JP2020019890A - Detergent composition for hard surface automatic washing machine - Google Patents

Abstract

To provide a detergent composition for a hard surface automatic washing machine having all of a glass corrosion inhibition function, a washing function, a scale generation inhibition function or the like.SOLUTION: A detergent composition contains (A) alkali agent, (B) amino carboxylic acid chelator, (C) aluminum compound, (D) organic carboxylic acid, and (E) polyelectrolyte polymer, the content of the (D) organic carboxylic acid relative to the (C) aluminum compound being 4-120 in mass.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a detergent composition for an automatic hard surface washer used when washing a hard surface of tableware, various containers, utensils, and the like with an automatic washer.

  2. Description of the Related Art Conventionally, automatic dishwashers have been widely used in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like to efficiently wash used dishes. In addition to tableware, various automatic washing machines are used in various manufacturing factories, processing factories, and the like to wash utensils, containers, plastic containers used for distribution, and the like.

  As a cleaning composition used in such an automatic cleaning machine for hard surface cleaning, a composition mainly containing an alkali agent and a chelating agent is generally used, but a glass cup using the above cleaning composition is generally used. When washing glass products such as, the metal ions in the glass are eluted by the chelating agent in the detergent composition, the glass surface is easily eroded by the alkali agent, the glass is cracked or chipped, the alkali is burned or whitened There is a problem that the appearance deteriorates due to the phenomenon.

  Further, a coating of a mineral component generated on the glass surface when water having high hardness is used for cleaning, and formation of a water spot due to residual adhesion of the cleaning component or reattachment of dirt also impair the appearance of the glass surface after cleaning. It is a factor.

  In the food and beverage industry, especially for high-end end-users, the beauty of the glass tableware handled is of particular importance.In this way, glass tableware washed using an automatic dishwasher can be completely beautiful. Since it is difficult, it is necessary to polish it with human hands, resulting in large labor costs.

  In addition, when used repeatedly, the glass surface is eroded and easily scratched as described above, so the frequency of cracking and chipping (breakage) of the glass tableware increases, and enormous costs are required for replacing and refilling the glass tableware. It depends.

  In view of the above, there have been proposed a number of cleaning compositions that claim to be excellent in cleaning properties and finish properties, particularly for glass surfaces. For example, Patent Document 1 described below discloses that “(A) 20 to 80% by mass of an alkali metal carbonate, (B) 1 to 40% by mass of a chelating agent, and (C) 0.1 to 10% by mass of a nonionic surfactant. % Of an enzyme, (D) 0.1 to 5% by mass of an enzyme, and (E) 0.1 to 10% by mass of a polycarboxylic acid or a salt thereof. The corrosion constant for Pb (II) and the stability constant for Ca (II) in a specific range, at any pH in the range of 0.0, to corrode the glass. And exhibits excellent cleaning performance without forming a lime film or a water spot. "

  Patent Document 2 below discloses “(a) 5 to 60% by weight of an alkali metal hydroxide, (b) 5 to 50% by weight of a sequestering agent, and (c) 0.01 to 10% by weight of an aluminum compound. % Or a hard surface cleaning composition containing (a) to (c), and another component copolymerizable with maleic acid or maleic anhydride represented by a specific formula as a component (d). A hard surface cleaning composition containing a copolymer obtained from a monomer or a water-soluble salt thereof has excellent detergency and ability to inhibit scale formation, even for crystal glass and the like. '' It has been done.

JP 2006-265463 A JP 2000-345194 A

  However, in the cleaning composition of Patent Document 1, the desired detergency cannot be obtained because the metal stability of the chelating agent is limited. Further, when the alkalinity is increased to increase the detergency, the effect of the chelating agent on inhibiting corrosion of the glass is reduced, which may affect the glass surface.

  Further, in the cleaning composition of Patent Document 2, the presence of an aluminum compound exerts a corrosion inhibitory effect on glass, but cannot suppress both surface discoloration and weight loss of glass, and either of them is insufficient. become. In addition, when the detergent composition is used after being diluted, if the hardness of water is high, the ability to suppress scale formation is reduced by the aluminum compound.

  As described above, the conventional cleaning composition does not have both the corrosion inhibitory ability for hard surfaces, particularly glass, and the general washing ability and scale formation inhibiting ability. There is a strong demand for providing a detergent composition that gives a feeling.

  The present invention has been made in view of such circumstances, and in particular, has both a corrosion inhibiting ability for glass and a washing performance, a scale formation inhibiting ability, and is used for an automatic hard surface washing machine capable of obtaining a high-quality finished feeling. The purpose is to provide a cleaning composition.

  In order to achieve the above object, the present invention provides (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, (C) an aluminum compound, (D) an organic carboxylic acid, and (E) a polymer electrolyte polymer. The cleaning composition for a hard surface automatic cleaning machine, wherein the content ratio (D / C) of the organic carboxylic acid (D / C) to the aluminum compound (C) is 4 to 120 on a mass basis. The agent composition is a first gist.

  In addition, among the above, the present invention particularly provides a detergent composition for an automatic hard surface washer containing the above-mentioned (C) aluminum compound in an amount of 0.05 to 6% by mass based on the whole composition. The third gist of the present invention is a detergent composition for an automatic hard surface washer in which the organic carboxylic acid (D) is contained in an amount of 5 to 30% by mass based on the whole composition.

Further, among these, the ratio of the chelating power Y of the (B) aminocarboxylic acid-based chelating agent to the alkalinity X of the (A) alkali agent (Y / X: numerical ratio, the same applies hereinafter) is preferred. , 1.5 to 9, wherein the alkalinity X of the alkali agent (A) in the composition is set to 2 to 14% in terms of KOH. A fifth aspect of the present invention is a cleaning composition for an automatic hard surface washer in which the chelating power Y of the (B) aminocarboxylic acid-based chelating agent in the composition is set to 15 to 60 CaCO ₃ mg / g.

  And among these, this invention especially makes the above-mentioned (E) the cleaning composition for hard surface automatic cleaners containing 0.5-6 mass% with respect to the whole composition the polymer electrolyte polymer. According to a sixth aspect, a cleaning composition for a hard surface automatic washing machine, which contains water together with the components (A) to (E) and is prepared as a liquid, is a seventh aspect.

  That is, the present inventor has conducted intensive studies to solve the above problems, and as a result, (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, (C) an aluminum compound, (D) an organic carboxylic acid, And (E) the detergent composition containing the polymer electrolyte polymer, in particular, the content ratio (D / C) of the (D) organic carboxylic acid to the (C) aluminum compound is 4 to 120 on a mass basis. It has been found that in the case of, the corrosion inhibitory effect on glass is effectively exhibited while maintaining excellent cleaning properties.

  Further, according to the above configuration, the action of the organic carboxylic acid (D) can suppress a decrease in the scale suppressing ability due to aluminum, and when the cleaning composition is a liquid containing (F) water, It has been found that the above (D) organic carboxylic acids suppress precipitation of the aluminum compound in the composition, and a homogeneous and easy-to-use detergent composition can be obtained.

  In the present invention, “organic carboxylic acids” mean at least one compound selected from organic carboxylic acids and salts thereof.

  The cleaning composition for a hard surface automatic cleaning machine of the present invention (hereinafter sometimes abbreviated as “cleaning composition”) comprises (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, and (C) an aluminum compound. , (D) organic carboxylic acids, and (E) a detergent composition containing a polymer electrolyte polymer, in particular, the content ratio of the above (D) organic carboxylic acids to the above (C) aluminum compound (D / C) Is 4-120 on a mass basis.

  The above-mentioned detergent composition has excellent detergency and suppresses corrosiveness to glass. In addition, the presence of the organic carboxylic acids (D) can suppress a decrease in the scale-inhibiting ability due to aluminum, and when the detergent composition is a liquid containing (F) water, the organic solvent (D) Since the precipitation of the aluminum compound (C) in the composition is suppressed by the carboxylic acids, the detergent composition has a stable appearance and is homogeneous and easy to use.

  In the present invention, particularly, those in which the above-mentioned (C) aluminum compound accounts for 0.05 to 6% by mass based on the whole composition are particularly those having anticorrosive properties against glass (synonymous with corrosion inhibitory properties, hereinafter the same). And the system stability is excellent, which is preferable.

  Further, among the present invention, those containing (D) the organic carboxylic acid in an amount of 5 to 30% by mass with respect to the whole composition are particularly excellent in scale formation suppressing performance and system stability. It is suitable.

  Furthermore, among the present invention, in particular, the ratio (Y / X) of the chelating power Y of the (B) aminocarboxylic acid-based chelating agent to the alkalinity X of the (A) alkali agent is 1.5 to 9; Some of them are particularly preferable because they have both excellent anticorrosion properties and cleaning properties against glass.

In the present invention, in particular, the alkalinity X of the alkali agent (A) is set to 2 to 14% in terms of KOH, and the chelating power Y of the aminocarboxylic acid-based chelating agent (B) in the composition. Is set to 15 to 60 CaCO ₃ mg / g, which is particularly excellent in both the anticorrosion property and the cleaning property for glass, and is also suitable.

  Among the present invention, those containing (E) the polyelectrolyte polymer in an amount of 0.5 to 6% by mass based on the whole composition are particularly suitable for the scale generation suppressing performance, cleaning performance and system performance. Are excellent in any of the above balances, which is preferable.

  Further, among the present invention, those containing (F) water together with the above-mentioned components (A) to (E) and being prepared as a liquid do not spatter like powders and particles, It does not require the trouble of replacing the cartridge as in the case of the solid, and is convenient and convenient.

  Next, an embodiment for carrying out the present invention will be described in detail.

  The cleaning composition of the present invention contains (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, (C) an aluminum compound, (D) an organic carboxylic acid, and (E) a polymer electrolyte polymer. It is.

  The above (A) alkali agent is blended for the purpose of improving detergency, and (A) the alkali agent is a hydroxide of an alkali metal such as sodium hydroxide (NaOH) or potassium hydroxide (KOH). / Silicates such as sodium silicate and potassium silicate / inorganic alkali agents such as carbonates such as sodium carbonate and potassium carbonate, and organic alkali agents such as alkanolamines such as monoethanolamine (MEA), diethanolamine and triethanolamine Is raised.

  The component (A) may be used alone or in combination of two or more. Of these, inorganic alkali agents are preferred from the viewpoint of detergency, and alkali metal hydroxide salts are particularly preferred.

  The content of the component (A) is not particularly limited, but the alkalinity X of the component (A) in the composition is calculated as KOH as long as the cleaning performance is maintained and the corrosion resistance of the glass is less reduced. Is preferably adjusted to be in the range of 2 to 14%. That is, if the alkalinity X is too low, the cleaning performance may decrease, and if the alkalinity X is too high, the glass anticorrosive effect may not be easily obtained. The alkalinity X is particularly preferably from 3 to 13%, and more preferably from 4 to 11%.

The “alkalinity X (KOH equivalent)” is measured by subjecting the detergent composition to neutralization titration with a 0.1 mol / L hydrochloric acid normal solution using a phenolphthalein indicator. This is a value calculated by the following general formula (1) with the point at which the pink color of the indicator disappears as the end point.
Alkalinity X (KOH equivalent)
= 0.1 × F × A × 56.1 / mass of sample (g) × 10 (1)
A: Titration of 0.1 mol / L hydrochloric acid normal solution (mL)
F: Factor of 0.1 mol / L hydrochloric acid normal solution

  The aminocarboxylic acid-based chelating agent (B) used in the cleaning composition of the present invention is compounded for the purpose of improving the ability to suppress scale formation, the stability of the system, and the cleaning property against oil stains. The component (B) includes ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, and methylglycinediacetic acid (MGDA). , Glutamic acid diacetate (GLDA), triethylenetetramine hexaacetic acid, ethylene glycol ether diaminetetraacetic acid, hydroxyethyl iminodiacetic acid (HIDA), cyclohexane-1,2-diaminetetraacetic acid, diencoric acid, dicarboxymethylglutaric acid, hydroxy Ethyl ethyl Njiamintori acetate, L- aspartic acid -N, N-diacetic acid (ASDA), and their alkali metal salts. These may be used alone or in combination of two or more.

  Among the above components (B), it is preferable to use NTA, MGDA, GLDA, and HIDA, particularly from the viewpoints of the ability to suppress scale formation, the stability of the system, and the excellent cleaning effect on oil stains. .

The content of the component (B) itself is not particularly limited, but the component (B) in the composition is defined as a range in which the reduction in the anticorrosiveness of the glass is small while maintaining the performance of suppressing scale formation and the performance of cleaning oil stains. Is preferably adjusted so that the chelating force Y of 15 to 60 mg / g of CaCO ₃ . That is, if the chelating force Y is too low, the scale generation suppressing performance and the oil stain cleaning performance tend to decrease. Conversely, if the chelating force Y is too high, the influence on the glass increases, Have a tendency to corrode. The above chelating force Y is particularly preferably a 18~52CaCO ₃ mg / g, it is 20~40CaCO ₃ mg / g are, wash performance in balance with other components, that the influence of the glass Is even more preferred.

The "chelating power Y" is measured by subjecting the detergent composition to substitution titration with a 0.01 mol / L calcium chloride normal solution using an eriochrome black T indicator. It is a value calculated by the following general formula (2), with the point at which the color changes from blue to magenta as the end point.
Chelation force Y (CaCO ₃ equivalent)
= 0.01 × F × A × 100/147 / mass of sample (g) × 100 (2)
A = Titration of 0.01 mol / L calcium chloride normal solution (mL)
F = Factor of 0.01 mol / L calcium chloride standard solution

  In addition, in the content ratio of the (A) alkali agent and the (B) aminocarboxylic acid-based chelating agent, the ratio of the chelating power Y of the (B) aminocarboxylic acid-based chelating agent to the alkalinity X of the (A) alkali agent (Y / X) is preferably set to be 1.5 to 9, particularly preferably 2 to 8, and more preferably 2.5 to 7. That is, in the above ratio (Y / X), if the ratio of the chelating force Y is too large, the corrosion resistance to glass tends to decrease, and if it is too small, the cleaning performance tends to decrease. is there.

  In the cleaning composition of the present invention, the aluminum compound (C) used together with the above-mentioned components (A) and (B) includes sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide Aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, potassium aluminum sulfate, and the like.

  The component (C) serves to reduce the effect of corrosion on glass, and among them, sodium aluminate and potassium aluminum sulfate are preferably used.

  The above component (C) may be used alone or in combination of two or more, and the content thereof is not particularly limited. However, the content ratio with the (D) organic carboxylic acid described below is important, and the content ratio (D / C) of the component (D) to the component (C) needs to be 4 to 120 on a mass basis. is there. That is, by adjusting the content ratio of both, as described above, not only excellent cleaning properties and stability of the system, but also extremely excellent anticorrosion property against glass can be exhibited. In terms of the above effects, the content ratio (D / C) is more preferably 5 to 100, and further preferably 7 to 50.

  In addition, on the premise that the content ratio (D / C) is satisfied, it is preferable that the component (C) is set to 0.05 to 6% by mass with respect to the entire detergent composition. . That is, when the amount of the component (C) is too small, the anticorrosion effect on glass tends to be small. On the other hand, if the amount of the component (C) is too large, the stability of the system tends to decrease, and the generation of scales derived from the aluminum compound tends to increase. The content of the component (C) is preferably set in the range of 0.3 to 4.5% by mass, and more preferably 0.5 to 3% by mass, from the viewpoint of the anticorrosion effect and the stability. The range is optimal.

  Further, the organic carboxylic acid as the component (D) is used for suppressing the scale generated when aluminum and the water hardness component coexist in the cleaning solution. When the detergent composition is a liquid, it also has the effect of suppressing the precipitation of aluminum compounds.

  Examples of the component (D) include citric acid, gluconic acid, oxalic acid, tartaric acid, malic acid, succinic acid, and salts thereof. These may be used alone or in combination of two or more. Among them, it is preferable to use citrate and gluconate in terms of effects.

  The content of the component (D) is not particularly limited as well as the component (C), but as described above, the content ratio of the component (D) to the component (C) (D / C) Needs to be 4 to 120 on a mass basis. The reason is as described above.

  In addition, on the premise that the content ratio (D / C) is satisfied, it is preferable that the component (D) is set to 5 to 30% by mass with respect to the entire detergent composition. That is, when the amount of the component (D) is too small, the ability to inhibit scale formation tends to decrease, and when the detergent composition is a liquid, the effect of preventing precipitation of an aluminum compound tends to decrease. On the other hand, if the amount of the component (D) is too large, it is not easy to balance with other components. Particularly, when the detergent composition is a liquid, the effect on the stability of the system is large, and the balance is obtained. Can be even more difficult. The content of the component (D) is more preferably 10 to 25% by mass, and particularly preferably 11 to 21% by mass.

  In the present invention, the (E) polyelectrolyte polymer is compounded for the purpose of improving sequestering effect, threshold effect, dispersing performance of water-insoluble substance, anti-redeposition performance, cleaning performance, and the like. It is. The component (E) includes, for example, acrylic acid polymers and salts thereof, maleic acid polymers and salts thereof, acrylic acid-maleic acid copolymers and salts thereof, poly-α-hydroxyacrylic acid and salts thereof, acrylic Acid-maleic acid-polyethylene glycol copolymer and its salt, olefin-maleic acid copolymer and its salt, acrylic acid-sulfonic acid copolymer and its salt. These salts include sodium salt, potassium salt, ammonium salt and ethanolamine salt, and among them, sodium salt and potassium salt are preferable. The salts of the above-mentioned polymers and copolymers may be all neutralized salts or partially neutralized salts.

  The component (E) may be used alone or in combination of two or more. And in particular, from the viewpoint of sequestering effect, anti-redeposition performance and cleaning performance, sodium polymaleate, sodium polyacrylate, sodium salt of acrylic acid-maleic acid copolymer, sodium poly-α-hydroxyacrylate, Acrylic acid-maleic acid-polyethylene glycol copolymer, olefin-maleic acid copolymer sodium salt, and acrylic acid-sulfonic acid copolymer sodium salt are preferably used.

  The maleic acid polymer, the acrylic acid polymer, and the salt of the copolymer of maleic acid and acrylic acid can be selected from commercially available products.For example, in the case of sodium polymaleate, the polymaleic acid is added in advance. Can be appropriately prepared by adding sodium hydroxide (neutralization reaction). Therefore, when adding sodium hydroxide and potassium hydroxide, a mixture of sodium polymaleate and potassium polymaleate can be obtained at any ratio.

  When, for example, a maleic acid polymer, an acrylic acid polymer or a salt thereof is used as the component (E), the weight average molecular weight is preferably from 600 to 15,000, and particularly preferably from 1,000 to 15,000. 15,000. Further, for example, when a copolymer of maleic acid and acrylic acid and a salt thereof are used, the weight average molecular weight is preferably from 1,000 to 100,000, and particularly preferably from 3,000 to 80,000. .

  The “weight average molecular weight” can be measured by gel permeation chromatography (GPC).

  The content of the component (E) is preferably set to 0.5 to 6% by mass based on the entire cleaning composition. That is, if the amount of the component (E) is too small, the desired scale formation suppressing ability and cleaning performance tend to be reduced. On the other hand, if the amount of the component (E) is too large, it is difficult to easily adjust the balance as a whole, and storage stability tends to decrease, and a synergistic effect with other components cannot be obtained any more. Be looked at. It is particularly preferable to set the content of the component (E) in the range of 0.5 to 4% by mass from the viewpoint of the ability to suppress scale formation.

  The cleaning composition of the present invention is prepared with the above-mentioned components (A) to (E) as essential components, and can be prepared as a liquid by using (F) water as an optional component.

  Examples of the (F) water include tap water, soft water, ion-exchanged water, pure water, purified water, and the like, and preferably, soft water, ion-exchanged water, and pure water are used. These may be used alone or in combination of two or more.

  The water (F) is the sum of water contained in the form of water of crystallization or an aqueous solution derived from each component constituting the detergent composition of the present invention, and water added from the outside. In this case, the remaining mass% excluding the essential components (A) to (E) and other optional components added as appropriate is the amount of water.

  And, in addition to the above-mentioned essential components (A) to (E) and the optional component (F), various optional components can be appropriately added to the detergent composition of the present invention as needed. Such optional components include coloring agents, fragrances, pH adjusters, bactericides, preservatives, deodorants, antistatic agents, and the like.

  The cleaning composition of the present invention can be prepared by using these components according to a general method for preparing a cleaning composition. The final form of the composition may be a lump solid, powdery or granular. Further, as described above, the liquid detergent composition can be prepared by adding (F) water.

  The cleaning composition of the present invention thus obtained comprises (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, (C) an aluminum compound, (D) an organic carboxylic acid, and (E) It contains a molecular electrolyte polymer and is set so that the content ratio (D / C) of the component (D) to the component (C) is within a specific range.

  According to this configuration, it is possible to have excellent cleaning properties and to greatly suppress the corrosiveness to glass. In addition, the presence of the organic carboxylic acid (D) can suppress a reduction in the scale-inhibiting property due to aluminum. Moreover, when the detergent composition is a liquid containing (F) water, the (D) organic carboxylic acids suppress precipitation of the aluminum compound (C) in the composition, so that the appearance is stable, The resulting detergent composition is homogeneous and easy to use.

  Therefore, when cleaning glassware or the like using the cleaning composition of the present invention, a beautiful appearance can be obtained, so that the conventionally required wiping operation is unnecessary, and labor costs can be significantly reduced. it can. Further, since corrosion deterioration of the glass surface is suppressed, the breakage rate of glass tableware and the like can be significantly reduced, and the cost burden can be reduced.

  The cleaning composition of the present invention is not only suitable for cleaning hard surfaces such as glass, porcelain, metals, and plastics, but also used in various manufacturing factories, processing factories, and the like. It can also be used as an automatic cleaning machine for cleaning containers and the like. In addition, it can be preferably used for cleaning hard surfaces such as tiles and floors in food factories and food processing factories, cleaning containers such as glass bottles and beer bottles for beverages, and cleaning metal surfaces. In particular, it can be suitably used for automatic dishwashers in hotels, restaurants, schools, hospitals, restaurants, catering companies, company cafeterias, and the like.

  In addition, the detergent composition of the present invention is usually 0.02 to 0.5% by mass of a detergent aqueous solution in consideration of the type of stain, the amount (degree) of stain, the quality of water used for washing, and the like. As a result, an excellent finish effect can be obtained for the target object by supplying it to the automatic washing machine.

  Next, examples will be described together with comparative examples. Note that the present invention is not limited to the following embodiments.

[Examples 1 to 35, Comparative Examples 1 to 11]
Detergent compositions having the compositions described in Tables 1 to 10 described below were prepared and evaluated for the following evaluation items. The results are shown in the table below. In addition, the numerical value which shows the composition of each component in a table | surface is shown by the effective content (mass%, pure content conversion) of each component. In addition, specific conditions (such as alkalinity X, chelating power Y, etc.) relating to the materials of each detergent composition are also shown.

[Scale control ability]
Test method The detergent composition was diluted to 0.2% by mass with artificial hard water (total hardness: 150 mg / L), 50 mL was poured into a colorimetric tube having a capacity of 100 mL, and the incubator (IS800, manufactured by Yamato Scientific Co., Ltd.) ) And kept for 4 hours in an atmosphere at 60 ° C., and then the amount of scale generated was visually determined according to the following criteria. In addition, there are scales that float on the test solution and scales that adhere to the bottom and sides of the colorimetric tube, both of which were evaluated.
Evaluation criteria ◎: No scale was generated.
：: Almost no scale was generated.
Δ: Scale was generated.
X: Scale adhesion was remarkable.

[Detergency]
-Test method The prepared detergent composition was put into a commercial automatic dishwasher (DW-RD61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. Then, the following porcelain dishes to be cleaned were cleaned as a set of 10 sheets, and the cleaning performance was evaluated according to the evaluation criteria described later. In addition, beef tallow and egg yolk were prepared as dirt, and each dirt was evaluated for washing.
・ Operating conditions Detergent concentration: 0.2% by mass
Washing temperature: 60 ° C
Rinse temperature: 80 ° C
Cleaning course: Standard cleaning cycle (washing: 43 seconds, rinsing: 15 seconds)
Tap water hardness: 70 to 80 mg / L (as CaCO ₃ )
Tallow dirt: Purified tallow adhering to a porcelain dish having a diameter of 25 cm so as to be 4 g / sheet was used.
Yolk stain: 4 g of egg yolk is attached to a 25 cm diameter porcelain dish, dried at room temperature (about 23 ± 2 ° C) for 1 hour, and immersed in 40 ° C hot water for 30 minutes immediately before washing. Was used.
Evaluation Criteria For tallow dirt, oil red liquid was applied to a porcelain dish after washing, and for yolk dirt, the degree of dirt removal was visually judged according to the following criteria. Note that the oil red liquid contains an azo dye and dyes oils and fats red.
◎: Stain removal of 90% or more ○: Stain removal of 70% to less than 90% △: Stain removal of 50% to less than 70% X: Stain removal of less than 50%

[System stability]
Test Method The prepared detergent composition was placed in a 250 mL polypropylene container, placed in a constant temperature bath (SLI-4S, manufactured by Sunaka Rika Kogyo Co., Ltd.) under an atmosphere of 40 ° C., and stored in that state for one month. Similarly, the prepared detergent composition was put in a 100 mL glass bottle as it was in an undiluted solution, and placed in an atmosphere controlled by a program from −5 ° C. to 5 ° C. by an incubator (MTH-2400, manufactured by SANYO). Stored in the state for one month. These appearances were visually observed, and evaluated based on the following evaluation criteria.
Evaluation criteria ◎: very good (after 1 month, there was no change in appearance such as turbidity, separation and precipitation).
：: Good (after one month, slight changes in appearance such as turbidity, separation, and precipitation were observed).
Δ: Possible (slight changes in appearance such as turbidity / separation or precipitation were observed after 2 weeks).
×: Bad (immediately after compounding, there was an appearance change such as turbidity / separation or precipitation).

[Corrosion protection against soda glass]
(1) Appearance change / test method A commercially available tumbler glass (7 oz soda glass tumbler, manufactured by Toyo Sasaki Glass Co., Ltd.) was immersed in the prepared detergent composition under the following conditions. Then, the state of the tumbler glass after immersion was visually observed and evaluated according to the following evaluation criteria.
・ Immersion conditions Detergent concentration: 0.2% by mass
Immersion temperature: 60 ° C
Immersion time: 1 week ・ Evaluation criteria…: No discoloration or corrosion is observed on the surface of the tumbler glass.
…: The surface of the tumbler glass is slightly discolored.
Δ: Discoloration on the surface of the tumbler glass is large.
×: Corrosion on the surface of the tumbler glass is large.
(2) Weight Change The weight of the tumbler glass used for evaluating the change in appearance was measured before and after immersion, and the presence or absence of a change in weight due to corrosion was evaluated according to the following evaluation criteria.
A: There is no change in weight.
…: Weight change of less than 20 mg, negligible.
Δ: Weight change of 20 mg or more and less than 40 mg, slightly corroded.
×: Weight change of 40 mg or more, large corrosion.

  The results are shown in Tables 1 to 10 below.

  From the above results, it can be seen that the products of Examples 1 to 35 have generally excellent evaluations for all evaluation items. On the other hand, Comparative Examples 1 to 11 in which any one of the components (A) to (E) is not contained or the D / C is not in the range of 4 to 120 even if all of the components are contained, any of the evaluation items In the evaluation of "x", there is a problem in the anticorrosive properties against glass, scale suppression ability and detergency on the finish after cleaning, and the stability of the system related to the handling in use of the detergent composition Understand.

  In Example 34, even if the stability of the system was evaluated as “Δ”, if it was not liquid but powder as in Example 35, it could be stored for a long period without loss of quality. Yes, practically no problem. Similarly, in another example of a liquid, even if the stability of the system is evaluated as “△”, if it is prepared as a solid such as a powder or a block, the quality is stable for a long time. Therefore, there is no practical problem.

  Further, when taking a closer look at the comparative examples, Comparative Examples 1 to 3 containing no (D) organic carboxylic acids as described in Japanese Patent Application Laid-Open No. 2000-345194 show cleaning power and scale. Although the inhibitory ability is sufficient, since it does not contain (D) organic carboxylic acids, the anticorrosion property against glass and the stability of the system are poor. Comparative Example 4 does not contain the aluminum compound (C), and therefore has poor corrosion resistance to glass. In Comparative Example 5, since the (B) aminocarboxylic acid-based chelating agent was not contained, the appearance change of the glass was large, and the scale-inhibiting ability and the detergency against oil were also inferior. Comparative Example 6 does not contain (E) the polymer electrolyte polymer, so that the appearance change of the glass is large and the scale suppressing ability is inferior. Comparative Example 7 does not contain (A) an alkali agent, and thus has anticorrosion properties against glass, but has poor cleaning power and poor system stability. In the absence of the alkali agent (A), the aluminum compound (C) hardly dissolves in the detergent composition, so that the stability of the system decreases.

  In addition, in Comparative Examples 8 to 11, which contain all of the components (A) to (E) but have a D / C outside the range of 4 to 120, Comparative Example 8 in which the D / C is less than 4 is , (C) the aluminum compound is sufficiently contained, but (D) the amount of organic carboxylic acids is small, so that the scale derived from aluminum is slightly generated and the stability of the system is poor. This is due to insufficient dissolution of (C) aluminum compound by (D) organic carboxylic acids. Further, in the case of Comparative Example 9 in which D / C is less than 4 as in Comparative Example 8, the content of (D) organic carboxylic acids is slightly smaller, and (C) aluminum compound is less than (D) organic carboxylic acids. Due to the large amount, the stability of the system and the corrosion resistance of the glass are inferior. This is presumed to be due to insufficient dissolution of the (C) aluminum compound by the (D) organic carboxylic acid, and a reduction in the dissolved aluminum is related to a reduction in the corrosion resistance. In Comparative Examples 10 and 11, D / C exceeds 120, and the corrosion resistance is insufficient because the amount of the aluminum compound (C) is too small.

  INDUSTRIAL APPLICABILITY The present invention can be used particularly for a cleaning composition for a hard surface automatic cleaning machine, which has both a corrosion inhibiting ability for glass, a washing ability, and a scale formation inhibiting ability and can provide a high-quality finished feeling.

Claims (7)

  A cleaning composition comprising (A) an alkali agent, (B) an aminocarboxylic acid-based chelating agent, (C) an aluminum compound, (D) an organic carboxylic acid, and (E) a polymer electrolyte polymer, (C) The detergent composition for an automatic hard surface washer, wherein the content ratio (D / C) of the organic carboxylic acid (D / C) to the aluminum compound is 4 to 120 on a mass basis.   The cleaning composition according to claim 1, wherein the aluminum compound (C) is contained in an amount of 0.05 to 6% by mass based on the whole composition.   The cleaning composition for an automatic hard surface cleaning machine according to claim 1 or 2, wherein the organic carboxylic acid (D) is contained in an amount of 5 to 30% by mass based on the whole composition.   The ratio (Y / X) of the chelating force Y of the (B) aminocarboxylic acid-based chelating agent to the alkalinity X of the (A) alkali agent is from 1.5 to 9, and is in a range of 1.5 to 9. The cleaning composition for a hard surface automatic cleaning machine according to item 6. The alkalinity X of the alkaline agent (A) in the composition is set to 2 to 14% in terms of KOH, and the chelating power Y of the aminocarboxylic acid-based chelating agent (B) in the composition is 15 to 60 CaCO ₃ mg. The cleaning composition for an automatic hard surface cleaning machine according to any one of claims 1 to 4, wherein the cleaning composition is set to / g.   The cleaning composition for a hard surface automatic cleaning machine according to any one of claims 1 to 5, wherein the polymer electrolyte polymer (E) is contained in an amount of 0.5 to 6% by mass based on the whole composition.   The cleaning composition for a hard surface automatic cleaning machine according to any one of claims 1 to 6, comprising (F) water together with the components (A) to (E) and prepared as a liquid.