JP2000096098A - Aqueous liquid cleanser - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a stable low-foamable aqueous liquid cleanser having a high antibacterial washing performance and free from cloudiness, separation, or the like. SOLUTION: This aqueous liquid cleanser comprises 0.5-50 wt.% of an alkali agent, 0.05-20 wt.% of a cationic antibacterial agent, 0.05-50 wt.% of a metal chelating agent, 0.1-25 wt.% of a low foamable nonionic surfactant, 0.1-10 wt.% (as a fatty acid) of the fatty acid of the formula: R-COOH (R is a 3-13C linear aliphatic hydrocarbon group or a 3-13C branched aliphatic hydrocarbon group) or its salt, and 0.1-30 wt.% or a glycol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sterilizing aqueous liquid detergent suitable for an automatic washing machine.

[0002]

2. Description of the Related Art Automatic washing machines are used to wash a wide variety of dishes, cups, cans, bottles, plastic containers, shopping baskets, vehicles, floors, etc. Containers, tableware, food bottles, cans, and the like are often contaminated with food-derived fats, oils, proteins, starch, and the like. In addition, a large amount of oil and dirt adheres to other containers and shopping baskets.

[0003] For this reason, a surfactant, especially a nonionic surfactant, is used in combination with an alkali agent to solubilize dirt by a hydrolysis action, etc., to wash and remove the dirt, and to improve the oil detergency. Has been done. In the case of spray cleaning using an automatic cleaning machine, if there is much foaming of the surfactant,
Since the foam overflows and the discharge pressure of the spray device decreases, low foaming properties are required.

On the other hand, in general, aqueous liquid detergents using an alkali agent and a nonionic surfactant in combination cause turbidity and separation.
Due to poor stability, a solubilizing agent or the like is used in combination. For example,
JP-A-64-4226 discloses the use of a specific carboxylic acid as a solubilizing agent in a strong alkaline agent and a nonionic surfactant.

[0005] Recently, it has been desired to perform sterilization as well as cleaning in order to raise awareness of prevention of food poisoning and increase the desire for cleanliness. For this reason, a bactericidal component, for example, a cationic bactericide or the like is often used in combination with a detergent for an automatic washing machine.

However, when the content of an alkali agent, a nonionic surfactant, a cationic bactericide, and an inorganic substance is increased, high-temperature washing is generally performed in an automatic washing machine, but under such usage conditions, it is not possible. Even when a solubilizing agent is used, the detergent becomes cloudy, precipitates and separates, and the detergency and the sterilization power are reduced.

An object of the present invention is to provide a stable, low-foaming aqueous liquid detergent which has high washing performance and sterilization performance and is free from cloudiness or separation.

[0008]

According to the present invention, there are provided (a) an alkali agent of 0.5 to 50% by weight, (b) a cationic fungicide of 0.05 to 20% by weight, (c) a metal chelating agent of 0.05 to 50% by weight, and (d) a low content of the metal chelating agent. Foaming nonionic surfactant 0.1 to 25% by weight (e) Fatty acid represented by the general formula (I) or a salt thereof 0.1 to 10% by weight (as a fatty acid) R-COOH (I) (where R is the number of carbon atoms) A linear aliphatic hydrocarbon group having 3 to 13 or a branched aliphatic hydrocarbon group having 3 to 17 carbon atoms.) (F) An aqueous liquid detergent containing 0.1 to 30% by weight of glycols is provided. .

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the alkaline agent (a) include amines such as monoethanolamine, diethanolamine and triethanolamine, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate and potassium carbonate. And alkali metal silicates such as alkali metal carbonate, sodium silicate and potassium silicate.
(a) 0.5 to 0.5%
50% by weight (%), preferably 4 to 30%, more preferably 5 to 25%.

As the cationic fungicide (b), benzethonium chloride, benzalkonium chloride, dialkyldimethylammonium halide, monoalkyltrimethylammonium halide or a cationic surfactant having a counterion of these fungicides converted into another anion Fungicides,
Examples include biguanide fungicides such as chlorhexidine and chlorohexidine gluconate, and amino acid surfactants such as alkyldiaminoethylglycine and alkylpolyaminoethylglycine. The component (b) is contained in the detergent in an amount of 0.05 to 20%, preferably 0.1 to 0.1, from the viewpoint of sterilization performance and stability.
-10% by weight, more preferably 0.5-5%.

As the metal chelating agent (c), phosphoric acid, polyphosphoric acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonic acids, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, fumaric acid, hydroxybenzyliminodiacetic acid, iminodiacetic acid and salts thereof. No. (c) Ingredients are 0.05-50% in detergent,
Preferably, 0.5 to 5% is blended. The component (c) is
From the viewpoint of the activity reduction preventing effect, it is 0.5 mol or more, especially 0.5 to 50 mol, more preferably 0.5 to 20 mol, relative to the component (b).
Furthermore, it is preferable to mix 1 to 20 times by mole.

In the present invention, a low-foaming nonionic surfactant is used.
(d) means those which exhibit sufficient water solubility or water dispersibility and do not generate excessive foam when used for machine washing. Specifically, one or more selected from the following general formulas (II) to (VII) are preferable. HO- (PO) _x- (EO) _y- (PO) _z -H (II) HO- (EO) _a- (PO) _b- (EO) _c -H (III) (Formula (II), (III) ), EO represents an oxyethylene group, PO represents an oxypropylene group, x, z and b represent the average number of moles of propylene oxide added, and x + z ≦ 60, preferably
10 to 50, b ≦ 60, preferably 10 to 50, and y and a and c each represent an average addition mole number of ethylene oxide;
≦ 150, preferably 2 to 50, a + c ≦ 150, preferably 2 to 50, and each of x, y, z, a, b, and c is 0.
Indicates a number that exceeds R ¹ -O (EO) _n -R ² (IV) (In the formula (IV), R ¹ represents a linear or branched alkyl group having 1 to 24 carbon atoms, EO represents an oxyethylene group, n represents an average number of moles of ethylene oxide of 8 to 30, and R ² represents a linear or branched alkyl group having 1 to 18 carbon atoms. R ³ -O- (EO) _x- (PO) _y- (EO) _z -R ⁴ (V) (In the formula (V), R ³ and R ⁴ are the same or different and have 1 to 24 carbon atoms.
Represents a linear or branched alkyl group or a cycloalkyl group having 3 to 12 carbon atoms (however, R ⁴ also includes a hydrogen atom),
EO represents an oxyethylene group, and PO represents an oxypropylene group. x and z are each 1 or more, preferably 2 to 10, each indicating the average addition mole number of ethylene oxide, and y is a 1 to 4 number indicating the average addition mole number of propylene oxide. (EO) _x , (PO) _y , and (EO) _z are linked in this order. R ⁵ -O- (EO) _x- (PO) _y -R ⁶ (VI) R ⁵ -O- (EO) _x- (BO) _z -R ⁶ (VII) (Formulas (VI) and (VII) Wherein R ⁵ and R ⁶ are the same or different and represent a linear or branched alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms (however, R ⁶ also includes a hydrogen atom); EO represents an oxyethylene group, PO represents an oxypropylene group, and BO represents an oxybutylene group. x, y, and z each represent an average number of moles of ethylene oxide, propylene oxide, and butylene oxide, and are 1 to 20 respectively. ].

The component (d) is incorporated in the detergent in an amount of 0.1 to 25%, preferably 0.5 to 5%, more preferably 0.5 to 2%, from the viewpoint of oil detergency and solution stability.

The fatty acid represented by the general formula (I) or its salt (e) according to the present invention includes n-butyric acid, valeric acid, sorbic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, Examples thereof include straight-chain fatty acids such as undecanoic acid and salts thereof, and branched-chain fatty acids such as isobutyric acid, 2-ethylhexanoic acid, isopalmitic acid and isostearic acid, and salts thereof. The component (e) is 0.1% as a fatty acid in the detergent because preferable solution stability is obtained.
-10%, preferably 0.5-5%, more preferably 1-5
%. The component (e) is usually present in the detergent as a salt neutralized by the component (a).

The glycols (f) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (Mw = 200 to 12000), propylene glycol, dipropylene glycol, tripropylene glycol, and polypropylene glycol (Mw = 60).
0 to 4000), 1,3-butanediol, 1,4-butanediol, polytetramethylene ether glycol (Mw = 650
~ 1000), 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,6-
Hexanediol, 2-ethyl-1,3-hexanediol and the like can be mentioned. Particularly, propylene glycol and 1,4-butanediol are preferred. Component (f) is incorporated in the detergent in an amount of 0.1 to 30%, preferably 0.5 to 10%, and more preferably 1 to 5%, since a preferable solution stability can be obtained.

The aqueous liquid detergent of the present invention may further contain other additives, such as bleaching agents, other germicides, preservatives, organic solvents, thickeners, fragrances, coloring agents, acids, dehydrating agents, if necessary. A foaming agent or the like can be appropriately compounded within a range that does not impair the effects of the present invention.

The aqueous liquid detergent of the present invention is prepared by mixing and stirring when each component is a liquid, and when containing a solid substance, first dissolving in water, then adding another liquid component and mixing and stirring. The order of addition and dissolution is not particularly limited depending on the composition.

The aqueous liquid detergent of the present invention preferably has a 1% by weight aqueous solution (25 ° C.) having a pH of 10 or more, particularly 11 to 13.5.

[0019]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 5 and Comparative Examples 1 to 4 The aqueous liquid detergents shown in Table 1 were prepared. A detergent supply machine was installed on the DW-230L automatic dishwasher manufactured by Sanyo Electric Co., Ltd.
A cleaning agent was supplied from this supply machine, and a cleaning test was performed under the following conditions, and the cleaning property and the low foam property were evaluated based on the following criteria. In addition, storage stability and bactericidal activity were also evaluated.

[I] Detergency ・ Cleaning conditions Cleaning temperature: 60 ± 2 ° C. Cleaning time: 45 seconds Detergent concentration: 0.15% Rinse time: 15 seconds Rinse temperature: 80 ± 2 ° C. A magnetic dish (diameter: 5 g per one piece of composite model soil (a mixture of protein, oil and starch)
(200 mm x 30 mm height) 4 sheets Washing target 2: 4 polypropylene dishes (200 mm diameter x 30 mm height) coated with 5 g of salad oil per sheet ・ Criterion ◎: Dirt was completely removed. ：: Almost all dirt was removed. Δ: Insufficient removal of dirt. X: Almost no dirt is removed.

[II] Low-foaming property 30 ml of a 1% aqueous solution of a detergent is placed in a test tube (length 25 mm, inner diameter 30 m)
m), the solution was heated to 40 ° C., shaken 20 times, and the foaming height after 10 seconds was measured. Criteria 基準: Foam amount is small (foaming height is less than 10 mm). ：: Foam amount is normal (foaming height is 10 mm or more and less than 20 mm). Δ: The foam amount was slightly large (foaming height 20 mm or more and less than 50 mm). ×: A large amount of foam (bubble height of 50 mm or more).

[III] Stability The detergent is stored under conditions of 40 ° C. × 30 days or −5 ° C. × 30 days,
The stability was evaluated.・ Criteria ○: Transparent (cloudy, no separation) △: Slightly cloudy ×: Separated [IV] Bactericidal activity The bactericidal activity was evaluated using Escherichia coli IFO39 as a test bacterium.
72, using Staphylococcus aureus IFO12732, fixed the contact time to 60 seconds, 100% of the dilution when the detergent was diluted
The maximum dilution that can be sterilized was determined. That is, bacteria (about 10 ⁹ to 10 ¹⁰ c) pre-cultured on an SCD medium (manufactured by Nippon Pharmaceutical Co., Ltd.)
ell / ml), and the detergent was inoculated into 10 ml of a diluted solution diluted with sterilized 3.5 ° DH hard water, and allowed to act at room temperature for 60 seconds. After 60 seconds, one loopful of the bacterial contact solution was collected, and a micro-chalet containing 0.3 ml of SCD medium for post-culture (CORNING
96-Cell Wells). The cells were cultured at 30 ° C. for 3 days, and the growth of the bacteria was visually observed to determine the strength of the effect.
That is, the maximum dilution ratio at which no growth of bacteria was observed on the microplanter was determined, and the higher the ratio, the higher the bactericidal effect.

[0024]

[Table 1]

Nonionic surfactant 1: a compound of x = 21, y = 14, z = 22 in the general formula (II) Nonionic surfactant 2: R ¹ = C ₁₂ in the general formula (IV) n = 1
2, compound of R ² = C ₈・ Nonionic surfactant 3: R ³ = C ₁₂ , x = 7 in the general formula (V)
, Y = 1.5, z = 7, compound of R ⁴ ＝ C ₈・ Caprylic acid: Lunac 8-98, manufactured by Kao Corporation
The amount is as fatty acid

[0026]

The aqueous liquid detergent of the present invention is excellent in detergency, bactericidal power, low foaming property and storage stability, and is an aqueous liquid cleaner for an automatic washing machine that requires effective sterilization and cleaning in a short time. It is suitable as an agent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C11D 3/10 C11D 3/10 3/20 3/20 3/33 3/33 3/48 3/48 ( 72) Inventor Riichi Higashi 1334 Minato, Wakayama City, Wakayama Prefecture Kao Corporation Research Laboratory (72) Inventor Sumitomo Ito 1334 Minato, Wakayama City Wakayama Prefecture Kao Research Center F Term (reference) 4H003 AC08 AC23 AE05 BA12 DA05 DA11 DA12 DA19 DB02 EA09 EA15 EA21 EB04 EB07 EB08 EB16 ED02 ED28 FA07 FA16 FA28 FA34

Claims (5)

[Claims] (1) Alkaline agent 0.5 to 50% by weight (b) Cationic fungicide 0.05 to 20% by weight (c) Metal chelating agent 0.05 to 50% by weight (d) Low foaming nonionic surfactant 0.1 to 50% 25% by weight (e) Fatty acid represented by the general formula (I) or a salt thereof 0.1 to 10% by weight (as fatty acid) R-COOH (I) (wherein R is a straight-chain aliphatic having 3 to 13 carbon atoms) It represents a hydrocarbon group or a branched chain aliphatic hydrocarbon group having 3 to 17 carbon atoms.) (F) An aqueous liquid detergent containing 0.1 to 30% by weight of glycols. 2. The aqueous liquid detergent according to claim 1, wherein the low-foaming nonionic surfactant is a polyoxyethylene-polyoxypropylene block polymer represented by the following general formula (II) or (III). HO- (PO) _x- (EO) _y- (PO) _z -H (II) HO- (EO) _a- (PO) _b- (EO) _c -H (III) (Formula (II), (III) ), EO represents an oxyethylene group, PO represents an oxypropylene group, x, z and b represent the average number of moles of propylene oxide added, x + z ≦ 60, b ≦ 60, and y, a, c Represents the average number of moles of ethylene oxide added, y ≦ 150, a + c ≦ 150, x,
Each of y, z, a, b, and c indicates a number exceeding 0. ] 3. The aqueous liquid detergent according to claim 1, wherein the low-foaming nonionic surfactant is a polyoxyethylene dialkyl ether represented by the following general formula (IV). R ¹ -O (EO) _n -R ² (IV) [In the formula (IV), R ¹ represents a linear or branched alkyl group having 1 to 24 carbon atoms; EO represents an oxyethylene group; the number of 8 to 30 showing an average mole number of added ethylene oxide, R ² is a straight or branched chain alkyl group having 6 to 18 carbon atoms. ] 4. The aqueous liquid detergent according to claim 1, wherein the low-foaming nonionic surfactant is a polyoxyalkylene (di) alkyl ether represented by the following general formula (V). R ³ -O- (EO) _x- (PO) _y- (EO) _z -R ⁴ (V) (In the formula (V), R ³ and R ⁴ are the same or different and each have 1 to 24 carbon atoms.
Represents a linear or branched alkyl group or a cycloalkyl group having 3 to 12 carbon atoms (however, R ⁴ also includes a hydrogen atom),
EO represents an oxyethylene group, and PO represents an oxypropylene group. x and z are each 1 or more numbers indicating the average addition mole number of ethylene oxide, and y is a number of 1 to 4 indicating the average addition mole number of propylene oxide. (EO) _x , (PO) _y ,
(EO) _z is block-connected in this order. ] 5. The aqueous liquid detergent according to claim 1, wherein the low-foaming nonionic surfactant is a polyoxyalkylene (di) alkyl ether represented by the following general formula (VI) or (VII). R ⁵ -O- (EO) _x- (PO) _y -R ⁶ (VI) R ⁵ -O- (EO) _x- (BO) _z -R ⁶ (VII) (In formulas (VI) and (VII) , R ⁵ and R ⁶ are the same or different and each represent a linear or branched alkyl group having 1 to 24 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms (however, R ⁶ also includes a hydrogen atom); Represents an oxyethylene group, PO represents an oxypropylene group, and BO represents an oxybutylene group. x, y, and z each represent an average number of moles of ethylene oxide, propylene oxide, and butylene oxide, and are 1 to 20 respectively. ]