JP5197988B2 - Aqueous liquid detergent composition - Google Patents

Description

  The present invention relates to an aqueous liquid detergent composition used for cleaning hard surfaces such as food processing equipment, various facilities such as food / beverage filling equipment, and environments such as walls and floors, particularly hard surfaces partially containing aluminum materials. Related to things.

In order to remove severe and deteriorated dirt derived from foods and beverages adhering to a hard surface, such as various equipment such as food processing equipment, a detergent containing an alkaline component is generally widely used. Furthermore, for various facilities and the like that require a higher degree of hygiene, a cleaning agent using a bactericide such as hypochlorite or a cationic surfactant has been proposed and generally used. On the other hand, many parts made of aluminum or aluminum alloy materials are used in these facilities, etc., and contact with alkali components causes corrosion of these aluminum and aluminum alloys. Cleaning agents using silicates have been proposed for a long time. However, when a detergent containing silicate is used, the insoluble scale derived from silicate adheres to and accumulates on the object, causing whitening, and not only the appearance is greatly impaired, but also the object surface is soiled. It becomes easy to adhere and forms a hotbed of bacteria, resulting in a very unsanitary state.

Various proposals have been made against this background. Patent Documents 1 and 2 propose a cleaning agent that reduces corrosion of a material containing aluminum without containing silicate.
US Pat. No. 5,710,120 JP 2004-123979 A

  However, these Patent Documents 1 and 2 also satisfy in a well-balanced manner the performances such as the ability to clean severe and dirty soil derived from foods and beverages that adhere to hard surfaces, the ability to prevent aluminum corrosion, and the ability to prevent adhesion and accumulation of scales. Furthermore, an aqueous liquid detergent composition that satisfies long-term storage stability at a higher level has not been achieved.

  Therefore, the object of the present invention is excellent in the cleaning property of the severe soil which has deteriorated due to the food / beverage adhering to the hard surface, can prevent both aluminum corrosion and scale adherence / accumulation, and also has storage stability. It is to provide an excellent aqueous liquid detergent composition.

  The present invention includes (A) an alkali agent, (B-1) a calcium compound, (B-2) a magnesium compound, (C) an organic acid or an alkali metal salt, an ammonium salt or an alkanolamine salt thereof, and (D) phosphone. An acid or an alkali metal salt thereof, an ammonium salt or an alkanolamine salt, and one or more compounds selected from a polymeric carboxylic acid or an alkali metal salt thereof, an ammonium salt or an alkanolamine salt, and (B-2) / ( It is related with the aqueous liquid detergent composition whose molar ratio of B-1) is 0.01-0.2.

  In addition, the present invention provides (A) an alkali agent (hereinafter referred to as component (A)), (B-1) a calcium compound, (B-2) a magnesium compound [hereinafter referred to as (B-1) and (B-2). (C) organic acid or alkali metal salt thereof (hereinafter referred to as (C) component), ammonium salt or alkanolamine salt, and (D) phosphonic acid or alkali metal salt thereof, An ammonium salt or an alkanolamine salt, and a polymer carboxylic acid or one or more compounds selected from alkali metal salts, ammonium salts or alkanolamine salts thereof (hereinafter referred to as “component (D)”); 2) It is related with the aqueous liquid detergent composition whose molar ratio of (B-1) is 0.01-0.2.

  The present invention also relates to a cleaning method in which the aqueous liquid detergent composition of the present invention is used at a calcium atom concentration of 10 ppm or more derived from (B-1) of the composition.

  ADVANTAGE OF THE INVENTION According to this invention, the aqueous | water-based liquid detergent composition which can achieve highly washability and can prevent the corrosion of aluminum and adhesion and accumulation | storage of a hardly soluble scale is provided. Moreover, since these effects are stably maintained for a long period of time, they can be used without worrying about the occurrence of corrosion and scale, and a high degree of hygiene can be maintained over a long period of time. Moreover, the aqueous liquid detergent composition of the present invention exhibits better storage stability.

<(A) component>
The component (A) is a component that contributes to detergency. Specific examples include alkali metal hydroxides, alkali metal carbonates, alkanolamines such as monoethanolamine, and among them, alkali metal hydroxides are preferable. In some cases, it is also effective to increase the detergency more synergistically by using an alkali metal hydroxide or an alkali metal carbonate and an alkanolamine together. The amount of component (A) in the composition is preferably 0.01% by weight or more, more preferably 0.1 to 30% by weight, still more preferably 0.5 to 20% by weight, and still more preferably. Is 1 to 10% by weight, and the cleaning performance can be further improved by adjusting the content within these ranges.

<(B) component>
Among the components (B), the calcium compound (B-1) (hereinafter referred to as the component (B-1)) reduces metal corrosion, particularly surface corrosion of aluminum materials, by interaction with the component (C). Have a role. The component (B-1) is preferably a compound that releases calcium ions in the cleaning composition of the present invention or in a diluted aqueous solution of the cleaning composition to be used. Specifically, water-soluble calcium salts such as calcium acetate, calcium chloride, and calcium nitrate are preferable. Of these, calcium acetate and calcium chloride are preferred. (B-1) The compounding quantity of a component is 0.003 to 10 weight% in a composition, Furthermore, 0.1 to 5 weight% is preferable. Moreover, in this invention, it is aluminum anticorrosive property to mix | blend (B-1) component in a cleaning composition so that it may be used as a washing | cleaning medium whose calcium atom concentration derived from (B-1) is 10 ppm or more. More preferable from the viewpoint.

  On the other hand, among the components (B), the magnesium compound (B-2) [hereinafter referred to as the component (B-2)] imparts superior stability in the presence of the component (B-1). It is a component that brings about an effect. Specifically, water-soluble magnesium salts such as magnesium acetate, magnesium chloride, and magnesium nitrate are suitable. Of these, magnesium acetate and magnesium chloride are preferred. (B-2) The compounding quantity of a component is 0.001-1.8 weight% in a composition, Furthermore, 0.005-0.9 weight%, More preferably, 0.01-0.2 weight% is preferable.

  As for (B) component, it is preferable that at least one of (B-1) component and (B-2) component is 1 or more types of compounds chosen from an acetate and a chloride.

  In the cleaning composition of the present invention, from the viewpoint of storage stability and aluminum corrosion resistance, the molar ratio of (B-2) / (B-1) is preferably 0.02 to 0.2, more preferably 0. 0.03 to 0.2, more preferably 0.03 to 0.1.

<(C) component>
The component (C) plays a role of reducing metal corrosion, particularly surface corrosion of an aluminum material, by interaction with the component (B). Component (C) is an organic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof, a hydroxycarboxylic acid having 1 to 4 hydroxyl groups and 2 to 4 carboxyl groups in the molecule, or an alkali thereof. Metal salts (especially sodium salts and potassium salts), ammonium salts and alkanolamine salts are preferred, and those having a total carbon number of 3 to 10 are preferred. Of these, tartaric acid, citric acid, and alkali metal salts, ammonium salts, or alkanolamine salts of these alkali metal salts are preferable. More preferred is tartaric acid or its alkali metal salt, ammonium salt or alkanolamine salt. (C) As a preferable compounding quantity of a component, it is 0.01 weight% or more in a composition, More preferably, it is 0.1-30 weight%, More preferably, it is 0.5-20 weight%, More preferably Is 1 to 10% by weight, and by adjusting within these ranges, the corrosion resistance of aluminum is further enhanced.

<(D) component>
The component (D) plays a role of preventing carbonate scale adhesion and accumulation typified by calcium carbonate. Since the dispersibility of the scale component particles is excellent, the present invention is selected from phosphonic acid or its alkali metal salt, ammonium salt or alkanolamine salt, and high-molecular carboxylic acid or its alkali metal salt, ammonium salt or alkanolamine salt. One or more compounds are used as component (D).

Specific examples of the phosphonic acid or its alkali metal salt, ammonium salt or alkanolamine salt include 1-hydroxyethane-1,1-diphosphonic acid << CH ₃ C (OH) [PO (OH) ₂ ] ₂ >> (abbreviation: HEDP), amino tri (methylene phosphonic acid) "N [CH ₂ PO (OH) _{2] 3"} (abbreviation: ATMP), ethylenediaminetetra (methylenephosphonic _{acid) "N 2 (CH 2)} 2 [CH ₂ PO (OH) _{2] 4} ", diethylenetriamine penta (methylene phosphonic acid)" N ₃ (CH _{2) 2} [CH ₂ PO (OH) _{2] 5} ', 2-phosphono-1,2,4-butane tricarboxylic acid "PO (OH) _{2 CH 2 CCH 2 CH 2 (} COOH) 3 "( abbreviation: PBTC) or the like, and their sodium or potassium salts, ammonium salts or alkanolamine salts, Among them HEDP, ATMP, PBTC, and their sodium or potassium salts, ammonium salts or alkanolamine salts are preferred,, HEDP, PBTC, and more preferably their sodium or potassium salts.

  Specific examples of the high-molecular carboxylic acid include acrylic acid-based polymers and maleic acid-based polymers. Among them, one or more selected from polyacrylic acid, polymaleic acid, and acrylic acid-maleic acid copolymers are preferable. Some or all of these may be alkali metal salts, ammonium salts, or alkanolamine salts, and the salts are preferably alkali metal salts such as sodium and potassium. The weight average molecular weight of the polyacrylic acid is preferably 2,000 to 20,000, more preferably 2,000 to 15,000. The maleic acid polymer is a homopolymer of maleic acid, a copolymer with other monomers copolymerizable with maleic anhydride, or a water-soluble salt thereof, and has a structure represented by the following general formula (I) Those having the following are preferred.

[Wherein R ₁ , R ₂ , R ₃ , R ₄ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, an alkoxy group, or a carboxyl group, and M represents a hydrogen atom, an alkali metal, or It is an organic amine, x / y (molar ratio) = 1/10 to 10/1, and the average molecular weight is 2,000 to 100,000. ]

  In the above general formula (I), x / y (molar ratio) is 1/10 to 10/1, preferably 3/7 to 7/3. The weight average molecular weight of the maleic acid polymer represented by the general formula (I) is 2,000 to 100,000, preferably 2,000 to 80,000, and more preferably 5,000 to 80,000. Is preferred. Among the polymers having the structure represented by the general formula (I), acrylic acid-maleic acid copolymers are preferable as the maleic acid copolymer.

<(E) component>
In the cleaning composition of the present invention, chlorite can be further added as the component (E) in order to improve bactericidal properties. Specific examples include alkali metal chlorites such as sodium chlorite, potassium chlorite, and lithium chlorite. Sodium chlorite and lithium chlorite are preferred. (E) As a preferable compounding quantity of a component, it is 0.01 to 10 weight% in a composition, More preferably, it is 0.03 to 5 weight%, More preferably, it is 0.1 to 5 weight%.

<(F) component>
In the cleaning composition of the present invention, a surfactant such as an anionic surfactant is further used as the component (F) in order to further improve foaming properties, emulsification cleaning properties of oil stains and storage stability. Agent, nonionic surfactant, amphoteric surfactant can be blended. The imparting of foaming property is suitable as a means for distributing a cleaning liquid when cleaning various devices and facilities in a food factory. In this case, a surfactant having a high foaming property is preferable, and the cleaning liquid adheres to the object to be cleaned in the form of foam and is maintained for a certain period of time. Benefits such as further improvement can be expected. The salt of the surfactant is preferably an alkali metal salt such as sodium salt or potassium salt, or an amine salt such as ammonium salt or alkanolamine.

  Specifically, examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfates, higher alcohol sulfonates, sulfates of higher alcohol ethers, sulfonates of higher alcohol ethers, and alkylbenzene sulfonates. preferable. As the nonionic surfactant, alkyl polyglycosides and polyalkylene alkyl ethers are preferable. As the amphoteric surfactant, alkyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, alkylcarboxymethylhydroxyethylimidazolinium betaine, and alkyldimethylamine oxide are preferable. Of these, alkylpolyglycoside, alkyldimethylamine oxide, and alkylcarboxymethylhydroxyethylimidazolinium betaine are preferable. These surfactants preferably have an alkyl group having 6 to 22 carbon atoms, more preferably have an alkyl group having 8 to 20 carbon atoms, and more preferably 10 to 18 carbon atoms.

  The component (F) is preferably blended in the range of 0.05 to 30% by weight in the cleaning composition of the present invention, more preferably 0.5 to 20% by weight, still more preferably 1 to 15% by weight. It is.

  Moreover, in order to improve the foam sustainability and the emulsification detergency of oil stains at the same time as imparting high foamability, it is effective to use two or more of these in combination, a combination of alkylamine oxide and alkyl polyglycoside, and A combination of the above alkyl carboxymethyl hydroxyethyl imidazolinium betaine and an alkyl polyglycoside is preferred. By using the alkylpolyglycoside in combination, it is possible to improve the detergency of oil stains and the foam persistence. In this case, the weight ratio of alkylamine oxide / alkyl polyglycoside is preferably more than 1/2, and the weight ratio of alkylcarboxymethylhydroxyethyl imidazolinium betaine / alkyl polyglycoside is preferably more than 1/2. .

<Other optional components>
The cleaning composition of the present invention comprises the above components (A) to (D), and if necessary, further blended (E) to (F). Furthermore, as an optional component, a solvent, You may contain a fragrance | flavor, a coloring agent, antiseptic | preservative, a viscosity modifier, etc.

<How to use the cleaning composition>
Although the typical usage method of the cleaning composition of this invention is shown below, it is not limited at all. When the cleaning composition of the present invention is used, it is preferably diluted to 1 to 100% by weight and applied to an object to be cleaned. A more preferable dilution concentration is 2 to 20% by weight, still more preferably 2 to 10% by weight.

  The cleaning composition of the present invention is preferably used for cleaning at a calcium atom concentration of 10 ppm or more derived from the component (B-1), particularly for cleaning hard surfaces, from the viewpoint of corrosion resistance of aluminum. It is used after diluting to obtain such a concentration.

  In order to add the component (F) to the cleaning composition of the present invention and apply it to the object to be washed in the form of foam, when using the above-described foam cleaning machine, the expansion ratio [foam volume (mL) / foam weight (g ))] Is preferably 3 to 50 times, more preferably 5 to 40 times, and even more preferably 7 to 30 times. When using a hand sprayer such as a trigger sprayer or a former player, the expansion ratio is preferably 2 to 30 times, more preferably 2 to 20 times, and even more preferably 3 to 10 times.

  Liquid cleaning compositions shown in Tables 1 and 2 were prepared and evaluated as follows. The results are shown in Tables 1 and 2.

(Detergency test)
The surface of an iron plate (15 cm × 30 cm) polished and polished with No. 240 sandpaper is uniformly coated with 1.5 g of rapeseed oil [chemical reagent, manufactured by Sigma Aldrich Japan Co., Ltd.] and oven at 180 ° C. Then, heat treatment was carried out for 1 hour to prepare a modified oil stain test piece. Absorbent cotton (1 cm × 2 cm; thickness 0.3 cm) is placed on the modified oil-stained test piece, and 1 g of a 10% by weight aqueous solution of the cleaning composition shown in Tables 1 and 2 is dropped on the absorbent cotton and left at 25 ° C. for 15 minutes. did. Thereafter, the absorbent cotton was removed and rinsed with running water, and the state of the iron plate surface was visually observed and evaluated according to the following criteria.
* Criteria A: Oil layer is completely removed.
○: The oil layer is almost removed.
Δ: Part of the oil layer is removed, or swelling is observed and discolored.
X: Almost no change was observed in the oil layer.

(Aluminum corrosion test)
An aluminum test piece (JIS A1050 alumite treated with sulfuric acid, 3 cm × 8 cm × 0.1 cm, Nippon Test Panel Co., Ltd.) is installed at an angle of about 45 degrees with respect to the horizontal plane. To this, 13 mL of a diluted solution of the cleaning composition shown in Tables 1 and 2 diluted to 5% by weight in advance with sterilized water was spread over a wide angle at 60 ° with an injection hole diameter of 1 mm in 1 second. Distribute from the cone type nozzle [operation (1)]. After leaving for 10 minutes [operation (2)], 40 mL of tap water is sprayed from another similar nozzle for 3 seconds to form a rinsing step [operation (3)]. After the rinsing step, the drying step [operation (4)] is performed by applying cold air for 30 seconds using a dryer. This operation (1)-(4) was repeated 100 times, the state change of the aluminum test piece was confirmed visually, and the aluminum anticorrosiveness was determined according to the following criteria.
* Criteria ◎; Almost no change is observed, and the weight loss of the test piece is 15 mg or less.
○: Slightly white corrosion is not observed, and the weight loss of the test piece is more than 15 mg and 30 mg or less.
Δ: Pale white corrosion is observed as a whole, but the weight loss of the test piece is more than 30 mg and 45 mg or less.
X: Corrosion that turned completely white was observed, and the weight loss of the test piece exceeded 45 mg.

(Scale adhesion test)
Using a stainless steel test piece (SUS304, 3 cm x 8 cm x 0.1 cm, Nippon Test Panel Co., Ltd.), the same operation as the above aluminum corrosion test was performed, and the scale adhesion state on the surface of the stainless steel test piece (scale prevention ability) Was determined according to the following criteria.
* Criteria A: No change is observed.
○: Almost no change is observed.
Δ: Rainbow-like change is observed.
X: Whitening was recognized partially or entirely.

(Storage stability test)
The cleaning compositions shown in Tables 1 and 2 were filled in polypropylene containers and stored at 40 ° C. Changes in appearance were observed, and storage stability was evaluated by the number of days until changes in appearance were observed, such as precipitates and precipitates such as precipitates and gelation.

(Bactericidal test)
E. coli ( Escherichia Coli IFO3972) is pre-cultured on SCD agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) at 35 ° C. for about 24 hours. It became cloudy. This suspension was subjected to centrifugal washing, adjusted to a bacterial concentration of about 10 ⁸ to 10 ⁹ cells / mL with an appropriate amount of sterilized water, and used as a bacterial solution. 0.05 ml of this bacterial solution was inoculated into 2 mL of a diluted solution of the cleaning composition shown in Table 2 that had been diluted to 1% by weight with sterile water in advance, and contacted at 25 ° C. for 5 minutes. Immediately thereafter, 0.1 mL of the detergent composition diluted solution inoculated with this bacterial solution was added to 2 mL of SCDLP medium (Nippon Pharmaceutical Co., Ltd.) supplemented with 1 wt% sodium thiosulfate, and involved in sterilization. Inactive ingredients. This inactivated solution is smeared in 0.2 mL on a standard agar medium having a diameter of 9 cm, cultured at 35 ° C. for 24 hours, and the number of colonies formed on the medium is counted as the number of remaining bacteria. Judged by criteria.
* Criteria ◎; colony formation is not recognized.
A: The number of colonies formed is less than 30.
Δ: The number of colonies formed is 30 or more and less than 300.
X: The number of colonies formed is 300 or more.

  In Tables 1 and 2, lauryl polyglucoside has an average degree of sugar condensation of 1.3.

Claims (7)

(A) Alkaline agent, (B-1) Calcium compound, (B-2) Magnesium compound, (C) Organic acid or its alkali metal salt, ammonium salt or alkanolamine salt, and (D) phosphonic acid or its alkali A metal salt, an ammonium salt or an alkanolamine salt, and a polymer carboxylic acid or one or more compounds selected from alkali metal salts, ammonium salts or alkanolamine salts thereof, (B-2) / (B-1) An aqueous liquid detergent composition having a molar ratio of 0.01 to 0.2. (A) Alkaline agent, (B-1) Calcium compound, (B-2) Magnesium compound, (C) Organic acid or its alkali metal salt, ammonium salt or alkanolamine salt, and (D) phosphonic acid or its alkali Compound (B-2) / (B-), comprising a metal salt, an ammonium salt or an alkanolamine salt, and a polymer carboxylic acid or one or more compounds selected from alkali metal salts, ammonium salts or alkanolamine salts thereof. An aqueous liquid detergent composition having a molar ratio of 1) of 0.01 to 0.2. The aqueous liquid cleaning composition according to claim 1 or 2, wherein at least one of (B-1) and (B-2) is one or more compounds selected from acetates and chlorides. The aqueous liquid cleaning composition according to any one of claims 1 to 3, wherein (B-2) is one or more magnesium compounds selected from magnesium acetate and magnesium chloride. (C) is a hydroxycarboxylic acid having 1 to 4 hydroxyl groups and 2 to 4 carboxyl groups in the molecule, or an alkali metal salt, ammonium salt or alkanolamine salt thereof. The aqueous cleaning composition of Claim 1. Furthermore, the aqueous liquid cleaning composition in any one of Claims 1-5 containing (E) chlorite. A cleaning method using the aqueous liquid cleaning composition according to any one of claims 1 to 6 at a calcium atom concentration of 10 ppm or more derived from (B-1) of the composition.