Cartridge cleaner, cleaning method, method for sterilizing microorganisms or method for removing bacterial flora agglomerates, and method for manufacturing cartridge cleaner

Abstract

To provide a cartridge detergent capable of making damage given to a cleaning object less, and, capable of removing dirt or bacteria accumulated on the cleaning object.SOLUTION: A cartridge detergent for an automatic cleaning machine of a method in which a water-insoluble vessel having a supply port of a content is installed with the supply port directed downward, the content is supplied while dissolving the content by injecting water to the supply port, the content is a solid detergent composition containing an alkali agent (A), a chelate agent (B) and a coated chlorine agent in which the surrounding of the chlorine agent is coated with a coating agent (C), the cartridge detergent is installed to a supply device additional to the automatic cleaning machine, when an effective chlorine concentration of the detergent obtained by dissolving the solid detergent composition in water of 35°C is measured over from use start to use end of the cartridge detergent in a cleaning liquid in which a concentration of the solid detergent composition becomes 0.10 wt%, at least one peak where the effective chlorine concentration in the detergent liquid becomes 15 ppm or higher exists.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a cartridge cleaner, a cleaning method, a method for sterilizing microorganisms or removing bacterial flora agglomerates, and a method for producing a cartridge cleaner. [Background technology]

[0002] In recent years, due to labor shortages, hygiene management, and the like, automatic dishwashers have been used in hotels, restaurants, and the like. Detergent compositions used in such automatic dishwashers may contain a chlorine agent in addition to cleaning components such as alkaline agents and chelating agents. Chlorine agents have the effect of removing pigment stains such as proteins, starches, tea stains, and coffee stains that accumulate on dishes and the like and cause stubborn stains, as well as a disinfecting effect such as killing microorganisms, and are therefore incorporated into detergent compositions in anticipation of these effects.

[0003] In addition, various bacteria may grow inside the automatic dishwasher, causing the dishwasher to become covered with a bacterial colony aggregate (also called a biofilm).To clean such stains, a detergent composition for automatic dishwashers containing a chlorine agent may be used.

[0004] Patent Document 1 discloses a cartridge detergent that can use a solid detergent composition. Patent Document 1 describes that water is sprayed onto the cartridge detergent to obtain a detergent solution (meaning a liquid immediately after dissolving the solid detergent composition), and that the detergent solution is introduced into an automatic dishwasher. Patent Documents 2 and 3 disclose solid detergent compositions containing chlorine bleach. However, they do not mention the concentration of chlorine. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-8267 [Patent Document 2] Japanese Patent Application Laid-Open No. 2017-186549 [Patent Document 3] Japanese Patent Application Publication No. 2018-115296 Summary of the Invention [Problem to be solved by the invention]

[0006] The cartridge detergent is installed in a supply device attached to the automatic dishwasher, and is used repeatedly for multiple washes while supplying the detergent solution little by little. The dishes, etc., that are washed in the automatic dishwasher are used repeatedly in hotels, restaurants, etc. That is, the same cartridge detergent is used to clean the same object on a daily basis.

[0007] As described above, a chlorine agent may be added to a detergent composition for automatic dishwashers, and the addition of a chlorine agent can remove dirt and germs adhering to an object to be washed. When adding chlorine, it is effective to use a cleaning solution (the solution used to clean the inside of the cleaning tank) that has as high an effective chlorine concentration as possible to remove dirt and germs. Therefore, when a chlorine agent is added to a cleaning composition to clean an object, it has been considered preferable to use a cleaning solution with a high effective chlorine concentration.Furthermore, from the viewpoint of achieving a uniform cleaning effect, it has been considered preferable to always use a cleaning solution with a high effective chlorine concentration.

[0008] However, chlorine agents have the side effect of damaging the objects being washed, such as dishes, due to their strong oxidizing properties, and the inventors have recognized a new problem in that using a cleaning solution with a high concentration of available chlorine for each wash is not necessarily effective.

[0009] The present invention has been made to solve the above problems, and aims to provide a cartridge cleaner that can reduce damage to the object to be cleaned and remove dirt and germs that have accumulated on the object to be cleaned. [Means for solving the problem]

[0010] The cartridge detergent of the present invention is a cartridge detergent for an automatic washing machine in which a water-insoluble container having a supply port for contents is placed with the supply port facing downward, and water is sprayed into the supply port to dissolve and supply the contents, wherein the contents are a solid detergent composition containing an alkaline agent (A), a chelating agent (B), and a coated chlorine agent (C) in which a chlorine agent is coated with a coating agent, and the cartridge detergent is placed in a supply device attached to the automatic washing machine, and the solid detergent composition is dissolved in water at 35°C to obtain a cleaning solution. When the effective chlorine concentration of the cleaning solution is measured from the start to the end of use of the cartridge detergent in a cleaning solution with a solid detergent composition concentration of 0.10 wt %, at least one peak in the effective chlorine concentration of the cleaning solution is 15 ppm or more.

[0011] The cartridge detergent of the present invention contains a coated chlorine agent in a solid detergent composition, which has a low reactivity with the alkali agent and chelating agent coexisting in the solid detergent composition, thereby preventing a decrease in the available chlorine concentration. Furthermore, when the cartridge detergent of the present invention is installed in a supply device attached to an automatic dishwasher and used, when the effective chlorine concentration is measured from the start of use of the cartridge detergent to the end of use (the point at which the detergent is consumed), there is at least one peak in the cleaning liquid where the concentration of the solid detergent composition is 0.10 wt % and the effective chlorine concentration is 15 ppm or more. When such a cartridge cleaner is used to repeatedly clean an object, cleaning with a cleaning solution having a high concentration of available chlorine can be performed at least once during the period from the start to the end of use of the cartridge cleaner, thereby minimizing damage to the object and removing dirt and germs that have accumulated on the object.

[0012] In the cartridge cleaning agent of the present invention, the available chlorine concentration at the peak is preferably 60 ppm or less. This can reduce damage to the object to be cleaned.

[0013] In the cartridge detergent of the present invention, it is preferable that the average value of the available chlorine concentration in the cleaning solution from the start of use of the cartridge detergent to the end of use is not more than two-thirds of the maximum available chlorine concentration. The average effective chlorine concentration in the cleaning solution from the start to the end of cartridge use is an indicator of the damage caused to the object by the chlorine agent when the same cartridge is used to clean the same object repeatedly. By keeping this average value at or below two-thirds of the maximum effective chlorine concentration, damage to the object can be reduced. In the cartridge cleaning agent of the present invention, there is at least one peak in the cleaning solution where the effective chlorine concentration is 15 ppm or more during the period from the start of use of the cartridge cleaning agent to the end of use. Therefore, the fact that the average effective chlorine concentration is less than two-thirds of the maximum effective chlorine concentration means that the effective chlorine concentration is controlled to a lower level than the peak effective chlorine concentration during periods other than the peak.

[0014] When the cartridge cleaner of the present invention is used to repeatedly clean an object to be cleaned, it is preferable that the minimum value of the available chlorine concentration is 0 or more and less than 5 ppm in the section excluding the start and end of supply. The fact that there are sections where cleaning is performed using a cleaning solution with a minimum effective chlorine concentration of 0 or more but less than 5 ppm in sections excluding the beginning and end of supply means that there are sections where the effective chlorine concentration drops significantly in sections other than the peak, and in this case, damage to the object being cleaned can be reduced.

[0015] The cartridge detergent of the present invention has an absolute value of the difference between the specific gravity of the coated chlorine agent (C) and the specific gravity of the components other than the coated chlorine agent (C) contained in the solid detergent composition of 0.5 g / cm 3 It is preferable that this is equal to or greater than this.

[0016] If there is a large difference in the specific gravity of the coated chlorine agent and the components other than the coated chlorine agent, the coated chlorine agent will be unevenly distributed on the surface or bottom of the container. As a result, the area where the coated chlorine agent is unevenly distributed will be dissolved and the cleaning agent solution will be supplied, causing a peak in the available chlorine concentration in the cleaning solution of 15 ppm or more.

[0017] In the cartridge detergent of the present invention, the coating agent is preferably a salt of one or more aromatic carboxylic acids selected from the group consisting of benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, and pt-butylbenzoic acid. When the coating agent is a salt of the aromatic carboxylic acid, it is possible to prevent the coating agent from reacting with other components in the solid detergent composition, and since the coating agent dissolves in water, it is effective in allowing the effect of the chlorine agent to be exerted in the cleaning solution.

[0018] In the cartridge detergent of the present invention, the solid detergent composition is in a solid form in which the contents are integrated, and it is preferable that the coated chlorine agent (C) is unevenly distributed in at least one location within the solid detergent composition. With the above-mentioned configuration, when the portion where the coated chlorine agent is unevenly distributed is dissolved, the available chlorine concentration becomes locally high. Therefore, the cleaning agent solution supplied by dissolving the portion can generate a peak of the available chlorine concentration in the cleaning solution of 15 ppm or more.

[0019] In the cartridge detergent of the present invention, it is preferable that the coated chlorine agent (C) is a solid chlorine agent, and the solid detergent composition includes a layer of the solid chlorine agent and a layer of a detergent component other than the solid chlorine agent. With the above configuration, when the layer of the solid chlorine agent is dissolved, the effective chlorine concentration becomes locally high, and therefore, the cleaning agent solution supplied by dissolving the layer of the solid chlorine agent can generate a peak in the effective chlorine concentration in the cleaning solution of 15 ppm or more.

[0020] The cartridge detergent of the present invention is also a cartridge detergent for an automatic washing machine, in which a water-insoluble container having a supply port for contents is placed with the supply port facing downward, and water is sprayed into the supply port to dissolve and supply the contents, the content being a solid detergent composition containing an alkaline agent (A) and a chelating agent (B), the container consisting of a container body, an inner lid, and an outer lid, the inner lid containing a solid chlorine agent, and a partition for preventing movement of the solid chlorine agent or the solid detergent composition is provided between the container body and the inner lid, and the cartridge detergent is placed in a supply device attached to the automatic washing machine, and the solid detergent composition is dissolved in water at 35°C to obtain a cleaning solution. When the effective chlorine concentration of the cleaning solution is measured from the start to the end of use of the cartridge detergent in a cleaning solution with a solid detergent composition concentration of 0.10 wt%, at least one peak in the effective chlorine concentration of the cleaning solution is 15 ppm or more.

[0021] When such a cartridge cleaner is used to repeatedly clean an object, cleaning with a cleaning solution having a high concentration of available chlorine can be performed at least once during the period from the start to the end of use of the cartridge cleaner, thereby minimizing damage to the object and removing dirt and bacteria that have accumulated on the object. Note that, since the peak can be generated by the solid chlorine agent contained in the inner lid, the contents do not need to contain a chlorine agent.

[0022] The cleaning method of the present invention is a cleaning method in which an object to be cleaned is repeatedly cleaned using a cartridge cleaner for an automatic cleaning machine, in which a water-insoluble container having a supply port for contents is placed with the supply port facing downwards and water is sprayed into the supply port to dissolve the contents as it is supplied.The cartridge cleaner is the cartridge cleaner of the present invention, and is characterized in that when the same cartridge cleaner is used to repeatedly clean an object to be cleaned, dirt accumulated on the object to be cleaned is removed by cleaning with a cleaning solution having a high chlorine concentration such that the effective chlorine concentration in the cleaning solution is 15 ppm or more at least once during the period from the start to the end of use of the cartridge cleaner.

[0023] With the above method, dirt accumulated on the object to be cleaned can be removed by cleaning with a cleaning solution having a high chlorine concentration at least once during the period from the start to the end of use of the cartridge cleaning agent. During other periods, cleaning is not performed with a cleaning solution having a high chlorine concentration, so damage to the object to be cleaned can be reduced.

[0024] In the cleaning method of the present invention, when the object to be cleaned is repeatedly cleaned, it is preferable that the minimum value of the available chlorine concentration is 0 or more and less than 5 ppm in the section excluding the start and end of the supply. This can reduce damage to the object to be cleaned.

[0025] In the cleaning method of the present invention, cleaning is preferably performed with a cleaning solution in which the average effective chlorine concentration in the cleaning solution from the start to the end of use of the cartridge cleaner is not more than two-thirds of the maximum effective chlorine concentration. This can reduce damage to the object to be cleaned.

[0026] The method for sterilizing microorganisms or removing bacterial flora agglomerates of the present invention is characterized by allowing the high chlorine concentration cleaning solution used in the cleaning method of the present invention to act on bacteria or bacterial flora in an automatic cleaning machine. According to the above method, the cleaning solution with a high chlorine concentration is allowed to act on the bacteria or bacterial flora formed in the automatic washer, thereby making it possible to suitably remove the microorganisms or bacterial flora aggregates.

[0027] In the present invention, the bacterial flora aggregate is preferably a red- or orange-colored bacterial flora aggregate. The method for sterilizing microorganisms or the method for removing bacterial flora aggregates of the present invention is useful for preventing the occurrence of or sterilizing red- or orange-colored bacterial flora aggregates.

[0028] In the present invention, the bacterial flora clump preferably contains at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas. The coated chlorine agent (C) has disinfecting power against microorganisms of the genera Meiothermus and Tepizimonas. On the other hand, when bacterial colony aggregates form in a washing machine such as an automatic dishwasher, the microorganisms are protected by dirt and organic matter, reducing the disinfecting effect of the chlorine agent. To disinfect bacterial colony aggregates, it is important to remove organic matter, etc., to expose the microorganisms inside the bacterial colony aggregates and make them more accessible to the disinfectant, thereby enabling the disinfectant to exert its disinfecting effect. To achieve this, the solid detergent composition must have good disinfecting power as well as good detergency. By containing the alkaline agent (A) and the chelating agent (B), the solid detergent composition has good disinfecting power against the microorganisms and good detergency. Therefore, the solid detergent composition is useful for preventing the formation of or disinfecting bacterial colony aggregates containing at least one microorganism selected from the group consisting of Meiothermus and Tepizimonas. For example, the solid detergent composition can be used in a washing machine in which bacterial colony aggregates containing the microorganisms are present and allowed to act on the bacterial colony aggregates, thereby enabling the bacterial colony aggregates to be disinfected. Furthermore, the solid detergent composition can be applied to the microorganisms in a washing machine to disinfect the microorganisms. The solid detergent composition is suitable as a detergent composition for a washing machine in which bacterial colony aggregates containing the microorganisms are present.

[0029] Preferably, the bacterial flora clot further contains at least one microorganism selected from the group consisting of Bacillus cereus, Tepidophilus, Lysinibacillus, and Diferrisoma. Since the coated chlorine agent (C) has a disinfecting effect against these microorganisms, the method for removing bacterial flora clumps of the present invention is useful for preventing the occurrence of or disinfecting bacterial flora clumps containing at least one of the above-mentioned microorganisms in addition to at least one species selected from the group consisting of the genera Meiothermus and Tepizimonas. The solid detergent composition is suitable as a detergent composition for a washing machine in which bacterial flora clumps containing the above-mentioned microorganisms exist.

[0030] In one aspect, the method for sterilizing microorganisms or the method for removing bacterial flora agglomerates of the present invention is suitably applied to a washing machine in which the bacterial flora agglomerates are present, for sterilizing the bacterial flora agglomerates while washing an object to be washed. The method for sterilizing microorganisms or the method for removing bacterial flora agglomerates of the present invention has cleaning power and sterilizing power against microorganisms, and is therefore suitable for use in washing machines in which bacterial flora agglomerates are present, making it possible to sterilize bacterial flora agglomerates while washing objects having hard surfaces.

[0031] The method for producing a cartridge detergent of the present invention comprises mixing a raw material composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated coated chlorine agent (C) in warm water to prepare a mixed molten liquid, preparing a water-insoluble container having a supply port for contents, pouring the mixed molten liquid into the container, and cooling and solidifying the mixed molten liquid in the container, thereby producing a cartridge detergent, wherein the absolute value of the difference between the specific gravity of the coated chlorine agent (C) and the specific gravities of components other than the coated chlorine agent (C) contained in the mixed molten liquid is 0.5 g / cm 3 The present invention is characterized in that the above is satisfied.

[0032] In this way, the coated chlorine agent is unevenly distributed on the surface or bottom of the container during the process of cooling and solidifying the mixed molten liquid, so that a cartridge detergent in which the coated chlorine agent is unevenly distributed within the solid detergent composition can be produced. When the area where the coated chlorine agent is unevenly distributed dissolves, such a cartridge detergent has a locally high effective chlorine concentration, and therefore, can generate a peak of effective chlorine concentration of 15 ppm or more in the cleaning liquid. [Effects of the Invention]

[0033] According to the present invention, it is possible to reduce damage to the object to be cleaned and remove dirt and germs accumulated on the object to be cleaned. [Brief explanation of the drawings]

[0034] [Figure 1] FIG. 1 is a cross-sectional view schematically illustrating one embodiment of a cartridge cleaner. [Figure 2] 2(a), 2(b), and 2(c) are cross-sectional views that schematically show how water is sprayed onto the supply port of the cartridge detergent, dissolving the solid detergent composition in water to obtain a detergent solution. [Figure 3] FIG. 3 is a cross-sectional view schematically showing another embodiment of the cartridge detergent of the present invention. [Figure 4] FIG. 4 is a cross-sectional view schematically showing another embodiment of the cartridge detergent of the present invention. [Figure 5] 5(a), 5(b), and 5(c) are conceptual diagrams that schematically show an embodiment of the inner lid body and the outer lid body that constitute the cartridge detergent shown in FIG. [Figure 6] FIG. 6 is a graph showing the results of measuring the effective chlorine concentration for the cartridge detergents of Examples 4 and 5 and Comparative Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0035] The cartridge detergent of the present invention is a cartridge detergent for an automatic cleaning machine in which a water-insoluble container having a supply port for contents is placed with the supply port facing downward, and water is sprayed into the supply port to dissolve and supply the contents, the contents being a solid detergent composition containing an alkaline agent (A), a chelating agent (B), and a coated chlorine agent (C) in which a chlorine agent is coated with a coating agent, the cartridge detergent is placed in a supply device attached to the automatic cleaning machine, and the solid detergent composition is dissolved in water at 35°C to obtain a cleaning solution. When the effective chlorine concentration of the cleaning solution is measured from the start to the end of use of the cartridge detergent in a cleaning solution with a solid detergent composition concentration of 0.10 wt%, at least one peak in the effective chlorine concentration of the cleaning solution is 15 ppm or more. In particular, from the viewpoint of more thoroughly removing dirt and germs accumulated on the object to be cleaned, the effective chlorine concentration at the peak is preferably 20 ppm or more. Furthermore, from the viewpoint of minimizing damage to the object to be cleaned, the available chlorine concentration at the peak is preferably 60 ppm or less, more preferably 50 ppm or less, and even more preferably 24 ppm or less.

[0036] The cartridge cleaner of the present invention will now be described. In this specification, the content (wt %) of each component of the solid detergent composition in the cartridge detergent refers to the content of the pure content (solid content) in the solid detergent composition, unless otherwise specified.

[0037] FIG. 1 is a cross-sectional view schematically illustrating one embodiment of a cartridge cleaner. The cartridge detergent 1 shown in FIG. 1 comprises a water-insoluble container 10 containing a solid detergent composition 20 as its content. In this example, the solid cleaning composition 20 is a solid body that has solidified into the shape of the container 10 . The container 10 has a supply port 11. The supply port 11 serves as an inlet through which water is sprayed into the container 10 and as an outlet through which a detergent solution produced by dissolving the solid detergent composition 20 exits the container 10. The solid detergent composition 20 contains an alkaline agent, a chelating agent, and a chlorine agent. Water is sprayed into the supply port 11 to dissolve the solid detergent composition 20 contained therein, and the detergent solution is supplied to the automatic washing machine. The solid detergent composition 20 has a high-chlorine layer 21 containing a large amount of chlorine agent and a detergent layer 22 containing a lower amount of chlorine agent than the high-chlorine layer. In FIG. 1, the high chlorine layer 21 is a layer provided on the supply port side of the cartridge detergent, but it may be a layer provided on the bottom side of the cartridge detergent. These layers will be described in more detail below.

[0038] When the cartridge detergent of the present invention is placed in a supply device attached to an automatic cleaning machine, and the effective chlorine concentration of the cleaning solution obtained by dissolving the solid detergent composition in water at 35°C is measured from the start to the end of use of the cartridge detergent in a cleaning solution with a solid detergent composition concentration of 0.10 wt%, there is at least one peak where the effective chlorine concentration of the cleaning solution is 15 ppm or more. The measurement of the available chlorine concentration of the cleaning solution will be described below.

[0039] 2(a), 2(b), and 2(c) are cross-sectional views that schematically show how water is sprayed onto the supply port of the cartridge detergent, dissolving the solid detergent composition in water to obtain a detergent solution. Figure 2(a) shows the start of using the cartridge detergent, Figure 2(b) shows the point when about half of the cartridge detergent has been used, and Figure 2(c) shows the point when the cartridge detergent is almost finished being used.

[0040] As shown in Figure 2(a), when the cartridge detergent 1 is used, the spray water 60 passes through the supply port 11 and reaches the solid detergent composition 20 contained in the container 10, producing a detergent solution 61 in which the solid detergent composition 20 is dissolved. This detergent solution 61 drops down from the supply port 11 and flows into the cleaning tank of the automatic cleaning machine, and is introduced into the automatic cleaning machine. At the beginning of use of the cartridge detergent 1 shown in FIG. 2(a), the high-chlorine layer 21, which is a layer containing a large amount of chlorine agent, is dissolved, so the concentration of available chlorine in the resulting detergent solution 61 is high.

[0041] 2(b), when about half of the cartridge detergent 1 is used, the detergent layer 22 containing a small amount of chlorine agent is dissolved. Therefore, the concentration of available chlorine in the detergent solution 62 produced at this stage is low.

[0042] As shown in Fig. 2(c), just before the end of use of the cartridge detergent 1, the detergent layer 22 containing a small amount of chlorine agent is dissolved, as shown in Fig. 2(b). Therefore, the available chlorine concentration in the detergent solution 62 produced at this stage is low.

[0043] The available chlorine concentration in the resulting cleaning solution was measured from the start of use of the cartridge cleaner shown in Figure 2(a) to the end of use of the cartridge cleaner shown in Figure 2(c). Specifically, cleaning solution samples were taken at 10% intervals, including the start and end of use, for a total of at least 11 samples, such as at the start of use of the cartridge cleaner (when 0-5% of the total amount has been used), when about 1 / 10 of the cartridge cleaner has been used (when 5-15% of the total amount has been used), when about 2 / 10 of the cartridge cleaner has been used (when 15-25% of the total amount has been used), when about 9 / 10 of the cartridge cleaner has been used (when 85-95% of the total amount has been used), and when the cartridge cleaner has been used to completion (when 95-100% of the total amount has been used).

[0044] Then, create a graph with the measured effective chlorine concentration on the vertical axis and the amount of cartridge cleaner used on the horizontal axis, and check whether there is at least one peak where the effective chlorine concentration is 15 ppm or higher during the period from the start to the end of cartridge cleaner use.

[0045] When determining the peak of effective chlorine concentration, it is necessary that there is a period other than the beginning and end of the period from the start to the end of use of the cartridge cleaner where the effective chlorine concentration is less than one-third of the maximum effective chlorine concentration. If all measurement results during use are one-third or more of the maximum effective chlorine concentration, it is not considered that there is a peak where the effective chlorine concentration is 15 ppm or more. There may be multiple peaks, for example, at least one in the first half of the period from the start to the end of use of the cartridge cleaner and at least one in the second half. Even in this case, there must be a period other than the beginning and end of the period from the start to the end of use of the cartridge cleaner where the effective chlorine concentration is less than one-third of the maximum effective chlorine concentration, but the chlorine concentration in the period between the peak in the first half and the peak in the second half does not need to be less than one-third of the maximum effective chlorine concentration.

[0046] When measuring the available chlorine concentration, the amount of water sprayed is adjusted to obtain a cleaning solution with a solid detergent composition concentration of 0.10% by weight, and the temperature of the cleaning solution is set to 25°C. The conditions of a cleaning solution temperature of 25°C and a solid detergent composition concentration of 0.10 wt% are necessary for measuring the available chlorine concentration specified in the present invention. The temperature of the cleaning solution and the concentration of the solid detergent composition when using the cartridge detergent of the present invention are not limited.

[0047] The available chlorine concentration in the cleaning solution is measured as follows. The available chlorine concentration is measured in an aqueous solution at 25°C. (1) Weigh out 100 g of the aqueous solution in the cleaning tank, add 5 g of aluminum sulfate and 5 g of potassium iodide, and stir thoroughly. (2) Add 10 mL of glacial acetic acid to the above aqueous solution. (3) After mixing uniformly, titrate with N / 100 aqueous sodium thiosulfate solution. (4) The endpoint is when the solution changes from pale yellow to colorless. (5) Calculate the effective chlorine concentration from the amount of sodium thiosulfate solution added at the end point using the following formula (1). Available chlorine concentration (ppm) = N / 100 Amount of sodium thiosulfate solution added (mL) × 3.546 (1) (6) The above measurements (1) to (5) are repeated from the start of use of the cartridge cleaner to the end of use.

[0048] The cartridge cleaner of the present invention contains a chlorine agent in the solid cleaning agent composition, and when the effective chlorine concentration is measured from the start of use of the cartridge cleaner to the end of use, there is at least one peak in the cleaning solution where the effective chlorine concentration is 15 ppm or more during the period from the start of use of the cartridge cleaner to the end of use. When such a cartridge cleaner is used to repeatedly clean an object, cleaning can be performed with a high-chlorine concentration cleaning solution with an effective chlorine concentration of 15 ppm or more at least once during the period from the start to the end of use of the cartridge cleaner, thereby minimizing damage to the object and removing dirt and germs that have accumulated on the object. Furthermore, if the effective chlorine concentration exceeds 60 ppm, the chlorine smell may be unpleasant to the cleaners, and the impact on the material of the items being washed will be enhanced.

[0049] In the cartridge cleaning agent of the present invention, the average value of the effective chlorine concentration in the cleaning solution from the start of use of the cartridge cleaning agent to the end of use is preferably not more than two-thirds of the maximum effective chlorine concentration, more preferably not more than one-third, even more preferably not more than one-quarter, and particularly preferably not more than one-fifth. The average effective chlorine concentration in the cleaning solution from the start to the end of cartridge use is an indicator of the damage caused to the object by the chlorine agent when the same cartridge is used to clean the same object repeatedly. By keeping this average value at or below two-thirds of the maximum effective chlorine concentration, damage to the object can be reduced. In the cartridge cleaning agent of the present invention, there is at least one peak in the period from the start of use of the cartridge cleaning agent to the end of use where the effective chlorine concentration in the cleaning solution is 15 ppm or more. Therefore, the fact that the average effective chlorine concentration is less than two-thirds of the maximum effective chlorine concentration means that the effective chlorine concentration is controlled to a lower level than the peak effective chlorine concentration during periods other than the above peak.

[0050] The average value of the available chlorine concentration is preferably 3 ppm or more and 60 ppm or less, more preferably 45 ppm or less, even more preferably 40 ppm or less, and even more preferably 30 ppm or less. The average effective chlorine concentration can be calculated as the average value of the effective chlorine concentration at each measurement point when a graph is drawn with the measured effective chlorine concentration on the vertical axis and the amount of cartridge cleaner used on the horizontal axis.

[0051] When the cartridge cleaner of the present invention is used to repeatedly clean an object to be cleaned, it is preferable that the minimum value of the available chlorine concentration is 0 or more and less than 5 ppm in the section excluding the start and end of supply. The fact that there are sections where cleaning is performed using a cleaning solution with a minimum effective chlorine concentration of 0 or more but less than 5 ppm in sections excluding the beginning and end of supply means that there are sections where the effective chlorine concentration drops significantly in sections other than the peak, and in this case, damage to the object being cleaned can be reduced.

[0052] Each component constituting the solid detergent composition will be described below. The solid detergent composition contains an alkaline agent (A), a chelating agent (B), and a coated chlorine agent (C). It may also contain other components such as an anticorrosive, a surfactant, and a polymer dispersant.

[0053] The alkaline agent (A) may be any water-soluble alkaline agent, and may be, for example, an alkali metal salt or an alkaline earth metal salt. The alkali metal salt is preferably at least one compound selected from the group consisting of alkali metal hydroxides, alkali metal phosphates, alkali metal carbonates, and alkali metal silicic acid salts. Examples of preferred alkali metal salts include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal phosphates such as trisodium phosphate; alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; and alkali metal silicic acid salts such as sodium silicate (sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, and sodium silicate No. 4) and potassium silicate (potassium metasilicate, potassium sesquisilicate, and potassium orthosilicate). These alkaline agents may be in the form of hydrates. Among these, alkali metal hydroxides and alkali metal silicic acid salts are more preferred, and alkali metal silicic acid salts are even more preferred. It should be noted that compounds exemplified as chelating agents, which will be described later, are not included in the alkaline agents of the present invention.

[0054] The content of the alkaline agent is preferably 5 to 85% by mass based on the total mass of the solid detergent composition. When the content of the alkaline agent is within this range, the detergency is enhanced. The content of the alkaline agent is preferably 10 to 70% by mass. The content of the alkaline agent is more preferably 25% by mass or more. When two or more alkaline agents are contained, the content is defined as the total content of each alkaline agent. Furthermore, when the alkaline agent is in the form of a hydrate, the content includes the water component contained in the hydrate.

[0055] Examples of the chelating agent (B) include aminocarboxylic acid-based, hydroxycarboxylic acid-based, phosphoric acid-based, ether carboxylate, phosphonic acid-based, etc. Compounds such as sodium polyacrylate, which are exemplified as polymer dispersants described below, are not included in the chelating agents of the present invention.

[0056] Examples of the aminocarboxylic acid chelating agent include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methylglycine diacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), glutamic acid diacetic acid (GLDA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2-hydroxypropanehexaacetic acid (DPTA-OH), aspartic acid diacetic acid (ASDA), ethylenediaminesuccinic acid (EDDS), and salts thereof.

[0057] Examples of the hydroxycarboxylic acid-based chelating agent include malic acid, succinic acid, citric acid, lactic acid, tartaric acid, gluconic acid, and salts thereof. Examples of the phosphoric acid-based chelating agent include tripolyphosphate and hexametaphosphate.

[0058] Examples of the phosphonic acid chelating agent include hydroxyethylidene diphosphonic acid (HEDP), nitrilotrismethylenephosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), and salts thereof.

[0059] Examples of the salts of the chelating agents include salts of alkali metals such as potassium and sodium, magnesium salts, and salts of alkaline earth metals such as calcium. Of these, alkali metal salts are preferred, and sodium salts or potassium salts are more preferred.

[0060] The chelating agent in the present invention is preferably an aminocarboxylic acid-based or phosphonic acid-based chelating agent, more preferably ethylenediaminetetraacetic acid, nitrilotriacetic acid, methylglycinediacetic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid, or a salt thereof, and even more preferably ethylenediaminetetraacetic acid, nitrilotriacetic acid, methylglycinediacetic acid, or a salt thereof.

[0061] The content of the chelating agent is preferably 5 to 85% by mass based on the total mass of the solid detergent composition. If the content of the chelating agent is less than 5% by mass, the generation of calcium-derived scale may become a problem. If the content of the chelating agent is more than 85% by mass, the detergency may be reduced. The content of the chelating agent is more preferably 10 to 60% by mass. When two or more types of chelating agents are contained, the content is defined as the total content of each chelating agent.

[0062] The coated chlorine agent (C) is preferably a coated chlorine agent comprising a chlorine agent and a coating agent that coats the periphery of the chlorine agent. By coating the periphery of the chlorine agent with a coating agent, it is possible to prevent the chlorine agent from being deactivated due to reaction with other components contained in the solid detergent composition, such as a chelating agent or an alkaline agent. Therefore, when the chlorine agent is contained in the solid detergent composition in the form of a coated chlorine agent, it is possible to obtain a solid detergent composition containing the chlorine agent in an effective state.

[0063] Examples of chlorine agents constituting the coating chlorine agent include dichloroisocyanuric acid (chlorinated isocyanuric acid) salts (sodium dichloroisocyanurate (sodium chlorinated isocyanurate), potassium dichloroisocyanurate (potassium chlorinated isocyanurate), etc.), trichloroisocyanuric acid, and hypochlorites (sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc.). These chlorine agents may be hydrates. Among them, dichloroisocyanuric acid salts, trichloroisocyanuric acid, and hypochlorites are preferred as chlorine agents. Sodium dichloroisocyanurate is preferred as dichloroisocyanurate. The chlorine agent may be one type of chlorine agent or a combination of two or more types of chlorine agents.

[0064] Examples of the coating agent include carboxylates and silicates. Examples of the carboxylate include aromatic carboxylates, acyclic dicarboxylates, and acyclic monocarboxylates having 1 to 7 carbon atoms. Examples of aromatic carboxylates include benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, cinnamic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, phenylacetic acid, 2-phenylpropionic acid, phenoxyacetic acid, phenylpyruvic acid, ot-butylbenzoic acid, mt-butylbenzoic acid, pt-butylbenzoic acid, 3,5-di-t-butylbenzoic acid, 3,5-di-t-butylsalicylic acid, o-benzoylbenzoic acid, m-benzoylbenzoic acid, and p-benzoylbenzoic acid. Examples of the aromatic carboxylic acid salts include salts of aromatic carboxylic acids such as benzoic acid, anthranilic acid, 1-naphthoic acid, 2-naphthoic acid, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 3-hydroxy-2-naphthoic acid, 2-hydroxyphenylacetic acid, 3-hydroxyphenylacetic acid, 4-hydroxyphenylacetic acid, D-mandelic acid, L-mandelic acid, trimellitic acid, pyromellitic acid, 2-methoxyphenylacetic acid, 3-methoxyphenylacetic acid, and 4-methoxyphenylacetic acid, and these can be used alone or in combination of two or more.

[0065] Examples of the acyclic dicarboxylate include succinate, glutarate, adipate, suberate, azelaate, sebacate, undecane diacid salt, dodecane diacid salt, and tetradecane diacid salt. Examples of the acyclic monocarboxylic acid salts having 1 to 7 carbon atoms include formates, acetates, propionates, butyrates, valerates, hexanoates, and heptanoates.

[0066] Examples of silicates include orthosilicate, metasilicate, and metadisilicate.

[0067] Among these, at least one selected from the group consisting of benzoates, o-phthalates, m-phthalates, p-phthalates, trimellitates, pt-butylbenzoates, and metasilicates is preferred from the viewpoints of safety, non-reactivity with chlorine agents, ease of molding as a coating agent, etc., and benzoates are more preferred. Benzoates have good stability against chlorine agents, so using a coated chlorine agent coated with a benzoate-containing coating agent can effectively prevent decomposition of the chlorine agent, etc., during storage of the solid detergent composition, thereby suppressing a decrease in the available chlorine content and a decrease in detergency and disinfecting power. Furthermore, benzoates have excellent rapid solubility, so they can exhibit good detergency and disinfecting power when used in cleaning with the solid detergent composition. Furthermore, benzoates have low foaming properties, making them less likely to reduce cleaning efficiency when used in, for example, an automatic washing machine. Examples of benzoates include sodium benzoate, potassium benzoate, calcium benzoate, and magnesium benzoate, with sodium benzoate being preferred from the viewpoint of solubility.

[0068] Examples of the salts in the chlorine agent and coating agent include salts of alkali metals such as potassium and sodium, magnesium salts, and salts of alkaline earth metals such as calcium. Among these, alkali metal salts are preferred, and sodium salts and potassium salts are more preferred.

[0069] The coated chlorine agent preferably comprises a chlorine agent and at least one selected from the group consisting of benzoate, o-phthalate, m-phthalate, p-phthalate, trimellitate, pt-butylbenzoate, and metasilicate as a coating agent that coats the periphery of the chlorine agent. A coated chlorine agent in which the chlorine agent is sodium dichloroisocyanurate and the coating agent is sodium benzoate is more preferred.

[0070] The weight ratio of the chlorine agent / coating agent is, for example, preferably 1 to 9, more preferably 1.5 to 4. The method for coating the chlorine agent is not particularly limited. For example, a method in which a solution or suspension of a benzoate in a solvent such as water, methanol, ethanol, or ether is sprayed onto a solid chlorine agent, followed by drying to coat; a method in which a fine powder of a benzoate is mixed with a solid chlorine agent, and then a binder such as water is sprayed onto the solid chlorine agent to coat it; and the method for tableting or granulating the chlorine agent are not particularly limited. For example, a binder or the like can be added to the chlorine agent, followed by tableting or granulation.

[0071] The specific gravity of the coated chlorine agent is 1.0 to 2.0 g / cm 3 It is preferable that:

[0072] The solid detergent composition may contain an uncoated chlorine agent, but the content of the uncoated chlorine agent in 100% by mass of the solid detergent composition is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. It is particularly preferred that the solid detergent composition does not substantially contain an uncoated chlorine agent.

[0073] When the solid detergent composition contains an anticorrosive, the corrosion prevention effect (anticorrosion action) of the solid detergent composition is improved. As the anticorrosive agent, it is preferable to use an anticorrosive agent for aluminum, copper, or copper alloys. As such an anticorrosive agent, for example, benzotriazole or its derivatives (e.g., benzotriazole, tolyltriazole, 5-dodecylbenzotriazole, 5-octylbenzotriazole, 5-hexylbenzotriazole, 5-butylbenzotriazole, 5-methylbenzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, carboxybenzotriazole methyl ester, carboxybenzotriazole butyl ester, carboxybenzotriazole hexyl ester, benzotriazole octyl ester, dicarboxypropylbenzotriazole, etc.), benzimidazole or its derivatives (e.g., benzimidazole, 2-mercaptobenzimidazole, thiazolylbenzimidazole, thiabendazole, etc.), benzothiazole or its derivatives (e.g., benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole, etc.) can be suitably used. Among them, benzimidazole, benzotriazole, and tolyltriazole are preferred.

[0074] When the solid detergent composition contains an anticorrosion agent, the content of the anticorrosion agent is preferably 0.001 to 5 mass% based on the total mass of the solid detergent composition. If the content of the anticorrosion agent is less than 0.001 mass%, the anticorrosion agent may not exhibit a sufficient corrosion prevention effect. If the content of the anticorrosion agent is more than 5 mass%, the influence of the odor specific to the anticorrosion agent may become strong. The content of the anticorrosion agent is preferably 0.1 to 2 mass%. When two or more types of anticorrosion agents are contained, the content is defined as the total content of each anticorrosion agent.

[0075] The solid detergent composition may contain a surfactant. The surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like, preferably a nonionic surfactant. Examples of the nonionic surfactant include polyoxyalkylene dialkyl ether, reverse Pluronic block polymer, polyoxyalkylene alkylphenyl ether, fatty acid alkanolamide, polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, polyoxyethylene methyl ether fatty acid ester, and polyoxyalkylene alkylamine.

[0076] When the solid detergent composition contains a surfactant, the content thereof is preferably 0.1 to 20 mass %, more preferably 1 to 10 mass %, based on the total mass of the solid detergent composition. When two or more surfactants are contained, the content is defined as the total content of the surfactants.

[0077] The solid detergent composition may contain a polymer dispersant, the weight-average molecular weight of which is preferably 3,000 to 300,000, for example. The inclusion of such a polymer dispersant improves the scale prevention ability. The polymer dispersant may be used alone or in combination of two or more kinds. Examples of the polymer dispersant include polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, sulfonated polymaleic acid, olefin-maleic acid copolymer, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer, maleic anhydride ethylene crosslinked copolymer, maleic anhydride acrylic acid copolymer, and maleic anhydride vinyl acetate copolymer. Examples of the carboxylic acid copolymer include maleic anhydride, maleic anhydride-acrylonitrile copolymer, maleic anhydride-acrylic ester copolymer, maleic anhydride-butadiene copolymer, maleic anhydride-isoprene copolymer, poly-β-ketocarboxylic acid derived from maleic anhydride and carbon monoxide, itaconic acid, ethylene copolymer, itaconic acid-aconitic acid copolymer, itaconic acid-maleic acid copolymer, itaconic acid-acrylic acid copolymer, malonic acid methylene copolymer, itaconic acid-fumaric acid copolymer, ethylene glycol ethylene terephthalate copolymer, vinylpyrrolidone-vinyl acetate copolymer, and metal salts thereof. Examples of metal salts include salts of alkali metals such as potassium and sodium, and salts of alkaline earth metals such as magnesium and calcium. Of these, alkali metal salts are preferred, and sodium salts or potassium salts are more preferred. As the polymer dispersant, polyacrylates and salts of olefin-maleic acid copolymers are preferred, and sodium polyacrylate and sodium salts of olefin-maleic acid copolymers are more preferred. The weight average molecular weight can be determined by gel permeation chromatography using a phosphate buffer solution and acetonitrile as a developing solvent and polyacrylic acid as a standard substance.

[0078] When the solid detergent composition contains a polymer dispersant, the content thereof is preferably 0.1 to 20 mass %, more preferably 1 to 10 mass %, based on the total mass of the solid detergent composition. When two or more polymer dispersants are contained, the content is defined as the total content of each polymer dispersant.

[0079] The solid detergent composition may contain other components such as a solubilizer, a bleaching agent, a disinfectant, an enzyme, a bulking agent, an antifoaming agent, a solvent (e.g., water), etc. Even if some of the components constituting the solid detergent composition are liquid, it is acceptable as long as the entire detergent composition is solid, for example, by being impregnated in other components.

[0080] The pH of the solid detergent composition when dissolved in water is not particularly limited, but is preferably in the neutral to alkaline range, for example. The pH of the solid detergent composition when dissolved in water is measured by mixing 10 g of the detergent composition with 90 g of water (the concentration of the detergent composition is 10 wt %). For a neutral detergent composition, the pH is preferably 6 or more and less than 9. For a weakly alkaline detergent composition, the pH is preferably 9 or more and less than 12. For a strongly alkaline detergent composition, the pH is preferably 12 or more. The pH can be measured using a Horiba D-21 pH meter.

[0081] Below, we will explain an example of an embodiment of the cartridge cleaning agent of the present invention, which, when used, will result in at least one peak in the cleaning solution where the effective chlorine concentration is 15 ppm or more during the period from the start to the end of use of the cartridge cleaning agent.

[0082] The cartridge detergent 1 shown in FIG. 1 is one embodiment of the cartridge detergent of the present invention. In this cartridge detergent, the solid detergent composition is a solid in which the contents are integrated, and there is at least one location in the solid detergent composition where the chlorine agent (C) is unevenly distributed.

[0083] In the cartridge detergent 1 shown in Figure 1, the solid detergent composition 20 is provided with a high-chlorine layer 21, which is a layer containing a large amount of chlorine agent, and a detergent layer 22, which has a lower content of chlorine agent than the high-chlorine layer. The high-chlorine layer 21 can be said to be a location where the coated chlorine agent (C) is unevenly distributed. In Fig. 1, the high-chlorine layer 21 is a layer provided on the supply port side of the cartridge detergent, but it may be a layer provided on another location (for example, the bottom side) of the cartridge detergent.

[0084] FIG. 2 shows how the cartridge cleaner 1 is used to obtain a detergent solution. As shown in FIG. 2(a), when the cartridge cleaning agent 1 is first used, the high-chlorine layer 21, which is a layer containing a large amount of chlorine agent, is dissolved, and the concentration of available chlorine in the resulting cleaning agent solution 61 becomes high. 2(b), when about half of the cartridge detergent 1 is used, the detergent layer 22 containing a small amount of chlorine agent is dissolved. Therefore, the concentration of available chlorine in the detergent solution 62 produced at this stage is low. As shown in FIG. 2(c), when the cartridge detergent 1 is nearing the end of use, the detergent layer 22 containing a small amount of chlorine agent is dissolved, as shown in FIG. 2(b), and the available chlorine concentration in the resulting detergent solution 63 becomes low.

[0085] Therefore, at the start of use of the cartridge detergent 1, the concentration of available chlorine in the generated detergent solution is high, and the concentration of available chlorine in the cleaning solution reaches a peak of 15 ppm or more. In addition, the available chlorine concentration does not become very high except at the time when the cartridge cleaning agent 1 is first used.

[0086] Next, another embodiment of the cartridge cleaner of the present invention will be described. FIG. 3 is a cross-sectional view schematically showing another embodiment of the cartridge detergent of the present invention. In this cartridge detergent, the coated chlorine agent (C) is a solid chlorine agent (c1), and the solid detergent composition includes a layer of the solid chlorine agent (c1) and a layer of a detergent component other than the solid chlorine agent, and the layer of the solid chlorine agent (c1) is present in at least one place in the cartridge detergent.

[0087] The cartridge detergent 101 shown in FIG. 3 is configured such that a water-insoluble container 10 contains a solid detergent composition 120 as its content. Solid detergent composition 120 consists of three layers: solid chlorine agent layer 121B containing solid chlorine agent 123, and layers 122A and 122C of detergent components other than the solid chlorine agent. Solid chlorine agent layer 121B is present in the center of the cartridge detergent volumetrically, but may also be present in the upper half or the lower half.

[0088] As the solid chlorine agent, a chlorine agent solidified by adding a bonding auxiliary agent to the chlorine agent can be suitably used. Also, as the chlorine agent used in the solid chlorine agent, the chlorine agent exemplified as the chlorine agent constituting the coated chlorine agent can be used. Also, a coated chlorine agent solidified by adding a bonding auxiliary agent can be used.

[0089] As the layer of detergent components other than the solid chlorine agent, a solid detergent composition containing an alkaline agent and a chelating agent and, if necessary, other components can be used. The alkaline agent, chelating agent, and other components may be the same as those described as components constituting the solid detergent composition, and may be the same components as those in the detergent layer 22 in the cartridge detergent 1 shown in Figure 1. The solid detergent composition constituting the layer of detergent components other than the solid chlorine agent may contain a chlorine agent. In this case, it is preferable to incorporate a small amount of the chlorine agent in consideration of the available chlorine concentration during use.

[0090] When the cartridge cleaning agent 101 shown in FIG. 3 is used, the concentration of available chlorine in the cleaning agent solution produced when the layer 121B of the solid chlorine agent dissolves increases, and the available chlorine concentration in the cleaning solution peaks at 15 ppm or more. Furthermore, at the time when the layers 122A and 122C of the cleaning agent components other than the solid chlorine agent in the cartridge cleaning agent 101 are dissolved, the available chlorine concentration does not become so high.

[0091] Further, another embodiment of the cartridge cleaner of the present invention will be described. FIG. 4 is a cross-sectional view schematically showing another embodiment of the cartridge detergent of the present invention. 5(a), 5(b), and 5(c) are conceptual diagrams that schematically show an example of the inner lid body and the outer lid body that constitute the cartridge detergent shown in FIG.

[0092] In this cartridge detergent, the container consists of a container body, an inner lid body, and an outer lid body. The container body contains a solid detergent composition. The inner lid body contains a solid chlorine agent (c2) separately from the chlorine agent (C). A partition is provided between the container body and the inner lid body to prevent movement of the solid chlorine agent (c2) or the solid detergent composition. The peak of the available chlorine concentration in the cleaning solution of 15 ppm or more occurs due to the dissolution of the solid chlorine agent (c2).

[0093] In FIG. 4, the cartridge cleaner 201 is shown divided into a container body 210, an inner lid body 232, an outer lid body 233, and a cover part 234 which is a partition. The container body 210 is a water-insoluble container that contains a solid detergent composition 220 as its content. The solid detergent composition 220 is composed of a detergent layer. Although not shown, a high-chlorine layer containing a large amount of chlorine agent may be provided in addition to the detergent layer. The components constituting the detergent layer may be the same as those of the detergent layer 22 in the cartridge detergent 1 shown in FIG.

[0094] The container body 210 is a cylindrical container whose diameter gradually decreases toward the bottom, forming a so-called funnel shape. The cylindrical member 212 is formed with a screw 212a for screwing in the inner lid body 232. Although not shown, the cylindrical member may be configured to fix the inner lid body by a fitting type using a claw structure instead of by screwing.

[0095] The inner lid body 232 contains a solid chlorine agent 223. This is the solid chlorine agent (c2), and as the solid chlorine agent (c2), a solidified chlorine agent obtained by adding a bonding assistant to the chlorine agent can be suitably used. In addition, as the chlorine agent used in the solid chlorine agent, the chlorine agents listed as the chlorine agents constituting the coated chlorine agent can be used. In addition, the coated chlorine agent may be solidified by adding a bonding assistant to the coated chlorine agent.

[0096] The inner lid body 232 shown in Figure 5(a) has a cylindrical shape with a bottom, and the bottom 232b is provided with a cylindrical member 232d for passing the spray water and an opening 232a for passing the cleaning agent solution in which the solid cleaning agent composition and the solid chlorine agent 223 (see Figure 5(b)) are dissolved, and the inner wall of the cylindrical portion 232c of the inner lid body 232 is provided with a screw 320a for screwing into the tubular member 212 (see Figure 4). The portion of the inner lid body 232 for placing the solid chlorine agent 223 thereon, including the opening 232a and the bottom 232b, is the placing portion. The bottom 232b has a mesh shape with many openings 232a formed therein. The mesh shape of the bottom 232b with many openings 232a has the advantage that the detergent solution can easily pass through the bottom of the inner lid body and be discharged evenly.

[0097] Furthermore, the inner lid body 232 is further provided with an inner cylinder 232e, and is configured so that the solid chlorine agent 223 can be accommodated inside the inner cylinder 232e (see FIG. 5(b)). The solid chlorine agent to be accommodated in the inner lid body 232 is preferably solid chlorine agent 223 having a size that will not drop through the mesh-shaped opening 232a of the bottom part 232b. Furthermore, partitioning members 232f for restricting the movement of the solid chlorine agent 223 are provided at a plurality of locations within the inner cylinder 232e of the inner lid body 232, and the space within the inner cylinder 232e is partitioned. The intervals between the partitioning members 232f are preferably determined so that the solid chlorine agent 223 is contained between the partitioning members 232f. By restricting the movement of the solid chlorine agent 223 in this manner, each solid chlorine agent can be dissolved uniformly.

[0098] Furthermore, it is desirable that the partitioning member 232f partitions the space inside the inner cylinder 232e loosely, rather than completely. "Loosely" means that the space inside the inner cylinder 232e is partitioned to the extent that the partitioning member 232f restricts the movement of the solid chlorine agent 223, while providing space between the partitioning member 232f and the inner wall of the inner cylinder 232e and / or between the partitioning member 232f and the outer wall of the cylindrical member 232d, allowing liquids such as water and detergent solution to move freely within the inner cylinder 232e. In this state, even if liquids such as water and detergent solution are sprayed onto a specific portion, the liquid is not unevenly distributed within the inner cylinder 232e, preventing only specific solid chlorine agents 223 from dissolving.

[0099] As shown in FIG. 5(b), a ring-shaped cover portion 234 is provided to hold the solid chlorine agent 223 in a state where it is accommodated inside the inner cylinder 232e. The cover portion is provided between the container body and the inner lid body, and is a partition that prevents the solid chlorine agent or the solid detergent composition from moving.

[0100] FIG. 5(c) shows a state in which a film member 233 as an outer lid body is adhered to the back surface of the inner lid body 232 shown in FIG. 5(a). The film member 233 may be adhered to the inner cover 232 with an adhesive that can be peeled off when the cartridge cleaner is used. The film member 233 can be peeled off by grasping the protruding portion 233a, which is not coated with adhesive, with one's hand. The film member may also be a water-soluble film that dissolves and disappears when it comes into contact with water.

[0101] When using such a cartridge cleaner, the film member 233 serving as the outer lid body is peeled off from the inner lid body 232 . The jet of water passes through the space between the cylindrical members 232d and reaches the solid detergent composition 220 contained in the container body 210 (see FIG. 4), and a detergent solution is produced in which the solid detergent composition 220 is dissolved. The detergent solution enters the inner lid body 232 through the opening 234a of the cover part 234 and dissolves the solid chlorine agent 223, thereby producing a detergent solution containing the solid detergent composition and the solid chlorine agent. This detergent solution drops down from the opening 232a at the bottom of the inner lid 232 and flows into the cleaning tank of the automatic washer, and the detergent solution containing the chlorine agent derived from the coated chlorine agent and the solid chlorine agent is introduced into the automatic washer. In this form of cartridge cleaning agent, the cylindrical member 232d and the opening 232a at the bottom of the inner lid 232 correspond to the supply port.

[0102] When the cartridge detergent 201 shown in FIG. 4 is used, first, the concentration of available chlorine in the detergent solution produced when the solid chlorine agent 223 contained in the inner lid body 232 dissolves increases, and the available chlorine concentration in the cleaning solution peaks at 15 ppm or more. This peak usually occurs in the first half of the period from the start of use to the end of use of the cartridge cleaner. The amount of solid chlorine agent blended is preferably set to such an extent that dissolution is almost completed in the first half of the period from the start of use to the end of use of the cartridge cleaner. For a while after the solid chlorine agent 223 is dissolved, the cleaning agent layer containing a small amount of chlorine agent is dissolved. Therefore, the available chlorine concentration in the cleaning agent solution produced at this stage is low.

[0103] Next, the cleaning method of the present invention will be described. The cleaning method of the present invention is a cleaning method in which an object to be cleaned is repeatedly cleaned using a cartridge cleaner for an automatic cleaning machine, in which a water-insoluble container having a supply port for contents is placed with the supply port facing downwards and water is sprayed into the supply port to dissolve the contents as it is supplied.The cartridge cleaner is the cartridge cleaner of the present invention, and is characterized in that when the same cartridge cleaner is used to repeatedly clean an object to be cleaned, dirt accumulated on the object to be cleaned is removed by cleaning with a cleaning solution having a high chlorine concentration such that the effective chlorine concentration in the cleaning solution is 15 ppm or more at least once during the period from the start to the end of use of the cartridge cleaner.

[0104] With the above method, dirt accumulated on the object to be cleaned can be removed by cleaning with a high-chlorine concentration cleaning solution with an effective chlorine concentration of 15 ppm or more at least once during the period from the start to the end of use of the cartridge cleaning agent. During other periods, cleaning is not performed with a cleaning solution having a high chlorine concentration, so damage to the object to be cleaned can be reduced. In addition, the peak effective chlorine concentration is preferably 60 ppm or less. If the effective chlorine concentration exceeds 60 ppm, the cleaning worker may feel uncomfortable due to the chlorine odor, and even if the effective chlorine concentration is increased beyond 60 ppm, the effect of improving cleaning performance is small. The peak effective chlorine concentration is more preferably 30 ppm or less, even more preferably 25 ppm or less, and particularly preferably 20 ppm or less.

[0105] In the cleaning method of the present invention, it is preferable that the average value of the available chlorine concentration in the cleaning solution from the start to the end of use of the cartridge cleaner is not more than two-thirds of the maximum available chlorine concentration. This can reduce damage to the object to be cleaned.

[0106] The average value of the available chlorine concentration is preferably 3 ppm or more and 60 ppm or less, more preferably 45 ppm or less, and even more preferably 40 ppm or less. The average effective chlorine concentration can be calculated as the average value of the effective chlorine concentration at each measurement point when a graph is drawn with the measured effective chlorine concentration on the vertical axis and the amount of cartridge cleaner used on the horizontal axis.

[0107] In the cleaning method of the present invention, when repeatedly cleaning an object to be cleaned, it is preferable to perform cleaning with a cleaning liquid having a minimum effective chlorine concentration of 0 or more and less than 5 ppm in the section excluding the start and end of supply. By doing so, damage to the object to be cleaned can be reduced.

[0108] Dirt accumulated on objects to be cleaned includes complex dirt containing a mixture of oils, fats, proteins, starches, etc. Examples of objects to be cleaned include tableware, cutlery, cooking utensils, metal fittings, jigs, containers, trays, etc.

[0109] By using the cartridge cleaner of the present invention, it is possible to clean with a cleaning solution that has a high effective chlorine concentration and a high cleaning effect while minimizing damage to the object to be cleaned, thereby making it possible to effectively sterilize microorganisms and remove bacterial flora clumps. The method for sterilizing microorganisms or removing bacterial flora agglomerates of the present invention is characterized by allowing the high chlorine concentration cleaning solution used in the cleaning method of the present invention to act on bacteria or bacterial flora in an automatic cleaning machine. According to the above method, the cleaning solution with a high chlorine concentration is allowed to act on the bacteria or bacterial flora formed in the automatic washer, thereby making it possible to suitably remove the microorganisms or bacterial flora aggregates.

[0110] The bacterial flora clumps removed by the method for sterilizing microorganisms or the method for removing bacterial flora clumps of the present invention are preferably red- or orange-colored bacterial flora clumps. The cartridge cleaner of the present invention is useful for preventing the occurrence of or sterilizing red- or orange-colored bacterial flora clumps. An example of a bacterial flora clot is a bacterial flora clot containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas. Bacterial flora clots containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas tend to be red or orange in color. The cartridge cleaning agent of the present invention has a disinfecting effect against microorganisms of the genus Meiothermus and the genus Tepizimonas, and is suitable for use in preventing the occurrence of or disinfecting bacterial flora clots containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas. In one aspect, the cartridge detergent of the present invention is used in a washing machine in which a bacterial colony containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas is present, and exhibits high cleaning power and disinfecting power against the bacterial colony.

[0111] Microorganisms in the genus Meiothermus include Meiothermus ruber, Meiothermus taiwanensis, Meiothermus sylvanus, Meiothermus tylarophilus, Meiothermus cerveleus, Meiothermus granaticius, Meiothermus rosaceus, Meiothermus rufus, and Meiothermus thymidus. Microorganisms in the genus Tepizimonas include Tepizimonas taiwanensis, Tepizimonas fonticardii, Tepizimonas aquatica, Tepizimonas ignava, and Tepizimonas thermorum. The microorganisms of the genus Meiothermus and the microorganisms of the genus Tepizimonas may each be one species or two or more species. Preferred microorganisms of the genus Meiothermus are Meiothermus ruber, Meiothermus taiwanensis, and Meiothermus sylvanus, and preferred microorganisms of the genus Tepizimonas are Tepizimonas taiwanensis and Tepizimonas fonticcardi. In one embodiment, the cartridge cleaner of the present invention is suitable for sterilizing at least one microorganism selected from the group consisting of Meiothermus ruber, Meiothermus taiwanensis, Meiothermus sylvanus, Tepizimonas taiwanensis, and Tepizimonas fonticcardi.

[0112] The cartridge cleaner of the present invention is also useful for disinfecting microorganisms belonging to the Bacillus cereus species (Bacillus cereus), the genus Tepidophilus, the genus Lysinibacillus, and the genus Difelisoma. The cartridge cleaner of the present invention can further be used for disinfecting at least one microorganism selected from the group consisting of the Bacillus cereus species, the genus Tepidophilus, the genus Lysinibacillus, and the genus Difelisoma. The microorganisms of the Bacillus cereus species, the Tepidophilus genus, the Lysinibacillus genus, and the Diferrisoma genus may each be one species or two or more species. Microorganisms in the genus Tepidiphilus include Tepidiphilus succinatimandens and Tepidiphilus thermophilus. Microorganisms in the genus Lysinibacillus include Lysinibacillus fusiformis, Lysinibacillus boronitoerans, Lysinibacillus gresorivorans, Lysinibacillus macroides, Lysinibacillus massiliensis, Lysinibacillus odyssei, Lysinibacillus parviboronicapiens, Lysinibacillus sinduriensis, Lysinibacillus sphaericus, and Lysinibacillus sillanilyticus. Microorganisms in the genus Difelisoma include Difelisoma camini and Difelisoma paleocoriens.

[0113] The bacterial flora may contain at least one microorganism selected from the group consisting of Bacillus cereus, Tepidophilus, Lysinibacillus, and Diferisoma. The cartridge cleaner of the present invention also has the ability to disinfect these microorganisms. The cartridge cleaner of the present invention is suitable for use in preventing the occurrence of or eliminating bacterial colony clumps containing at least one microorganism selected from the group consisting of the genera Meiothermus and Tepizimonas, and at least one microorganism selected from the group consisting of Bacillus cereus, Tepiziphilus, Lysinibacillus, and Difelisoma. Examples of microorganisms belonging to the genera Meiothermus, Tepizimonas, Bacillus cereus, Tepiziphilus, Lysinibacillus, and Difelisoma include the microorganisms mentioned above. The presence of the above-mentioned microorganisms in the bacterial flora clot can be confirmed, for example, by analyzing the 16S rDNA DNA sequence of the microorganisms that form the bacterial flora clot. 16S rDNA DNA sequence analysis can be performed by the method described in the Examples. In one embodiment, the cartridge cleaner of the present invention is also useful for eliminating microorganisms such as bacteria of the genus Escherichia in addition to the microorganisms mentioned above.

[0114] The method for applying the cleaning solution to the microorganisms or the bacterial flora agglomerates containing them is not particularly limited, and examples thereof include a method of contacting the cleaning solution with the microorganisms or the bacterial flora agglomerates containing them, a method of turning the cleaning solution into a mist and contacting the mist with the microorganisms or the bacterial flora agglomerates containing them, etc. When using the cleaning solution to wash objects such as dishes in an automatic washing machine, the cleaning solution may be brought into contact with the objects to be washed in the automatic washing machine.

[0115] When the cartridge detergent of the present invention is used to wash objects to be washed, such as tableware, in an automatic washing machine, the dishware or the like can be brought into contact with the cleaning solution obtained from the cartridge detergent in the automatic washing machine. When the cartridge detergent of the present invention is used to remove bacterial flora agglomerates in an automatic washing machine, the cleaning solution obtained from the cartridge detergent can be allowed to act on the bacterial flora agglomerates. When sterilizing microorganisms in an automatic washing machine in which bacterial flora agglomerates containing microorganisms are present, the cleaning solution can be circulated within the automatic washing machine.

[0116] A method for producing the cartridge cleaner of the present invention will now be described. The method for preparing the solid detergent composition used in the cartridge detergent of the present invention is not particularly limited, but examples include a method in which at least one type of solid material with a low chlorine agent content (e.g., no chlorine agent) and at least one type of solid material with a high chlorine agent content are produced, and the cartridge detergent is provided with at least one location where the chlorine agent is unevenly distributed.

[0117] Instead of producing a solid material with a high chlorine content, the chlorine agent may be sprinkled on the solid material with a low chlorine content at the solidification stage to immobilize it. Alternatively, the chlorine agent may be sprinkled on the bottom of the container and then filled with the solid material with a low chlorine content. It is also possible to use a solid chlorine agent as the chlorine agent, and alternately fill a solid material with a low chlorine agent content and the solid chlorine agent.

[0118] The chlorine agent and other raw materials used in producing the solid material can be those described above. In preparing raw materials for producing a solid material having a high content of a chlorine agent, a chlorine agent and other raw material compositions are mixed with water (hot water) to prepare a mixed molten liquid. The water is mixed with the raw material composition as warm water, or is mixed with the raw material composition as water and then heated to form warm water. The temperature of the warm water used to prepare the mixed molten liquid is preferably 30 to 90°C. In preparing raw materials for producing a solid material containing no chlorine agent, a mixed molten liquid may be prepared without using a chlorine agent, and the same procedure as above may be followed.

[0119] A solid can be produced by placing the molten mixture in a container and allowing the molten mixture to cool and solidify in the container. The solid detergent composition may be cooled to any temperature at which the components constituting the solid detergent composition solidify, and may be left at room temperature (for example, 20 to 35° C.), or such cooling may be omitted.

[0120] Furthermore, instead of a solid material with a low content of a chlorine agent (for example, containing no chlorine agent), a mixed molten liquid with a low content of a chlorine agent (for example, containing no chlorine agent) may be used. The chlorine agent can be placed at the bottom of the container by sprinkling a predetermined amount of the chlorine agent in the container and pouring a mixed molten liquid of the components of the solid detergent composition containing no chlorine agent thereon so that the position of the chlorine agent at the bottom of the container does not move too much. Alternatively, the chlorine agent can be placed on the supply opening side of the container by placing a molten mixture of the components of the solid detergent composition containing no chlorine agent in the container and sprinkling the chlorine agent on top of it. The molten mixture can then be solidified to form a solid detergent composition.

[0121] In the present production method, the preferred blending ratios of the chlorine agent and other raw material compositions can be the same as those explained in the section on the solid detergent composition. The weight ratio of water (warm water) in the mixed molten liquid is preferably 5 to 20% by weight.

[0122] Furthermore, if necessary, a solid chlorine agent may be placed inside the inner lid body so that the container can be used in combination with a solid detergent composition containing a chlorine agent. [Example]

[0123] Examples will be given below to explain the present invention more specifically, but the present invention is not limited to these examples.

[0124] (Preparation of Cartridge Cleaning Agent) Cartridge cleaners of Examples 1 to 12 and Comparative Examples 1 and 2 were prepared. Table 1 shows the overall formulation (composition) of the cartridge cleaners of Examples 1 to 12 and Comparative Examples 1 and 2. Table 1 shows the proportion of each component in % by weight.

[0125] In producing the solid detergent compositions in Examples 1 to 12 and Comparative Example 1, the components of the solid detergent compositions shown in Table 1, except for the chlorine agent, were mixed in warm water to prepare a molten mixture, which was then poured into a water-insoluble container and cooled to solidify. When the molten mixture was cooled to solidify, it was placed with the supply port facing upward.

[0126] The chlorine agent was placed as follows: When placing the chlorine agent at the "bottom of the container," a predetermined amount of the chlorine agent was sprinkled in the container, and a mixed molten liquid of the components of the solid detergent composition not containing the chlorine agent was poured on top of it in such a way that the position of the chlorine agent at the bottom of the container did not move much, so that the chlorine agent was placed at the bottom of the container. When placing the chlorine agent "on the container," a molten mixture of the components of the solid detergent composition, which does not contain a chlorine agent, is placed in the container, the chlorine agent is sprinkled on the molten mixture, and the molten mixture is solidified so that the chlorine agent is placed on the surface of the solid detergent composition ("on the container").

[0127] In producing the solid detergent composition in Comparative Example 2, the components of the solid detergent composition shown in Table 1 were mixed in warm water to prepare a molten mixture, which was then poured into a water-insoluble container and cooled and solidified in the container to produce a solid detergent composition in which the chlorine agent was uniformly distributed in the container (referred to as "uniform in container" in Table 1). When the molten mixture was cooled and solidified, it was placed with the supply port facing upward. [Table 1]

[0128] (Measurement of available chlorine concentration) The cartridge detergents of each Example and Comparative Example were placed in a supply device attached to an automatic dishwasher, and the amount of water sprayed was adjusted to obtain a cleaning solution with a solid detergent composition concentration of 0.10 wt %. The temperature of the sprayed water was 35°C, and the available chlorine concentration was measured using an aqueous solution at 25°C. The following procedures (1) to (5) were repeated every 30 minutes from the start of use of the cartridge cleaner to the end of use. (1) 100 g of the aqueous solution in the cleaning tank was weighed, and 5 g of aluminum sulfate and 5 g of potassium iodide were added and thoroughly stirred. (2) 10 mL of glacial acetic acid was added to the above aqueous solution. (3) After mixing uniformly, the mixture was titrated with a N / 100 aqueous solution of sodium thiosulfate. (4) The endpoint was when the color of the solution changed from pale yellow to colorless. (5) The effective chlorine concentration was calculated from the amount of sodium thiosulfate solution added at the end point using the following formula (1). Available chlorine concentration (ppm) = N / 100 Amount of sodium thiosulfate solution added (mL) × 3.546 (1)

[0129] FIG. 6 is a graph showing the results of measuring the effective chlorine concentration for the cartridge detergents of Examples 4 and 5 and Comparative Example 1. As shown in Figure 6, when the cartridge cleaners of Examples 4 and 5 were measured from the start of use to the end of use, there was one peak in the period from the start of use to the end of use where the available chlorine concentration in the cleaning solution was 15 ppm or higher. On the other hand, in the cartridge cleaning agents of Comparative Examples 1 and 2, there is no peak in the cleaning solution where the available chlorine concentration is 15 ppm or more during the above period.

[0130] Figure 6 shows a typical example of a graph showing the results of measuring the effective chlorine concentration, but when measurements were also taken in other examples from the start of use of the cartridge detergent to the end of use, there was one peak in the period from the start of use of the cartridge detergent to the end of use where the effective chlorine concentration in the cleaning solution was 15 ppm or higher. Furthermore, with the cartridge cleaners of Examples 4 and 5, when repeatedly cleaning an object to be cleaned, the minimum value of the available chlorine concentration was 0 or more and less than 5 ppm in the section excluding the start and end of supply. This was also the case with the other Examples.

[0131] Table 1 shows the peak effective chlorine concentration in each example and comparative example. For comparative examples 1 and 2, which do not have a peak effective chlorine concentration of 15 ppm or more, the maximum effective chlorine concentration is shown as the peak. The average value of the available chlorine concentration in each example and comparative example is also shown.

[0132] 1) Detergency evaluation (1) 70% (80 mL) of water and 0.3 g of complex soil were added to a tempered glass container (115 mL), mixed well, tilted twice to ensure that the soil was applied to the walls, and left to stand overnight in an incubator at 70°C. (2) For the washing, a Hoshizaki 650 (manufactured by Hoshizaki Corporation) was used as the automatic dishwasher, and the detergent concentration was 0.1% by weight. For each washing cycle, 40 mL of water (room temperature) and 0.3 g of complex dirt (room temperature) were added to the glass, mixed well, and then tilted and rotated twice as described above so that the dirt would adhere to the walls, and then left to stand in a 70°C incubator for 10 minutes. (3) (2) was repeated 10 times, and the finish of the glass was evaluated according to the following criteria. The evaluation was carried out using a cleaning solution having a composition that gives a peak value for the available chlorine concentration.

[0133] <Evaluation criteria> ◎: Few streaks and high transparency ○: There are streaks but the transparency is somewhat high △: Cloudy and streaky ×: Significant dirt

[0134] 2) Effects on melamine tableware Melamine tableware was washed 10 times with a detergent concentration of 0.1% by weight using a Hoshizaki 650 automatic dishwasher (manufactured by Hoshizaki Corporation). The evaluation was carried out using a cleaning solution having a composition that gives an average effective chlorine concentration.

[0135] <Evaluation criteria> ◎: Same as before cleaning ○: Almost no yellowing ×: Yellowing

[0136] 3) Antibacterial effect The test bacteria were cultured in a normal bouillon medium (manufactured by Eiken Chemical Co., Ltd.) at 60°C for 24 hours to prepare a bacterial suspension. Each sample (the composition prepared above) was diluted to 0.1% with ion-exchanged water, heated to 60°C, and mixed with the bacterial suspension at a ratio of 99:1 (volume ratio) to prepare a sample-added bacterial suspension. After a 15-second reaction, the sample-added bacterial suspension was neutralized with a pH 7 buffer solution containing sterilized sodium thiosulfate, and the neutralized sample-added bacterial suspension was serially diluted with physiological saline. 1000 μL of this diluted solution and 30 mL of standard agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.) were added to a plate. After incubating the plate at 60°C for 48 hours, the colony-forming units (CFU) were counted. The logarithm of the control and sample was calculated. 10 Difference in CFU (log 10 CFU-log of sample 10 The sterilizing power of the composition against the test bacteria was evaluated based on the logarithm of the control and the sample. 10Difference in CFU (log 10 CFU-log of sample 10 CFU) to Δlog 10 It is written as CFU. The evaluation was conducted at the peak of the effective chlorine concentration. Value of The cleaning was carried out using a cleaning solution having the following composition:

[0137] (Evaluation criteria for disinfection power) ◎:Δlog 10 Sterilization effect for CFU 5 or more ○:Δlog 10 Sterilization effect for CFU 3 or more and less than 5 △:Δlog 10 Sterilization effect for CFU 1 or more and less than 3 ×:Δlog 10 Effective in eliminating bacteria with a CFU of less than 1

[0138] These evaluation results show that the cartridge cleaners of Examples 1 to 12, which have at least one peak in the cleaning solution where the effective chlorine concentration is 15 ppm or higher from the start to the end of use of the cartridge cleaner, can remove dirt and germs that have accumulated on the object to be cleaned while minimizing damage to the object to be cleaned. By using a cleaning solution with a peak in effective chlorine concentration, dirt and germs that have accumulated on the object being cleaned can be removed.

[0139] Furthermore, with the cartridge cleaners of Comparative Examples 1 and 2, there was no point where the available chlorine concentration peaked at 15 ppm or more during the above period, so the dirt and germs that had accumulated on the object to be cleaned were not sufficiently removed. [Explanation of symbols]

[0140] 1, 101, 201 Cartridge Cleaning Agent 10 containers 11 Supply port 20, 120, 220 Solid detergent composition 21 High chlorine layer 22 Detergent layer 60 water jet 61, 62, 63 Detergent solution 121B Solid chlorine agent layer 122A, 122C Layer of cleaning agent components other than solid chlorine agents 210 Container body 212 Cylinder member 212a Screw 223 Solid chlorine agent 232 Middle lid 232a opening 232b bottom 232c Cylindrical part 232d Cylindrical member 232e inner cylinder 232f Partition member 233 Outer cover (film material) 233a Protrusion 234 Cover part 234a Cover opening 320a screw

Claims

1. A cartridge detergent for an automatic dishwasher, in which a water-insoluble container having a supply opening for contents is placed with the supply opening facing downward, and water is sprayed into the supply opening to dissolve and supply the contents, The content is a solid detergent composition including: an alkali agent (A) which is a silicate and / or a carbonate; a chelating agent (B) which is at least one selected from the group consisting of ethylenediaminetetraacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, and salts thereof; and a coated chlorine agent (C) which is a dichloroisocyanurate and is coated with a coating agent; In the solid detergent composition, the content of the alkaline agent (A) is 10 to 40% by mass, and the content of the chelating agent (B) is 10 to 60% by mass, the coated chlorine agent (C) is placed on the bottom side of the container so as to be contained in an amount of 3 to 8% by mass based on the total amount of the solid detergent composition; A cartridge detergent characterized in that when the cartridge detergent is placed in a supply device attached to an automatic dishwasher and the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid detergent composition in water at 35°C is measured in a cleaning liquid with a concentration of the solid detergent composition of 0.10% by weight from the start to the end of use of the cartridge detergent, there is at least one peak where the effective chlorine concentration of the cleaning liquid is 15 ppm or more, the average value of the effective chlorine concentration in the cleaning liquid from the start to the end of use of the cartridge detergent is 4 ppm or less, and there is a period other than the start and end of the cleaning period from the start to the end of use of the cartridge detergent where the effective chlorine concentration is less than one-third of the maximum effective chlorine concentration measured during use of the cartridge detergent.

2. 2. The cartridge cleaning agent according to claim 1, wherein the peak available chlorine concentration is 60 ppm or less.

3. 3. The cartridge cleaner according to claim 1, wherein the minimum value of the available chlorine concentration is 0 or more and less than 5 ppm in a section excluding the start and end of supply of the cleaner when repeatedly cleaning an object to be cleaned.

4. The cartridge cleaning agent according to any one of claims 1 to 3, wherein the coating agent is a salt of one or more aromatic carboxylic acids selected from the group consisting of benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid, and p-tert-butylbenzoic acid.

5. The cartridge detergent according to any one of claims 1 to 4, wherein the solid detergent composition is in a solid form in which the contents are integrated, and the coated chlorine agent (C) is unevenly distributed in at least one location in the solid detergent composition.

6. The coated chlorine agent (C) is a solid chlorine agent, The cartridge detergent according to any one of claims 1 to 5, wherein the solid detergent composition comprises a layer of the solid chlorine agent and a layer of a detergent component other than the solid chlorine agent.

7. A cleaning method for repeatedly cleaning an object to be cleaned using a cartridge detergent for an automatic dishwasher, in which a water-insoluble container having a supply opening for contents is placed with the supply opening facing downward, and water is sprayed into the supply opening to dissolve and supply the contents, The cartridge cleaner is the cartridge cleaner according to any one of claims 1 to 6, and the cleaning method is characterized in that when the same cartridge cleaner is used repeatedly to clean an object to be cleaned, at least once during the period from the start to the end of use of the cartridge cleaner, cleaning is carried out with a cleaning solution having a high chlorine concentration such that the effective chlorine concentration of the cleaning solution is 15 ppm or more, thereby removing dirt accumulated on the object to be cleaned, and that during the cleaning period from the start to the end of use of the cartridge cleaner, there is a period other than the start and end when the effective chlorine concentration is less than one-third of the maximum effective chlorine concentration measured during use of the cartridge cleaner.

8. 8. The cleaning method according to claim 7, wherein when the object to be cleaned is repeatedly cleaned, the minimum value of the available chlorine concentration is 0 or more and less than 5 ppm in the section excluding the start and end of supply of the cleaning agent.

9. A method for sterilizing microorganisms or removing bacterial flora agglomerates by the cleaning method according to claim 7 or 8, Among the above cleaning methods, a method for sterilizing microorganisms or removing bacterial flora agglomerates is characterized in that the high chlorine concentration cleaning liquid is allowed to act on bacteria or bacterial flora in an automatic dishwasher.

10. 10. The method for sterilizing microorganisms or removing bacterial flora clumps according to claim 9, wherein the bacterial flora clumps are reddish or orange in color.

11. 11. The method for sterilizing microorganisms or removing bacterial flora clumps according to claim 9 or 10, wherein the bacterial flora clumps contain at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepizimonas.

12. The method for sterilizing microorganisms or the method for removing bacterial flora clots according to claim 10, wherein the bacterial flora clots further contain at least one microorganism selected from the group consisting of Bacillus cereus, Tepidophilus, Lysinibacillus, and Difelisoma.

13. The method for sterilizing microorganisms or the method for removing bacterial colony clumps according to any one of claims 9 to 12, wherein the bacterial colony clumps are sterilized while washing an object to be washed in an automatic dishwasher in which the bacterial colony clumps are present.

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