JP2009035599A - Hard surface cleaning method - Google Patents

Abstract

The present invention provides a technique capable of stably using the composition in a usage mode in which the filling rate of the aqueous liquid detergent composition in the container varies.
An aqueous liquid detergent composition containing (A) an alkaline agent, (B) a calcium compound, (C) a specific hydroxycarboxylic acid or a specific salt thereof, and (D) a phosphonic acid or a specific salt thereof. A method for cleaning a hard surface using a container-containing aqueous liquid detergent obtained by filling a container with a container containing the composition having a capacity of 200 mL or more in order to obtain a cleaning liquid at every cleaning opportunity The aqueous liquid detergent composition in the container is discharged, and the amount of the composition in the container is 15% (volume ratio) or more and the filling amount between the first washing opportunity and the last washing opportunity. Maintain between 200 mL and 50 L.
[Selection figure] None

Description

  The present invention relates to hard surfaces such as food processing equipment, food / beverage filling facilities, and environments such as walls and floors, in particular hard surfaces partially containing aluminum material, and a predetermined container-containing aqueous liquid detergent. The present invention relates to a cleaning method that uses and cleans. Moreover, it is related with the container-containing aqueous liquid cleaning agent used for such a method, and its usage.

  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. In patent document 1, the cleaning agent which reduces the corrosion of the material which contains aluminum without containing a silicate is proposed.
JP 2004-123979 A

  An aqueous liquid detergent composition, particularly an aqueous liquid detergent composition for business use, is often used as a washing liquid by preparing a dilute solution from a stock solution having a predetermined concentration when actually used for washing. When used as such, the amount of the composition in the container will gradually decrease, that is, the filling rate will decrease, but the stability of the composition remaining in the container will be impaired accordingly. was there.

  The objective of this invention is providing the technique which can use the said composition stably in the use aspect which the filling rate of the aqueous liquid detergent composition in a container fluctuates.

The present invention provides (A) an alkali agent, (B) a calcium compound, (C) a hydroxycarboxylic acid having 1 to 4 hydroxyl groups and 2 to 4 carboxyl groups in the molecule, or an alkali metal salt or ammonium salt thereof. Or an alkanolamine salt, and (D) one or more compounds 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. A method for cleaning a hard surface using an aqueous liquid detergent contained in a container, the container comprising an aqueous liquid detergent composition contained in a container having a capacity of 200 mL or more.
For each cleaning opportunity, drain the aqueous liquid detergent composition in the container to obtain a cleaning liquid,
From the first cleaning opportunity to the last cleaning opportunity, the amount of the composition in the container is maintained at a filling rate of 15% (volume ratio) or more and a filling amount of 200 mL to 50 L.
The present invention relates to a method for cleaning a hard surface.

The present invention also includes (A) an alkali agent, (B) a calcium compound, (C) a hydroxycarboxylic acid having 1 to 4 hydroxyl groups and 2 to 4 carboxyl groups in the molecule, or an alkali metal salt thereof, One or more selected from ammonium salt or alkanolamine salt, and (D) phosphonic acid or alkali metal salt thereof, ammonium salt or alkanolamine salt, and polymeric carboxylic acid or alkali metal salt thereof, ammonium salt or alkanolamine salt A method for cleaning a hard surface using an aqueous liquid detergent contained in a container, comprising filling an aqueous liquid detergent composition containing a compound into a container having a capacity of 200 ml or more, the container containing the composition. ,
At each cleaning opportunity, the aqueous liquid detergent composition in the container is discharged to obtain a cleaning liquid, and the amount of the composition in the container is less than 15% (volume ratio) and less than 200 mL filling amount The composition in the container is used up within 60 days from the point of becoming at least one of
The present invention relates to a method for cleaning a hard surface.

The present invention also includes (A) an alkali agent, (B) a calcium compound, (C) a hydroxycarboxylic acid having 1 to 4 hydroxyl groups and 2 to 4 carboxyl groups in the molecule, or an alkali metal salt thereof, One or more selected from ammonium salt or alkanolamine salt, and (D) phosphonic acid or alkali metal salt thereof, ammonium salt or alkanolamine salt, and polymeric carboxylic acid or alkali metal salt thereof, ammonium salt or alkanolamine salt A method for using an aqueous liquid detergent contained in a container, comprising filling an aqueous liquid detergent composition containing a compound into a container having a capacity of 200 mL or more, and a container containing the composition.
In order to obtain a cleaning liquid, the composition is discharged from the container at every cleaning opportunity,
The last washing for using up the composition in the container within 60 days from the time when the amount of the composition in the container becomes at least one of the filling rate of less than 15% (volume ratio) and the filling amount of less than 200 mL. Create an opportunity,
Regarding usage.

  The present invention also includes (A) an alkali agent (hereinafter referred to as component (A)), (B) a calcium compound (hereinafter referred to as component (B)), (C) 1-4 hydroxyl groups in the molecule. Hydroxycarboxylic acid having 2 to 4 carboxyl groups, or an alkali metal salt, ammonium salt or alkanolamine salt thereof (hereinafter referred to as component (C)), and (D) phosphonic acid or an alkali metal salt, ammonium salt or An aqueous liquid detergent composition containing an alkanolamine salt and a polymer carboxylic acid or one or more compounds selected from an alkali metal salt, ammonium salt or alkanolamine salt thereof (hereinafter referred to as “component (D)”) In a container that has a capacity of 200 ml to 50 liters and is made of plastic, the filling rate is 15% or more. And formed by filling with a filling amount 200ML～50L, it relates packaged aqueous liquid detergent.

  ADVANTAGE OF THE INVENTION According to this invention, the washing | cleaning method of the hard surface which can maintain stability of a composition from the start to the end of use is provided using a predetermined aqueous liquid cleaning composition. The aqueous liquid detergent composition according to the present invention is also excellent in detergency, aluminum corrosion prevention, and poorly soluble scale adhesion prevention.

[Aqueous liquid detergent composition]
<(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>
The (B) component calcium compound plays a role of reducing metal corrosion, particularly surface corrosion of an aluminum material, through interaction with the (C) component. The component (B) is preferably a compound that releases calcium ions in the aqueous liquid detergent composition of the present invention or in a dilute aqueous solution of the 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) The compounding quantity of a component is 0.003 to 10 weight% in a composition, and also 0.1 to 5 weight% is preferable. Moreover, in this invention, it is from a viewpoint of aluminum anticorrosive property to mix | blend (B) component in an aqueous liquid detergent composition so that it may be used as a washing | cleaning medium whose calcium atom concentration derived from (B) is 10 ppm or more. More preferred.

<(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 phosphonic acid or its alkali metal salts, ammonium salts or alkanolamine salts, 1-hydroxyethane-1,1-diphosphonic acid "CH ₃ C (OH) [PO (OH) _{2] 2"} (approximately: 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. (D) As a preferable compounding quantity of a component, it is 0.01 to 10 weight% in a composition, More preferably, it is 0.05 to 5 weight%, More preferably, it is 0.1 to 3 weight%, and still more The content is preferably 0.2 to 2% by weight, and by adjusting within these ranges, both aluminum corrosion resistance and scale prevention can be achieved.

<(E) component>
The aqueous liquid cleaning composition according to the present invention may further contain chlorite as the component (E) in order to improve the 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 aqueous liquid detergent composition according to the present invention, in order to further enhance the foaming property, emulsification detergency of oil stains, storage stability, etc., as the component (F), a surfactant, for example, An anionic surfactant, a nonionic surfactant, and an 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 surfactant salt 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 aqueous liquid detergent composition according to the present invention in the range of 0.05 to 30% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 1. 15% by weight.

  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. .

  In addition, a magnesium compound [hereinafter referred to as (G) component] can be blended as a component that brings about an effect of imparting more excellent stability in the presence of the component (B). As the component (G), specifically, water-soluble magnesium salts such as magnesium acetate, magnesium chloride, and magnesium nitrate are preferable. Of these, magnesium acetate and magnesium chloride are preferred. (G) The compounding quantity of a component is 0.001-1.8 weight% in a composition, Furthermore, 0.005-0.9 weight%, Furthermore, 0.01-0.2 weight% is preferable.

  The component (B) is preferably one or more compounds selected from acetates and chlorides. Moreover, when (B) component and (G) component coexist, it is preferable that at least one is 1 or more types of compounds chosen from acetate and a chloride.

  In the aqueous liquid detergent composition according to the present invention, from the viewpoint of storage stability and aluminum corrosion resistance, the molar ratio of (G) / (B) is preferably 0.02 to 0.2, more preferably 0.8. It is 03-0.2, More preferably, it is 0.03-0.1.

<Other optional components>
The aqueous liquid detergent composition according to the present invention comprises the above components (A) to (D) and, if necessary, further blended with (E) to (G), and further, as optional components. , Solvents, fragrances, colorants, preservatives, viscosity modifiers and the like.

[Aqueous liquid cleaning agent in a container]
The container-containing aqueous liquid detergent of the present invention is obtained by filling a predetermined container with the above-described aqueous liquid detergent composition according to the present invention.

Various points such as material, storage volume, shape, and thickness are considered as the container. In the present invention, the composition is stored from the viewpoint of quality stability in long-term storage of the composition. Material, that is, the material of the storage wetted part and the storage volume are very important. Examples of the material of the containing liquid contact portion include plastics typified by fluorine resins such as polyethylene, polypropylene, vinyl chloride resin, and polytetrafluoroethylene, metals such as stainless steel and titanium, and glasses. Although not limited in any way, a plastic material is preferable, and polyethylene and polypropylene are particularly preferable. In the case of a container carried by the user by hand, the capacity of the container is preferably 200 mL to 50 L, more preferably 2 L to 30 L, and most preferably 3 to 25 L. In addition, there are cases where a large quantity of factories and facilities are supplied in containers exceeding 100L. In that case, drums (about 100～200L), the form of such a container (300L~2m ³⁾ are preferred. When the size is further increased, the product may be supplied in bulk and stored in a tank ( ^{3 to} 50 m ³ ). In the washing | cleaning method of this invention, the capacity | capacitance of the accommodating part of the composition in a container is 200mL-50L, Furthermore, what is 200mL-30L is suitable.

  Depending on the composition, there is a possibility that it may be sensitive to the influence of light and cause a deterioration in quality. In such a case, an opaque container or a container in which an ultraviolet absorber is embedded is preferable for the purpose of imparting light shielding properties. In the case of a composition containing a pigment, a fragrance or the like, sufficient consideration is required. In addition, since the chlorite of the component (E) is also highly sensitive to light, a light shielding container is preferable.

  As a filling amount, it is preferable to store 200 mL or more in a container from the viewpoint of quality stability in long-term storage of the composition. When a small amount of the present composition is filled, the composition may be deteriorated in quality, such as turbidity and precipitation, in a long-term storage stage. More preferably, it is 200 mL, More preferably, it is 2 L or more, and 3 L or more is optimal. Therefore, as described above, the capacity of the container is 200 mL or more. Moreover, about the filling rate of the composition initially filled in a container, 15% (volume ratio) or more is preferable with respect to the accommodation volume of the container, 20% (volume ratio), and further 50% (volume ratio) or more, It is more preferable from the viewpoint of quality stability in long-term storage. In addition, this filling rate is the ratio which the volume (S2) of a composition occupies with respect to the volume (S1) of the space provided in the accommodating part of a container in order to accommodate a composition. Accordingly, the filling rate is a value (volume%) obtained by (S2 / S1) × 100.

  The container-containing liquid cleaning agent of the present invention is preferably applied to an object to be cleaned after diluting the aqueous liquid cleaning composition according to the present invention to 1 to 100% by weight. A more preferable dilution concentration is 2 to 20% by weight, still more preferably 2 to 10% by weight. Specifically, when the composition according to the present invention is used, the component (A) is 0.01 to 10% by weight, further 0.05 to 2% by weight, and the component (B) is 0.003 to 5% by weight. Furthermore, 0.01 to 1 wt%, (C) component 0.01 to 10 wt%, further 0.03 to 2 wt%, (D) component 0.003 to 3 wt%, further 0.01 to It is preferably used as a cleaning liquid containing 1% by weight. The composition containing each component at these concentrations from the beginning can be used as it is without being diluted.

  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.

[Cleaning method]
The present invention relates to an appropriate method for using the aqueous liquid detergent composition of the present invention as described above. In the cleaning method of the present invention, the aqueous liquid detergent composition according to the present invention is accommodated in a predetermined container, and a cleaning liquid is obtained at each cleaning opportunity, for example, in order to prepare a diluted solution of the composition. A method for cleaning a hard surface, wherein the composition is discharged.

  In this cleaning method, a predetermined amount of the composition (stock solution) is discharged from the container at every cleaning opportunity and used as it is or for the preparation of a diluting solution, but the amount of the composition in the container is reduced accordingly. In the present invention, during the first cleaning opportunity to the last cleaning opportunity, the amount of the composition in the container is 15% (volume ratio) or more, preferably 20% or more, more preferably, the capacity of the container containing the composition in the container. Is maintained at a filling rate of 30% or more, more preferably 50 to 95%. Thereby, the composition in a container is kept stable and precipitation, suspension, etc. do not generate | occur | produce. In order to maintain the above range, the amount of the composition in the container may be monitored and the composition may be replenished as appropriate. In order to monitor the amount of the composition in the container, it is possible to mark a predetermined part of the container [for example, a part where the filling rate is 15% (volume ratio) or more]. In addition, in the present invention, after maintaining the filling rate, the amount of the composition in the container is further maintained at a filling amount of 200 mL to 50 L, and the specific filling amount at that time is the capacity of the container It changes in conjunction with the filling rate. In the cleaning method of the present invention, when the amount of the composition in the container becomes at least one of less than 15% (volume ratio) of the capacity of the container containing the composition in the container and less than 200 mL of the filling amount, The composition can be refilled in a container. Further, the composition in the container is within 60 days, more preferably within 30 days from the time when the amount of the composition in the container becomes at least one of a filling rate of less than 15% (volume ratio) and a filling amount of less than 200 mL. It is preferable to use up everything. That is, within 60 days from the time when the amount of the composition in the container becomes at least one of a filling rate of less than 15% (volume ratio) and a filling amount of less than 200 mL, and further within 30 days, It is a preferred method of use to provide a final cleaning opportunity to use up.

  Also, the interval from the first cleaning opportunity (the time when the composition contained in the container is used for the first cleaning) to the last cleaning opportunity (the time when the composition contained in the container is used for the last cleaning) is 1 It is preferable to be -120 days, further 1-60 days, and more preferably 1-30 days.

  The diluted composition is used as a cleaning liquid for cleaning hard surfaces. The dilution concentration is as described above.

  When a processing area such as a production line in a food processing factory is large, a foam washer is suitably used for cleaning the hard surface. In large-scale equipment such as a freezer and a beverage filling machine, an automatic operation foam cleaning system using an installed foam cleaning machine is employed. In this automatic operation foam cleaning system, a diluting liquid or foaming liquid of an arbitrary concentration is adjusted by a foam washer and supplied to an object to be cleaned through a pipe, and distributed by foam from an existing nozzle. The cleaning method of the present invention can be incorporated into such a system.

  Although the rinsing step is carried out for a certain period of time after foaming, the rinsing water does not necessarily pass through the same path as the diluent or foaming liquid of the cleaning composition. In other words, the diluent or foaming liquid of the cleaning composition remains in the pipe or the foam cleaning machine, and is not pushed out until the next operation. Therefore, when the frequency of the cleaning operation is once a day, the diluted solution of the cleaning agent composition that has been subjected to the spraying remains in the pipe or the foaming machine for about one day. In this case, a diluted solution of a cleaning composition that is stable for at least one day, preferably about three days is required. If the stability is insufficient and a precipitate derived from (B) or the like is generated, it will adhere to the inner wall of the pipe or the bubble washer, which is often a problem.

  Further, in the cleaning method using a movable foam cleaner (for example, “SCU-HF” manufactured by Spraying Co., Ltd., “KF-100” manufactured by Kao Corporation), etc., it is the same as the automatic operation foam cleaning system. Problems can arise. If the processing area is small, such as cooking utensils such as chopping boards and fixtures, and equipment, hand sprayers that can generate bubbles, such as trigger sprayers and former players, are preferably used. Problems can occur. Since the pressure of the gas to be mixed cannot be ensured as high as that of the bubble washer, the hand sprayer may cause nozzle clogging when the precipitate derived from the component (B) is generated.

  In the cleaning composition, the stability derived from 1 to 3 days can be obtained for a solution obtained by diluting the precipitate derived from the component (B) to 1 to 100% by weight of the cleaning composition.

  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 3 to 50 times, more preferably 5 to 40 times, and particularly preferably 7 to 30 times. When a hand sprayer such as a trigger sprayer or a foam player is used, the expansion ratio is preferably 2 to 30 times, more preferably 2 to 20 times, and particularly preferably 3 to 10 times.

  The aqueous liquid detergent composition shown in Table 1 was prepared, and the following storage stability test and performance evaluation were performed. The results are shown in Tables 2, 3 and 4.

(Storage stability test)
Fill the composition shown in Table 1 into a high-density polyethylene container (manufactured by NIKKO, standard bottle natural) to 100% (volume ratio) and 20% (volume ratio) of the announced capacity, and seal with a cap. It preserve | saved in the electric dryer which temperature-controlled at 50 degreeC, and the external appearance change of the composition was observed. The composition filling ratio with respect to the accommodation volume at that time was 91% (volume ratio) and 18% (volume ratio), respectively. That is, in this test, the filling rate was calculated on the assumption that a space larger than the published capacity of each container was a housing part (volumes are as shown in Tables 2 and 3). The criteria for appearance were evaluated as follows.
* Appearance criteria ◎: Abnormalities such as turbidity and precipitation were not observed for more than 8 weeks ○: Abnormalities such as turbidity and precipitation were observed from 4 to 8 weeks △: Slightly less than 4 weeks Abnormalities such as turbidity and minute amounts of precipitation were observed. X: Abnormalities such as obvious turbidity and precipitation were observed in less than 4 weeks.

<Performance evaluation>
The compositions of Examples 5 and 9 and Comparative Examples 2 and 4 used in the storage stability test were stored for 8 weeks, and then subjected to the following detergency test, aluminum corrosion test, and scale adhesion test. Performance evaluation was performed. About the composition in which precipitation etc. have arisen, it sampled so that precipitation might be included as much as possible, without performing homogenization operation, such as stirring, and used for the test. About the same composition, the same performance evaluation was implemented before the storage test, and the comparative evaluation was carried out.

(Detergency test)
The surface of an iron plate (15cm x 30cm) polished and polished with 240 sandpaper is uniformly coated with 1.5g of rapeseed oil, heat treated in an oven at 180 ° C for 1 hour, and a modified oil stain test piece It was created. Absorbent cotton (1 cm × 2 cm) was placed on the modified oil-stained test piece, and 1 g of a 10% by weight aqueous solution of the detergent composition shown in Table 4 was dropped on the absorbent cotton and left at 25 ° C. for 15 minutes. 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 ◎: The oil layer has been completely removed. Δ: The oil layer has been partially removed, or swelling has been observed and discolored.
×: Almost no change in oil layer

(Aluminum corrosion test)
An aluminum test piece (JIS A1050 alumite sulfate treatment, 3 cm × 8 cm × 0.1 cm, Nippon Test Panel Co., Ltd.) is installed at an angle of about 45 degrees. To this, 13 mL of a diluted solution of the cleaning composition shown in Table 4 previously diluted with sterilized water to 5% by weight is distributed from the nozzle for 1 second [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 ○: Partially white corrosion is observed, but there is no problem in practical use △; Corrosion that turns completely white is observed

(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) Was determined according to the following criteria.
* Criteria ◎: No change △: Rainbow-like change is observed ×: Whitening is observed partially or entirely

Claims (5)

(A) Alkaline agent, (B) Calcium compound, (C) 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 And an aqueous liquid containing (D) one or more compounds selected from (D) phosphonic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof, and a polymeric carboxylic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof A method for cleaning a hard surface using an aqueous liquid detergent contained in a container, wherein the detergent composition is filled in a container having a container containing the composition having a capacity of 200 mL or more,
For each cleaning opportunity, drain the aqueous liquid detergent composition in the container to obtain a cleaning liquid,
From the first cleaning opportunity to the last cleaning opportunity, the amount of the composition in the container is maintained at a filling rate of 15% (volume ratio) or more and a filling amount of 200 mL to 50 L.
How to clean hard surfaces. (A) Alkaline agent, (B) Calcium compound, (C) 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 And an aqueous liquid containing (D) one or more compounds selected from (D) phosphonic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof, and a polymeric carboxylic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof A method for cleaning a hard surface using an aqueous liquid detergent contained in a container, wherein the detergent composition is filled in a container having a capacity containing 200 ml or more of the container.
At each cleaning opportunity, the aqueous liquid detergent composition in the container is discharged to obtain a cleaning liquid, and the amount of the composition in the container is less than 15% (volume ratio) and less than 200 mL filling amount The composition in the container is used up within 60 days from the point of becoming at least one of
How to clean hard surfaces.   The cleaning method according to claim 1 or 2, wherein the container of the composition in the container is made of plastic. (A) Alkaline agent, (B) Calcium compound, (C) 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 And an aqueous liquid containing (D) one or more compounds selected from (D) phosphonic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof, and a polymeric carboxylic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof A method for using an aqueous liquid detergent contained in a container, wherein the detergent composition is filled in a container having a capacity containing 200 mL or more of the container.
In order to obtain a cleaning liquid, the composition is discharged from the container at every cleaning opportunity,
The last washing for using up the composition in the container within 60 days from the time when the amount of the composition in the container becomes at least one of the filling rate of less than 15% (volume ratio) and the filling amount of less than 200 mL. Create an opportunity,
how to use.   (A) Alkaline agent, (B) Calcium compound, (C) 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 And an aqueous liquid containing (D) one or more compounds selected from (D) phosphonic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof, and a polymeric carboxylic acid or an alkali metal salt, ammonium salt or alkanolamine salt thereof A container-containing aqueous liquid comprising a cleaning agent composition filled in a container having a capacity of 200 mL to 50 L in the container and made of plastic with a filling rate of 15% or more and a filling amount of 200 mL to 50 L. Washing soap.