4, x represents a number having an average value of 0 to 2, G represents a residue derived from a reducing sugar having 5 to 6 carbon atoms, and y represents a residue having an average value of 1 to 10 R ⁷ -NR ⁸ R ⁹ → O (6) (wherein, R ⁷ represents a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, and R ⁸ and R ⁹ represents an alkyl group having 1 to 3 carbon atoms which may be the same or different.) 6. The liquid detergent for dishes according to claim 2, wherein the amphoteric surfactant contains at least one selected from surfactants represented by the following general formulas (7) and (8). Composition. Embedded image (Wherein, R ¹⁰ represents an alkyl or alkenyl group of straight or branched chain 8 to 18 carbon atoms, R ¹¹ is 1 to carbon atoms
4 represents an alkylene group, and R ¹² and R ¹³ represent an alkyl group having 1 to 3 carbon atoms which may be the same or different. ^{) R 14 -N + R 15 R} 16 -CH 2 CH (OH) CH 2 SO 3 - (8) ( wherein, R ¹⁴ represents an alkyl group or an alkenyl group of straight or branched chain 8 to 18 carbon atoms And R ¹⁵ and R ¹⁶
Represents an alkyl group having 1 to 3 carbon atoms which may be the same or different. )