JP7233685B2 - Cartridge cleaning agent, cleaning method, and method for sterilizing microorganisms or removing clumps of bacterial flora - Google Patents

Description

The present invention relates to a cartridge cleaner, a cleaning method, and a method of sterilizing microorganisms or removing agglomerates of bacterial flora.

2. Description of the Related Art In recent years, automatic dishwashers are used in hotels, restaurants, and the like from the viewpoint of labor shortage, hygiene management, and the like. A detergent composition used in such an automatic dishwashing machine may contain a chlorine agent in addition to cleaning components such as an alkaline agent and a chelating agent. Chlorine agents have the effect of removing pigment stains such as protein, starch, tea stains, coffee, etc. that accumulate on tableware and become strong stains, and the disinfection effect of killing microorganisms, etc. Such effects are expected. and are blended in detergent compositions.

In addition, various bacteria may propagate in the automatic dishwasher and be covered with bacterial flora coagulum (also referred to as biofilm). A detergent composition for automatic dishwashers to which a chlorine agent is added is sometimes used to clean such stains.

Patent Literature 1 discloses a cartridge cleaning agent in which a solid cleaning agent composition can be used. In Patent Document 1, water is injected into a cartridge detergent to obtain a detergent solution (meaning a liquid immediately after dissolving a solid detergent composition), and the detergent solution is supplied to an automatic dishwasher. described to be introduced.
Patent Documents 2 and 3 disclose a solid detergent composition containing a chlorine bleach. However, there is no mention of the gradation of chlorine concentration.

JP 2017-8267 A JP 2017-186549 A JP 2018-115296 A

The cartridge detergent is installed in a supply device attached to an automatic dishwashing machine, and is repeatedly used for multiple washings while gradually supplying the detergent solution. Dishes and the like, which are objects to be washed by automatic dishwashers, are repeatedly used in hotels, restaurants, and the like.
That is, the same cartridge cleaning agent is used to clean the same cleaning object on a daily basis.

As described above, a chlorine agent may be added to the detergent composition for automatic dishwashers, and the addition of the chlorine agent can remove stains and germs adhering to the objects to be cleaned.
When a chlorine agent is added, it is effective to remove dirt and germs by washing with a cleaning solution that maximizes the effective chlorine concentration (refers to the solution used for cleaning the inside of the cleaning tank).
Therefore, when cleaning an object to be cleaned by adding a chlorine agent to the cleaning composition, it was considered preferable to use a cleaning liquid having a high available chlorine concentration. In addition, from the viewpoint of achieving a uniform cleaning effect, it has been considered preferable to always use a cleaning liquid having a high available chlorine concentration.

However, chlorine agents have the side effect of damaging objects to be washed, such as dishes, due to their strong oxidizing action. As recognized by the inventors.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and provides a cartridge cleaning agent capable of reducing damage to an object to be cleaned and removing dirt and germs accumulated on the object to be cleaned. intended to provide

The inventors of the present invention have investigated the above problem in line with the actual washing process in hotels, restaurants, etc., and found that the effective chlorine concentration is Accumulated dirt and germs can be removed at once by using a high-quality cleaning solution, which keeps the cleaning object sufficiently clean and causes less damage to the cleaning object. I found that it worked.

Subsequently, the inventors of the present invention have investigated the functions of the cartridge cleaning agent necessary to use a cleaning solution with a high effective chlorine concentration once every several cleanings when cleaning the object to be cleaned repeatedly as described above. investigated.
In the cartridge cleaning agent described in Patent Document 1, a cleaning agent solution having a special composition is automatically prepared at the initial stage of use of the cartridge cleaning agent by using a solid cleaning agent composition and a detergency enhancer together. It is said that it can be supplied in a dishwasher.
The present inventors have considered using a chlorine agent as a detergency enhancer in the cartridge cleaning agent described in Patent Document 1, but in this case, the effective chlorine concentration is only at the initial stage of use of the cartridge cleaning agent. Although a high detergent solution can be supplied, after that, a detergent solution with a high effective chlorine concentration cannot be supplied until the end of use of the cartridge detergent.

Based on the fact that the same cartridge cleaning agent is repeatedly used for a large number of cleaning steps over a relatively long period of time, the present inventors found that the first half of the period from the start of use to the end of use of the cartridge cleaning agent The cleaning liquid having a high effective chlorine concentration can be supplied at least once during the second period and at least once during the second half period. The present inventors have found that it is effective from the viewpoint of removing bacteria and various bacteria, and arrived at the present invention.

The cartridge cleaning agent of the present invention is supplied by installing a water-insoluble container having a content supply opening with the supply opening facing downward, and dissolving the contents by jetting water into the supply opening. A cartridge cleaning agent for an automatic cleaning machine of
The content is a solid detergent composition containing an alkaline agent (A), a chelating agent (B), and a chlorine agent (C),
The above cartridge cleaning agent is installed in a supply device attached to an automatic cleaning machine, and the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid cleaning composition in water at 35° C. is measured so that the concentration of the solid cleaning composition is 0.00. When measuring from the start of use of the cartridge cleaning agent to the end of use in the cleaning solution of 10% by weight, the peak at which the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less is the peak from the start of use of the cartridge cleaning agent to the end of use. At least one is present in the first half of the period and at least one is present in the second half.

The cartridge cleaning agent of the present invention contains a chlorine agent in the solid cleaning agent composition, and the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm when the effective chlorine concentration is measured from the start of use of the cartridge cleaning agent to the end of use. There is at least one peak in the first half and at least one in the second half of the period from the start of use of the cartridge cleaning agent to the end of use of the cartridge cleaning agent.
When an object to be cleaned is repeatedly washed using such a cartridge cleaning agent, the concentration of effective chlorine decreases at least once in the first half and at least once in the second half of the period from the start of use of the cartridge cleaning agent to the end of use. Since cleaning can be performed with a cleaning solution having a high chlorine concentration of 5 ppm or more, damage to the cleaning object can be reduced, and dirt and germs accumulated on the cleaning object can be removed.
Also, if the effective chlorine concentration exceeds 100 ppm, washing workers may feel unpleasant chlorine odor, and if the effective chlorine concentration exceeds 100 ppm, the material of the dishwasher and the objects to be washed will be affected.

In the cartridge cleaning agent of the present invention, it is preferable that the average effective chlorine concentration in the cleaning liquid from the start of use of the cartridge cleaning agent to the end of use is two-thirds or less of the maximum available chlorine concentration.
The average effective chlorine concentration in the cleaning solution from the start of use of the cartridge cleaning agent to the end of use is the amount of damage to the cleaning object caused by the chlorine agent when the same cleaning object is repeatedly washed using the same cartridge cleaning agent. be an indicator. By setting this average value to be two-thirds or less of the maximum effective chlorine concentration, damage to the cleaning object can be further reduced.
In the cartridge cleaning agent of the present invention, the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less, and there is at least one peak in the first half and at least one in the second half of the period from the start to the end of use of the cartridge cleaning agent. Therefore, the fact that the average value of the effective chlorine concentration is less than two-thirds of the maximum effective chlorine concentration means that the effective chlorine concentration is lower than the peak effective chlorine concentration in the period other than the above peak. means that it is controlled by

In the cartridge cleaning agent of the present invention, the minimum effective chlorine concentration is preferably 0 or more and less than 5 ppm in a section excluding the start and end of supply when repeatedly cleaning an object to be cleaned.
The fact that there is a section where the minimum effective chlorine concentration is 0 or more and less than 5 ppm in the section excluding the beginning and end of the supply means that there is a section where the effective chlorine concentration drops considerably in the section other than the two peaks. In this case, damage to the object to be cleaned can be reduced.

In the cartridge cleaning agent of the present invention, the chlorine agent (C) is preferably a coated chlorine agent comprising a chlorine agent and a coating agent that coats the circumference of the chlorine agent.
In addition, the coating agent contains 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. Acid salts are preferred.
When the chlorine agent is a coated chlorine agent, it is possible to prevent the chlorine agent from reacting with other components in the solid detergent composition and being deactivated. When the coating agent is a salt of the above aromatic carboxylic acid, it can be prevented from reacting with other components in the solid detergent composition, and since the coating agent dissolves in water, chlorine agents cannot be used in the cleaning liquid. It is effective because it can exhibit the effect of

In the cartridge cleaning agent of the present invention, the solid cleaning composition is in a solid form in which the contents are integrated, and the part where the chlorine agent (C) is unevenly distributed in the solid cleaning composition is the cartridge. It is preferable that there is at least one portion in the upper half and at least one portion in the lower half based on the volume of the cleaning agent.
With the above configuration, when a portion where the chlorine agent is unevenly distributed dissolves, the concentration of effective chlorine locally increases. A peak with a chlorine concentration of 5 ppm or more and 100 ppm or less can be generated.

In the cartridge cleaning agent of the present invention, the chlorine agent (C) is a solid chlorine agent (c1),
The solid detergent composition includes a layer of the solid chlorine agent (c1) and a layer of detergent components other than the solid chlorine agent (c1), and the layer of the solid chlorine agent (c1) is a cartridge detergent. It is preferable to have at least one in the upper half and at least one in the lower half on a volume basis.
With the above configuration, when the layer of the solid chlorine agent dissolves, the concentration of available chlorine locally increases. A peak with a chlorine concentration of 5 ppm or more and 100 ppm or less can be generated.

In the cartridge cleaning agent of the present invention, the container comprises a container body, an inner lid and an outer lid,
The container body contains the solid cleaning composition,
The inner lid contains a solid chlorine agent (c2) separately from the chlorine agent (C), and between the container body and the inner lid, the solid chlorine agent (c2) or A partition is provided to prevent movement of the solid detergent composition,
Of the peaks at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less, the peak occurring in the first half period is preferably caused by dissolution of the solid chlorine agent (c2).

In the cleaning method of the present invention, a water-insoluble container having a content supply port is installed with the supply port facing downward, and water is jetted to the supply port to dissolve the contents while supplying the contents. A cleaning method for repeatedly cleaning an object to be cleaned using a cartridge cleaning agent for an automatic cleaning machine,
The cartridge cleaning agent is the cartridge cleaning agent of the present invention, and when repeatedly cleaning an object to be cleaned using the same cartridge cleaning agent, the first half of the period from the start to the end of use of the cartridge cleaning agent At least once in the second half period and at least once in the second half period, cleaning is performed with a high chlorine concentration cleaning solution in which the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less, thereby removing dirt accumulated on the object to be cleaned. and

In the above method, cleaning is performed at least once in the first half of the period from the start of use to the end of use of the cartridge cleaning agent, and at least once in the second half of the period, with a high chlorine concentration cleaning solution having an effective chlorine concentration of 5 ppm or more. By doing so, the dirt accumulated on the cleaning object can be removed.
In addition, since cleaning with a high-chlorine-concentration cleaning solution is not performed during cleaning during other periods, damage to the cleaning object can be reduced.
Also, if the effective chlorine concentration exceeds 100 ppm, washing workers may feel unpleasant chlorine odor, and if the effective chlorine concentration exceeds 100 ppm, the material of the dishwasher and the objects to be washed will be affected.

In the cleaning method of the present invention, it is preferable that the average effective chlorine concentration in the cleaning liquid from the start of use of the cartridge cleaning agent to the end of use be two-thirds or less of the maximum available chlorine concentration.
By doing so, the damage given to the object to be cleaned can be further reduced.

In the cleaning method of the present invention, when repeatedly cleaning the 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 a section excluding the start and end of supply.
By doing so, the damage given to the object to be cleaned can be further reduced.

The method for sterilizing microorganisms or removing agglomerates of bacterial flora of the present invention is characterized by allowing the high-chlorine-concentrated cleaning solution used in the cleaning method of the present invention to act on bacteria and bacterial flora in an automatic washing machine.
According to the above-mentioned method, microorganisms or bacterial flora agglomerates can be preferably removed by allowing the cleaning liquid having a high chlorine concentration to act on the bacteria and bacterial flora formed in the automatic washing machine.

In the method for sterilizing microorganisms or removing clumps of bacterial flora of the present invention, the clumps of bacterial flora are preferably red-colored or orange-colored clumps of bacterial flora.
Moreover, it is preferable that the bacterial flora coagulum contains at least one microorganism selected from the group consisting of the genera Meiothermus and the genera Tepidimonas.
In addition, it is preferable that the bacterial lawn coagulum further contains at least one microorganism selected from the group consisting of Bacillus cereus sp., Tepidiphilus sp., Licinibacillus sp. and Diferisoma sp.
The highly concentrated cleaning solutions used in the cleaning method of the present invention are particularly effective against such species of bacterial lawn clumps.

In the method for sterilizing microorganisms or the method for removing agglomerates of bacterial flora of the present invention, it is preferable to eliminate the agglomerates of bacterial flora while washing the object to be cleaned in an automatic washing machine in which the agglomerates of bacterial flora exist. .
By removing the bacterial flora agglomerate while washing the object to be cleaned, the formation and accumulation of the bacterial flora agglomerate can be prevented. Also, a separate operation for removing bacterial lawn clumps is not required.

According to the present invention, it is possible to reduce the damage given to the object to be washed and to remove the dirt and germs accumulated on the object to be washed.

FIG. 1 is a cross-sectional view schematically showing one embodiment of the cartridge cleaning agent. FIGS. 2(a), 2(b) and 2(c) show how water is injected into the supply port of the cartridge cleaning agent and the solid cleaning agent composition is dissolved in water to obtain a cleaning agent solution. It is a sectional view showing typically. FIG. 3 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention. FIG. 4 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention. FIGS. 5(a), 5(b) and 5(c) are conceptual diagrams schematically showing an embodiment of the inner lid and the outer lid which constitute the cartridge cleaning agent shown in FIG. FIG. 6 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention. FIG. 7 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention. FIG. 8 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention. FIG. 9 is a graph showing the results of measurement of available chlorine concentrations for the cartridge cleaning agents of Examples 8 and 12 and Comparative Examples 1 and 4. FIG.

The cartridge cleaning agent of the present invention is supplied by installing a water-insoluble container having a content supply opening with the supply opening facing downward, and dissolving the contents by jetting water into the supply opening. wherein the content is a solid detergent composition containing an alkaline agent (A), a chelating agent (B) and a chlorine agent (C), and the cartridge The cleaning agent is installed in a supply device attached to an automatic cleaning machine, and the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid cleaning composition in water at 35° C. is determined so that the concentration of the solid cleaning composition is 0.10 wt. %, the peak at which the available chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less is the period from the start of use of the cartridge cleaning agent to the end of use. At least one is present in the first half period and at least one is present in the second half period.

The cartridge cleaning agent of the present invention will be described below.
In this specification, the content (% by weight) of each component of the solid detergent composition in the cartridge detergent is the pure content (solid content) in the solid detergent composition unless otherwise specified.

FIG. 1 is a cross-sectional view schematically showing one embodiment of the cartridge cleaning agent.
In the cartridge detergent 1 shown in FIG. 1, a water-insoluble container 10 contains a solid detergent composition 20 as its content.
In this example, the solid cleaning composition 20 is a solid solidified in the shape of the container 10 .
The container 10 has a supply port portion 11 . The supply port 11 serves as an inlet through which water is sprayed into the container 10 and an outlet through which the 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 jetted into the supply port 11 to dissolve the solid detergent composition 20, which is the content, while the detergent solution is supplied to the automatic washing machine.
The solid detergent composition 20 is provided with high-chlorine layers 21a and 21b, which are layers containing a large amount of chlorine agent, and a detergent layer 22 having a lower chlorine agent content than the high-chlorine layer.
The high-chlorine layer 21a is a layer provided on the supply port side of the cartridge cleaning agent, and the high-chlorine layer 21b is a layer provided on the bottom side of the cartridge cleaning agent.
Details of these layers will be described later.

The cartridge cleaning agent of the present invention is installed in a supply device attached to an automatic cleaning machine, and the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid cleaning composition in water at 35° C. is measured as follows: When measuring from the start of use of the cartridge cleaning agent to the end of use in the cleaning solution of 0.10% by weight, the peak at which the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less is the peak from the start of use of the cartridge cleaning agent to the end of use. At least one is present in the first half period and at least one is present in the second half period.
The measurement of the effective chlorine concentration of the cleaning liquid will be described below.

FIGS. 2(a), 2(b) and 2(c) show how water is injected into the supply port of the cartridge cleaning agent and the solid cleaning agent composition is dissolved in water to obtain a cleaning agent solution. It is a sectional view showing typically.
FIG. 2(a) shows the time when the cartridge cleaning agent is started to be used, FIG. 2(b) shows the time when the cartridge cleaning agent has been used about halfway, and FIG. .

As shown in FIG. 2(a), when using the cartridge cleaning agent 1, the jet water 60 passes through the supply port 11 and reaches the solid cleaning agent composition 20 contained in the container 10. A detergent solution 61 in which the solid detergent composition 20 is dissolved is produced.
This cleaning agent solution 61 drops downward from the supply port 11, flows into the cleaning tank of the automatic cleaning machine, and is introduced into the automatic cleaning machine.
When the cartridge cleaning agent 1 shown in FIG. 2(a) is first used, the high-chlorine layer 21a, which is a layer containing a large amount of the chlorine agent, is dissolved. Concentration increases.

As shown in FIG. 2B, when about half of the cartridge cleaning agent 1 is used, the cleaning agent layer 22 containing a small amount of chlorine agent is dissolved. Therefore, the effective chlorine concentration in the detergent solution 62 generated at this stage becomes low.

As shown in FIG. 2(c), when the cartridge cleaning agent 1 is about to be used, the high-chlorine layer 21b, which is a layer containing a large amount of the chlorine agent, is dissolved. The available chlorine concentration in becomes high.

From the start of use of the cartridge cleaning agent shown in FIG. 2(a) to the end of use of the cartridge cleaning agent shown in FIG. 2(c), the available chlorine concentration in the obtained cleaning solution is measured. Specifically, when starting to use the cartridge cleaning agent (when using 0 to 5% of the total amount), when using about 1/10 of the cartridge cleaning agent (when using 5 to 15% of the total amount), and when using 2/1 of the cartridge cleaning agent. When using about 10 (when using 15 to 25% of the total amount), when using about 9/10 of the cartridge cleaning agent (when using 85 to 95% of the total amount), when using the cartridge cleaning agent (95% of the total amount) The washing liquid is sampled so as to include at least a total of 11 points at intervals of 10%, including two points at the start and end of use, such as "at 100% use".
After sampling the cleaning liquid in this manner, the measurement results for the first half period when 0 to 50% of the total amount is used, and the second half period for the period exceeding 50% to 100% are used.

Then, a graph is created with the measured effective chlorine concentration on the vertical axis and the amount of the cartridge cleaning agent used on the horizontal axis. It is confirmed whether there is at least one in the first half period and at least one in the second half period.

When judging the peak of the available chlorine concentration, the available chlorine concentration is less than 1/3 of the maximum available chlorine concentration during the period from the start of use of the cartridge cleaning agent to the end of use, except at the start and end of use. It is necessary to have a period. During use of the cartridge cleaning agent, when all the measurement results other than at the start and end of use are 1/3 or more of the maximum available chlorine concentration, there is a peak where the available chlorine concentration is 5 ppm or more and 100 ppm or less. do not consider

When measuring the effective chlorine concentration, the amount of water to be sprayed is adjusted so as to obtain a cleaning liquid having a solid cleaning composition concentration of 0.10% by weight. Also, the temperature of the cleaning liquid is set to 25°C.
The cleaning liquid temperature of 25° C. and the solid cleaning composition concentration of 0.10% by weight are the conditions necessary for measuring the effective chlorine concentration defined in the present invention. The temperature of the cleaning liquid and the concentration of the solid cleaning composition when using the cartridge cleaning agent of the present invention are not limited.

The effective chlorine concentration in the cleaning liquid is measured as follows.
The effective chlorine concentration is measured using an aqueous solution at 25°C.
(1) 100 g of the aqueous solution in the washing tank is weighed, 5 g of aluminum sulfate and 5 g of potassium iodide are added, and the mixture is thoroughly stirred.
(2) Add 10 mL of glacial acetic acid to the above aqueous solution.
(3) Titrate with N/100 sodium thiosulfate aqueous solution after uniformly mixing.
(4) The end point is when the color of the solution changes from pale yellow to colorless.
(5) From the drop amount of the sodium thiosulfate aqueous solution at the end point, the available chlorine concentration is calculated by the following formula (1).
Available chlorine concentration (ppm) = N/100 drop amount of sodium thiosulfate aqueous solution (mL) x 3.546 (1)
(6) The above measurements (1) to (5) are repeated from the start of use of the cartridge cleaning agent to the end of use.

The cartridge cleaning agent of the present invention contains a chlorine agent in the solid cleaning agent composition, and the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm when the effective chlorine concentration is measured from the start of use of the cartridge cleaning agent to the end of use. There is at least one peak in the first half and at least one in the second half of the period from the start of use of the cartridge cleaning agent to the end of use of the cartridge cleaning agent.
When an object to be cleaned is repeatedly washed using such a cartridge cleaning agent, the concentration of effective chlorine decreases at least once in the first half and at least once in the second half of the period from the start of use of the cartridge cleaning agent to the end of use. Since cleaning can be performed with a cleaning solution having a high chlorine concentration of 5 ppm or more, damage to the cleaning object can be reduced, and dirt and germs accumulated on the cleaning object can be removed.
Also, if the effective chlorine concentration exceeds 100 ppm, washing workers may feel unpleasant chlorine odor, and if the effective chlorine concentration exceeds 100 ppm, the material of the dishwasher and the objects to be washed will be affected.
Also, the peak maximum value of the effective chlorine concentration in the cleaning liquid is preferably 80 ppm or less, more preferably 60 ppm or less.
When the effective chlorine concentration is 80 ppm or less, the unpleasantness of the chlorine odor is further reduced, and the effect on the material of the dishwasher and the washing items is weakened. Also, when the effective chlorine concentration is 60 ppm or less, the chlorine odor is further reduced, and the effect on the materials of the dishwasher and the objects to be washed is further weakened.

In the cartridge cleaning agent of the present invention, it is preferable that the average effective chlorine concentration in the cleaning liquid from the start of use of the cartridge cleaning agent to the end of use is two-thirds or less of the maximum available chlorine concentration.
The average effective chlorine concentration in the cleaning solution from the start of use of the cartridge cleaning agent to the end of use is the amount of damage to the cleaning object caused by the chlorine agent when the same cleaning object is repeatedly washed using the same cartridge cleaning agent. be an indicator. By setting this average value to be two-thirds or less of the maximum effective chlorine concentration, damage to the cleaning object can be further reduced.
In the cartridge cleaning agent of the present invention, the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less, and there is at least one peak in the first half and at least one in the second half of the period from the start to the end of use of the cartridge cleaning agent. Therefore, the fact that the average value of the effective chlorine concentration is less than two-thirds of the maximum effective chlorine concentration means that the effective chlorine concentration is lower than the peak effective chlorine concentration in the period other than the above peak. means that it is controlled by

Moreover, the average value of the effective chlorine concentration is preferably 3 ppm or more and 30 ppm or less.
The average value of effective chlorine concentration can be obtained as the average value of effective chlorine concentration at each measurement point when a graph is drawn with the measured effective chlorine concentration on the vertical axis and the usage amount of the cartridge cleaning agent on the horizontal axis.

In the cartridge cleaning agent of the present invention, the minimum effective chlorine concentration is preferably 0 or more and less than 5 ppm in a section excluding the start and end of supply when repeatedly cleaning an object to be cleaned.
The fact that there is a section where the minimum effective chlorine concentration is 0 or more and less than 5 ppm in the section excluding the beginning and end of the supply means that there is a section where the effective chlorine concentration drops considerably in the section other than the two peaks. In this case, damage to the object to be cleaned can be reduced.

Each component constituting the solid detergent composition will be described below.
The solid detergent composition contains an alkali agent (A), a chelating agent (B) and a chlorine agent (C). Other components may include, for example, anticorrosive agents, surfactants, polymer dispersants, and the like.

As the alkali agent (A), any water-soluble alkali agent can be used, and for example, an alkali metal salt or an alkaline earth metal salt can be used. 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. alkali metal hydroxides such as sodium oxide and potassium hydroxide; alkali metal phosphates such as trisodium phosphate; alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate; sodium silicate (sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4), potassium silicate (potassium metasilicate, sesquisilicate Alkali metal salts of silicic acid such as potassium, potassium orthosilicate) are preferred. These alkaline agents may be hydrates. Among them, alkali metal hydroxides and alkali metal salts of silicic acid are more preferable, and alkali metal salts of silicic acid are more preferable. Compounds exemplified as chelating agents to be described later are not included in the alkaline agent in the present invention.

The content of the alkaline agent is preferably 5 to 85% by mass with respect to the entire solid detergent composition. When the content of the alkaline agent is within the above range, the detergency becomes higher. The content of the alkali agent is preferably 10 to 70% by mass. When two or more alkaline agents are contained, the above content is defined as the total content of each alkaline agent. Moreover, when the alkaline agent is a hydrate, the above content includes the water component contained in the hydrate.

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

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

Examples of the hydroxycarboxylic acid-based chelating agents 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 tripolyphosphoric acid and hexametaphosphate.

Phosphonic acid-based chelating agents include hydroxyethylidene diphosphonic acid (HEDP), nitrilotrismethylene phosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylene phosphonic acid (EDTMP), salts thereof, and the like. are mentioned.

Examples of the salt in the chelating agent include alkali metal salts such as potassium and sodium; magnesium salts; and alkaline earth metal salts such as calcium. Among them, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.

The chelating agent used in the present invention is preferably an aminocarboxylic acid-based or phosphonic acid-based chelating agent such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, methylglycinediacetic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid, or Salts and the like are more preferred, and ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, or salts thereof are even more preferred.

The content of the chelating agent is preferably 5 to 85% by mass with respect to the entire solid detergent composition. If the chelating agent is less than 5% by mass, the generation of calcium-derived scale may become a problem. If the chelating agent exceeds 85% by mass, detergency may be lowered. The content of the chelating agent is more preferably 10 to 60% by mass. When two or more chelating agents are contained, the above content is defined as the total content of each chelating agent.

The chlorine agent (C) is preferably a coated chlorine agent comprising a chlorine agent and a coating agent that coats the circumference of the chlorine agent.
By coating the surroundings of the chlorine agent with a coating agent, other components contained in the solid detergent composition, such as a chelating agent and an alkali agent, are prevented from reacting with the chlorine agent and deactivating the chlorine agent. be able to. Therefore, when the chlorine agent is contained in the solid detergent composition in the form of a coated chlorine agent, the solid detergent composition can contain the chlorine agent in an effective state.

Examples of the chlorine agent constituting the coating chlorine agent include dichloroisocyanuric acid (chlorinated isocyanuric acid) salts (sodium dichloroisocyanurate (chlorinated sodium isocyanurate), potassium dichloroisocyanurate (chlorinated potassium isocyanurate), etc.), trichloroisocyanurate Chlorine agents such as acids and hypochlorites (sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc.) can be mentioned. These chlorine agents may be hydrates. Among them, dichloroisocyanurate, trichloroisocyanuric acid, and hypochlorite are preferable as the chlorine agent. Sodium dichloroisocyanurate is preferred as the dichloroisocyanurate. The chlorine agent may be one kind of chlorine agent or a combination of two or more kinds of chlorine agents.

Examples of coating agents include carboxylates and silicates.
Examples of carboxylates include aromatic carboxylates, non-cyclic dicarboxylic acid salts, non-cyclic monocarboxylic acid salts having 1 to 7 carbon atoms, and the like.
Examples of aromatic carboxylic acid salts include benzoic acid, salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, cinnamic acid, o-toluic acid, m-toluic acid, p-toluic acid, and 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, p-benzoylbenzoic 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- salts of aromatic carboxylic acids such as mandelic acid, L-mandelic acid, trimellitic acid, pyromellitic acid, 2-methoxyphenylacetic acid, 3-methoxyphenylacetic acid, and 4-methoxyphenylacetic acid; They can be used singly or in combination of two or more.

Acyclic dicarboxylic acid salts include succinate, glutarate, adipate, suberate, azelate, sebacate, undecanedioate, dodecanedioate, tetradecanedioate, and the like. .
Non-cyclic monocarboxylic acid salts having 1 to 7 carbon atoms include formates, acetates, propionates, butyrates, valerates, hexanoates, heptanoates and the like.

Examples of silicates include orthosilicates, metasilicates, metadisilicates, and the like.

Among them, benzoates, o-phthalates, m-phthalates, p-phthalates, and trimellitates are preferred for their safety, non-reactivity with chlorine agents, ease of molding as coating agents, etc. , pt-butyl benzoate, and metasilicate are preferred, and benzoate is more preferred. Since benzoate has good stability against chlorine agents, if a coated chlorine agent coated with a coating agent containing benzoate is used, decomposition of the chlorine agent, etc. during storage of the solid detergent composition can be prevented. It is possible to effectively prevent it, and it is possible to suppress a decrease in the effective chlorine content and a decrease in detergency and sterilization power. Moreover, since the benzoate is excellent in rapid dissolution, it can exhibit good detergency and sterilization power when washing using the solid detergent composition. In addition, benzoates are less foamy and, for example, are less likely to reduce cleaning efficiency when used in automatic cleaning machines.
The benzoate includes sodium benzoate, potassium benzoate, calcium benzoate, magnesium benzoate, etc. From the viewpoint of solubility, sodium benzoate is preferred.

Examples of salts in the chlorine agent and coating agent include salts of alkali metals such as potassium and sodium, salts of magnesium, and salts of alkaline earth metals such as calcium. Among them, alkali metal salts are preferable, and sodium salts and potassium salts are more preferable.

The coating chlorine agent includes a chlorine agent, and benzoate, o-phthalate, m-phthalate, p-phthalate, trimellitate, p- At least one selected from the group consisting of t-butyl benzoate and metasilicate is preferred. A combination of the coated chlorine agent in which the chlorine agent is sodium dichloroisocyanurate and the coating agent is sodium benzoate is more preferred.

The weight ratio of the chlorine agent/coating agent is, for example, preferably 1-9, more preferably 1.5-4. The method of coating the chlorine agent is not particularly limited. For example, a solid chlorine agent is sprayed with a solution obtained by dissolving or suspending a benzoate in a solvent such as water, methanol, ethanol, ether, etc., followed by drying and coating; Examples include a method of mixing powder and spraying a binder such as water to coat. The method of tableting the chlorine agent and the method of granulating are not particularly limited. For example, a binder or the like can be added to the chlorine agent and tableted or granulated.

The coating chlorine agent preferably has a specific gravity of 1.0 to 2.0 g/cm ³ .

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 is substantially free of uncoated chlorine agents.

When the solid detergent composition contains an anticorrosive agent, the anticorrosion action (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. Such anticorrosives include, for example, benzotriazole or derivatives thereof (eg, benzotriazole, tolyltriazole, 5-dodecylbenzotriazole, 5-octylbenzotriazole, 5-hexylbenzotriazole, 5-butylbenzotriazole, 5-methyl benzotriazole, 4-carboxybenzotriazole, 5-carboxybenzotriazole, carboxybenzotriazole methyl ester, carboxybenzotriazole butyl ester, carboxybenzotriazole hexyl ester, benzotriazole octyl ester, dicarboxypropylbenzotriazole, etc.), benzimidazole or its derivatives (eg, benzimidazole, 2-mercaptobenzimidazole, thiazolylbenzimidazole, thiabendazole, etc.), benzothiazole or derivatives thereof (eg, benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-mercaptobenzo thiazole, etc.) can be suitably used. Among them, benzimidazole, benzotriazole and tolyltriazole are preferred.

When the solid detergent composition contains an anticorrosive agent, the content of the anticorrosive agent is preferably 0.001 to 5% by mass based on the total solid detergent composition. If the anticorrosive is less than 0.001% by mass, the anticorrosive action may not be sufficient. If the content of the anticorrosive agent exceeds 5% by mass, the odor peculiar to the anticorrosive agent may have a strong influence. The content of the anticorrosive agent is preferably 0.1 to 2% by mass. When two or more anticorrosive agents are contained, the above content is defined as the total content of each anticorrosive agent.

The solid detergent composition may contain a surfactant.
As surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. can be used, and nonionic surfactants are preferred. Examples of nonionic surfactants include polyoxyalkylene dialkyl ethers, reverse pluronic block polymers, polyoxyalkylene alkylphenyl ethers, fatty acid alkanolamides, polyoxyalkylene fatty acid alkanolamides, polyoxyalkylene fatty acid esters, and polyoxyalkylene sorbitan fatty acids. esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, alkylpolyglycosides, polyoxyethylene methyl ether fatty acid esters, polyoxyalkylenealkylamines and the like.

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

The solid detergent composition may contain a polymeric dispersant. The weight-average molecular weight of the polymeric dispersant is preferably 3,000 to 300,000, for example.
When such a polymer dispersant is contained, the anti-scaling ability is improved. Only one type of polymer dispersant may be used, or two or more types may be used in combination.
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, and 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 cross-linked copolymer Polymer, maleic anhydride acrylic acid copolymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic acid 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 aconitic acid copolymer, itaconic maleic acid copolymer, acrylic itaconic acid Acid copolymers, methylene malonate copolymers, itaconic fumaric acid copolymers, ethylene glycol ethylene terephthalate copolymers, vinylpyrrolidone-vinyl acetate copolymers, metal salts thereof, and the like.
Examples of metal salts include salts of alkali metals such as potassium and sodium; salts of alkaline earth metals such as magnesium and calcium. Among them, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.
As the polymeric dispersant, polyacrylates and salts of olefin-maleic acid copolymers are preferred, and sodium polyacrylates and sodium salts of olefin-maleic acid copolymers are more preferred.
The weight-average molecular weight is determined by gel permeation chromatography using a phosphate buffer solution and acetonitrile as developing solvents and using polyacrylic acid as a standard substance.

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

The solid detergent composition may also contain other components such as solubilizers, bleaching agents, disinfectants, enzymes, extenders, antifoaming agents, and solvents (for example, water). Even if some of the components constituting the solid detergent composition are liquid, the detergent composition as a whole may be solid as long as it is impregnated with other constituent components.

The pH when the solid detergent composition is dissolved in water is not particularly limited, but is preferably in the neutral to alkaline range, for example.
The pH when the solid detergent composition is dissolved in water is a pH measured in a state where 10 g of the detergent composition is mixed with 90 g of water (the concentration of the detergent composition is 10% by weight), and is a neutral detergent. When used as a composition, the pH is preferably 6 or more and less than 9. When used as a weakly alkaline detergent composition, the pH is preferably 9 or more and less than 12. When used, the pH is desirably 12 or higher.
The pH can be measured using a D-21 type pH meter manufactured by Horiba, Ltd.

Hereinafter, when the cartridge cleaning agent of the present invention is used, at least one peak occurs in the first half of the period from the start of use of the cartridge cleaning agent to the end of use of the cleaning agent when the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less. , an example embodiment of a cartridge cleaning material to come to be present at least one in the second half period.

The cartridge cleaning agent 1 shown in FIG. 1 already shown is one embodiment of the cartridge cleaning agent of the present invention.
In this cartridge cleaning agent, the solid cleaning agent composition is in a solid form in which the contents are integrated, and the portion where the chlorine agent (C) is unevenly distributed in the solid cleaning agent composition is based on the volume of the cartridge cleaning agent. At least one location exists in the upper half and at least one location exists in the lower half.

In the cartridge cleaning agent 1 shown in FIG. 1, the solid cleaning agent composition 20 includes the high-chlorine layers 21a and 21b, which are layers containing a large amount of the chlorine agent, and the content of the chlorine agent is lower than that of the high-chlorine layers. A detergent layer 22 is provided.
It can be said that the high-chlorine layer 21a and the high-chlorine layer 21b are locations where the chlorine agent (C) is unevenly distributed. It can be said that the high-chlorine layer 21a exists in the upper half of the cartridge cleaning agent by volume, and the high-chlorine layer 21b exists in the lower half of the cartridge cleaning agent by volume.

FIG. 2 shows how the cartridge cleaning agent 1 is used to obtain the cleaning agent solution.
As shown in FIG. 2(a), when the cartridge cleaning agent 1 is first used, the high-chlorine layer 21a, which is a layer containing a large amount of chlorine agent, is dissolved. The available chlorine concentration in becomes high.
As shown in FIG. 2B, when about half of the cartridge cleaning agent 1 is used, the cleaning agent layer 22 containing a small amount of chlorine agent is dissolved. Therefore, the effective chlorine concentration in the detergent solution 62 generated at this stage becomes low.
As shown in FIG. 2(c), when the cartridge cleaning agent 1 is about to be used, the high-chlorine layer 21b, which is a layer containing a large amount of the chlorine agent, is dissolved. The available chlorine concentration in becomes high.

Therefore, at the start of use of the cartridge cleaning agent 1 and just before the end of use, the concentration of available chlorine in the generated cleaning agent solution becomes high, and a peak occurs in which the concentration of available chlorine in the cleaning solution ranges from 5 ppm to 100 ppm.
Also, the effective chlorine concentration does not become so high except when the cartridge cleaning agent 1 is started to be used and just before the end of use.

Next, another embodiment of the cartridge cleaning agent of the present invention will be described.
FIG. 3 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention.
In this cartridge detergent, the chlorine agent (C) is the solid chlorine agent (c1), and the solid detergent composition includes a layer of the solid chlorine agent (c1) and a layer of detergent components other than the solid chlorine agent. , At least one layer of the solid chlorine agent (c1) is present in the upper half and at least one layer in the lower half, based on the volume of the cartridge cleaning agent.

In the cartridge detergent 101 shown in FIG. 3, a water-insoluble container 10 contains a solid detergent composition 120 as its contents.
The solid detergent composition 120 consists of five layers: solid chlorine agent layers 121B and 121D containing a solid chlorine agent 123 and layers 122A, 122C and 122E of detergent components other than the solid chlorine agent. It can be said that the solid chlorine agent layer 121B exists in the upper half of the cartridge cleaning agent by volume, and the solid chlorine agent layer 121D exists in the lower half of the cartridge cleaning agent by volume.

As the solid chlorine agent, a solid chlorine agent obtained by adding a binding aid to the chlorine agent can be preferably used. Moreover, as the chlorine agent used for the solid chlorine agent, the chlorine agent mentioned as the chlorine agent constituting the coating chlorine agent can be used. Moreover, you may use what solidified by adding a binding aid to the coating chlorine agent.

As the layer of detergent components other than the solid chlorine agent, a solid detergent composition containing an alkali agent and a chelating agent and, if necessary, other components can be used.
As the alkaline agent, the chelating agent and other components, the components described as the respective components constituting the solid detergent composition can be used, and the detergent layer 22 in the detergent cartridge 1 shown in FIG. ingredients can be used.
Moreover, the chlorine agent may be contained in the solid detergent composition constituting the layer of the detergent component other than the solid chlorine agent. In this case, considering the effective chlorine concentration at the time of use, it is preferable to add a small amount of the chlorine agent.

When the cartridge cleaning agent 101 shown in FIG. 3 is used, the effective chlorine concentration in the cleaning agent solution generated at the time when the layer 121B of the solid chlorine agent dissolves and at the time the layer 121D of the solid chlorine agent dissolves increases, and the cleaning solution A peak occurs in which the available chlorine concentration is 5 ppm or more and 100 ppm or less.
The solid chlorine agent layer 121B is present in the upper half of the cartridge cleaning agent by volume, and the solid chlorine agent layer 121D is present in the lower half of the cartridge cleaning agent by volume. At least one peak having an available chlorine concentration of 5 ppm or more and 100 ppm or less occurs in the latter half of the period.
In addition, when the layers 122A, 122C, and 122E 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.

Further, another embodiment of the cartridge cleaning agent of the present invention will be described.
FIG. 4 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention.
5(a), 5(b) and 5(c) are conceptual diagrams schematically showing an embodiment of the inner lid and the outer lid constituting the cartridge cleaning agent shown in FIG. be.

In this cartridge cleaning agent, the container comprises a container body, an inner lid and an outer lid. The container body contains the solid detergent composition, and the inner lid contains a chlorine agent (C). Separately, the solid chlorine agent (c2) is contained, and a partition is provided between the container body and the inner lid to prevent the movement of the solid chlorine agent (c2) or the solid detergent composition. Among the peaks at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less, the peak occurring in the first half period is caused by the dissolution of the solid chlorine agent (c2).

FIG. 4 shows the cartridge cleaning agent 201 divided into a container body 210, an inner lid 232, an outer lid 233, and a cover portion 234 as a partition.
The container main body 210 is a water-insoluble container containing a solid detergent composition 220 as its contents.
The solid detergent composition 220 is provided with a high-chlorine layer 221 having a large amount of chlorine agent and a detergent layer 222 having a lower chlorine agent content than the high-chlorine layer.
The high-chlorine layer 221 is a layer provided on the bottom side of the cartridge cleaning agent.
As components constituting the high-chlorine layer 221 and the cleaning agent layer 222, the same components as those of the high-chlorine layer 21b and the cleaning agent layer 22 in the cartridge cleaning agent 1 shown in FIG. 1 can be used.

The container body 210 has a so-called funnel shape in which the diameter of the lower portion of the cylindrical container gradually decreases. There is a cylindrical member 212 at the bottom.
The cylindrical member 212 is formed with a screw 212a for screwing the inner lid body 232 thereon. Although not shown, the cylindrical member may be adapted to fix the inner lid member by fitting with a pawl structure instead of by screwing.

The inner lid 232 contains a solid chlorine agent 223 separately from the high-chlorine layer 221 contained in the solid cleaning composition 220 . This is the solid chlorine agent (c2), and as the solid chlorine agent (c2), a solidified chlorine agent obtained by adding a binding aid to the chlorine agent can be preferably used.
Moreover, as the chlorine agent used for the solid chlorine agent, the chlorine agent mentioned as the chlorine agent constituting the coating chlorine agent can be used. Moreover, you may use what solidified by adding a binding aid to the coating chlorine agent.

The inner lid 232 shown in FIG. 5(a) has a cylindrical shape with a bottom, and the bottom 232b includes a cylindrical member 232d for allowing jetted water to pass therethrough, a solid detergent composition and a solid chlorine agent 223 (see FIG. 5). (b)) is provided for passage of the detergent solution, and the inner wall of the cylindrical portion 232c of the inner lid 232 is provided with an opening 232a for screwing into the cylindrical member 212 (see FIG. 4). screw 320a is provided.
A portion for placing the solid chlorine agent 223 , including the opening 232 a and the bottom 232 b , is the placement portion of the inner lid 232 .
The bottom portion 232b has a mesh shape and is formed with a large number of openings 232a. When the bottom portion 232b has a mesh shape and a large number of openings 232a are formed, there is an advantage that the cleaning agent solution can easily pass through the bottom portion of the inner lid and be discharged uniformly.

Further, the inner lid 232 is further provided with an inner cylinder 232e, and is configured to accommodate the solid chlorine agent 223 inside the inner cylinder 232e (see FIG. 5(b)).
The solid chlorine agent 223 contained in the inner lid 232 is desirably a solid solid chlorine agent 223 of a size that does not drop from the mesh-shaped opening 232a of the bottom portion 232b.
Further, in the inner cylinder 232e of the inner lid body 232, a plurality of partitioning members 232f for restricting the movement of the solid chlorine agent 223 are provided to partition the space in the inner cylinder 232e. It is desirable to set the interval between the partitioning members 232f so that the solid chlorine agent 223 is placed between the partitioning members 232f. By restricting the movement of the solid chlorine agent 223 in this way, each solid chlorine agent can be uniformly dissolved.

Moreover, it is desirable that the partitioning by the partitioning member 232f loosely partition the space inside the inner cylinder 232e rather than completely partitioning it. "Loosely" means that the space in the inner cylinder 232e is divided by the dividing member 232f to such an extent that the movement of the solid solid chlorine agent 223 is regulated, while the space between the dividing member 232f and the inner wall of the inner cylinder 232e and/or a state in which a space is provided between the partition member 232f and the outer wall of the cylindrical member 232d so that liquid such as water or detergent solution can freely move between the inner cylinders 232e. In such a state, even if a liquid such as water or a cleaning agent solution is sprayed to a specific portion, the liquid is not biased in the inner cylinder 232e, so that only the specific solid chlorine agent 223 is sprayed. Dissolution is prevented.

Further, as shown in FIG. 5(b), a ring-shaped cover portion 234 is provided to hold the solid chlorine agent 223 in the inner cylinder 232e.
The cover part is a partition provided between the container body and the inner lid body to prevent movement of the solid chlorine agent or the solid detergent composition.

FIG. 5(c) shows a state in which a film member 233 as an outer lid is adhered to the back surface of the inner lid 232 shown in FIG. 5(a).
The film member 233 may be adhered to the inner lid 232 with an adhesive that can be peeled off when using the cartridge cleaning agent. The film member 233 can be peeled off by manually grasping the projecting portion 233a to which the adhesive is not applied. Alternatively, the film member may be a water-soluble film so that the film member dissolves and disappears upon contact with water.

When using such a cartridge cleaning agent, the film member 233 that is the outer cover is peeled off from the inner cover 232 .
The sprayed 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 the detergent solution in which the solid detergent composition 220 is dissolved. is generated.
The detergent solution enters the inner lid 232 through the opening 234a of the cover part 234, dissolves the solid chlorine agent 223, and generates a detergent solution containing the solid detergent composition and the solid chlorine agent. .
This cleaning agent solution falls from the opening 232a at the bottom of the inner lid 232 and flows into the cleaning tank of the automatic cleaning machine, and the cleaning agent solution containing the chlorine agent derived from the coated chlorine agent and the solid chlorine agent automatically cleans. introduced into the machine.
In the cartridge cleaning agent of this form, the cylindrical member 232d and the opening 232a at the bottom of the inner lid 232 correspond to the supply port.

When the cartridge cleaning agent 201 shown in FIG. 4 is used, first, when the solid chlorine agent 223 accommodated in the inner lid 232 dissolves, the effective chlorine concentration in the cleaning agent solution becomes high, and the effective chlorine concentration in the cleaning agent increases. A peak with a chlorine concentration of 5 ppm or more and 100 ppm or less is generated.
This peak is the peak that occurs in the first half period. Therefore, the amount of the solid chlorine agent to be blended is preferably such that dissolution is almost completed in the first half of the period from the start of use of the cartridge cleaning agent to the end of use.
For a while after the solid chlorine agent 223 is dissolved, the cleaning agent layer 222 containing a small amount of chlorine agent is dissolved. Therefore, the effective chlorine concentration in the detergent solution generated at this stage becomes low.
When the cartridge cleaning agent 201 is about to be used, the high-chlorine layer 221, which is a layer containing a large amount of the chlorine agent, is dissolved. A peak occurs in which the available chlorine concentration is 5 ppm or more and 100 ppm or less.
This peak is the peak that occurs in the second half period.

Further, another embodiment of the cartridge cleaning agent of the present invention will be described.
FIG. 6 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention.
In this cartridge cleaning agent 301, the solid cleaning agent composition 320 has a cleaning agent layer 322, a high-chlorine layer 321b, and a high-chlorine layer 321c.
The high-chlorine layer 321c is distributed in layers slightly above the center in the thickness direction of the solid cleaning composition 320, but is unevenly distributed in an area of about ⅓ of the same thickness of the solid cleaning composition 320. there is That is, the high-chlorine layer may not form a complete layer in the solid detergent composition.
When such a solid detergent composition 320 is used, the high-chlorine layer 321c is dissolved when the cartridge detergent 301 is used up to a little less than half. During the first half of the period, a peak occurs at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less.
In addition, since the high chlorine layer 321b is dissolved just before the end of use of the cartridge cleaning agent 301, the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm in the latter half of the period from the start of use of the cartridge cleaning agent to the end of use. The following peaks occur.
Although the chlorine agent contained in the high-chlorine layer of this embodiment is not particularly limited, it is preferably a coating chlorine agent. Moreover, the solid chlorine agent explained so far may be sufficient.

Further, another embodiment of the cartridge cleaning agent of the present invention will be described.
FIG. 7 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention.
In this cartridge cleaning agent 401 , the solid cleaning agent composition 420 includes a cleaning agent layer 422 as well as a high-chlorine layer 421 a and a high-chlorine layer 421 b.
The high-chlorine layer 421b is obliquely distributed at the bottom of the solid cleaning composition 420 .
That is, the high-chlorine layer may be formed so as to be inclined with respect to the thickness direction of the solid cleaning composition.
When the high-chlorine layer is formed so as to be inclined with respect to the thickness direction of the solid detergent composition, the available chlorine concentration can be gradually changed according to the dissolution of the solid detergent composition.
When such a solid cleaning composition 420 is used, the high-chlorine layer 421a is dissolved at the start of use of the cartridge cleaning agent 401, so that during the first half of the period from the start of use to the end of use of the cartridge cleaning agent, A peak occurs when the available chlorine concentration is 5 ppm or more and 100 ppm or less.
Also, when the cartridge cleaning agent 401 is used a little more than halfway, the dissolution of the high chlorine layer 421b begins, and the rate of dissolution of the high chlorine layer 421b gradually increases. During the latter half of the period up to , there occurs a peak at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less.
This peak is considered to be a somewhat broad peak.
Although the chlorine agent contained in the high-chlorine layer of this embodiment is not particularly limited, it is preferably a coating chlorine agent. Moreover, the solid chlorine agent explained so far may be sufficient.

Further, another embodiment of the cartridge cleaning agent of the present invention will be described.
FIG. 8 is a cross-sectional view schematically showing another embodiment of the cartridge cleaning agent of the present invention.
In this cartridge cleaning agent 501 , a solid cleaning agent composition 520 includes a cleaning agent layer 522 and a solid chlorine agent 523 a , a solid chlorine agent 523 b , and a solid chlorine agent 523 c.
The solid chlorine agent 523 a is arranged on the upper surface of the solid cleaning composition 520 , and the solid chlorine agent 523 b is arranged on the bottom surface of the solid cleaning composition 520 . Moreover, the solid chlorine agent 523c is arranged near the center of the solid cleaning composition 520 in the thickness direction.

Each solid chlorine agent arranged in the solid cleaning composition 520 is arranged in a position adjusted by a difference in specific gravity with respect to the cleaning agent layer 522 constituting the solid cleaning composition 520 .
As will be described later, in the production of the solid detergent composition, a mixed melt of components constituting the detergent layer is used, and the mixed melt and the solid chlorine agent are placed in a container.
The solid chlorine agent having a higher specific gravity than the mixed melt sinks to the bottom surface of the solid cleaning composition 520 and becomes a solid chlorine agent 523b.
The solid chlorine agent having a smaller specific gravity than the mixed melt floats on the surface of the solid cleaning composition 520 and becomes a solid chlorine agent 523a.
A solid chlorine agent having a specific gravity similar to that of the mixed melt becomes a solid chlorine agent 523c in the solid cleaning composition 520 without floating or sinking.

When such a solid cleaning agent composition 520 is used, the solid chlorine agent 523a is dissolved when the cartridge cleaning agent 501 is started to be used. A peak occurs when the available chlorine concentration is 5 ppm or more and 100 ppm or less.
In addition, since the solid chlorine agent 523b is dissolved just before the end of use of the cartridge cleaning agent 501, the effective chlorine concentration in the cleaning liquid is increased from 5 ppm to 100 ppm in the latter half of the period from the start of use of the cartridge cleaning agent to the end of use. The following peaks occur.
The solid chlorine agent 523c serves as a chlorine source that increases the effective chlorine concentration in the cleaning liquid in accordance with the timing of dissolution.

Next, the cleaning method of the present invention will be described.
In the cleaning method of the present invention, a water-insoluble container having a content supply port is installed with the supply port facing downward, and water is jetted to the supply port to dissolve the contents while supplying the contents. A cleaning method for repeatedly cleaning an object to be cleaned using a cartridge cleaning agent for an automatic cleaning machine, wherein the cartridge cleaning agent is the cartridge cleaning agent of the present invention, and the same cartridge cleaning agent is used. When the object to be cleaned is repeatedly washed, the available chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less at least once in the first half period and at least once in the second half period of the period from the start of use to the end of use of the cartridge cleaning agent. It is characterized by removing dirt accumulated on the cleaning object by cleaning with a cleaning liquid having a high chlorine concentration.

In the above method, cleaning is performed at least once in the first half of the period from the start of use to the end of use of the cartridge cleaning agent, and at least once in the second half of the period, with a high chlorine concentration cleaning solution having an effective chlorine concentration of 5 ppm or more. By doing so, the dirt accumulated on the cleaning object can be removed.
In addition, since cleaning with a high-chlorine-concentration cleaning solution is not performed during cleaning during other periods, damage to the cleaning object can be reduced.
Also, if the effective chlorine concentration exceeds 100 ppm, washing workers may feel unpleasant chlorine odor, and if the effective chlorine concentration exceeds 100 ppm, the material of the dishwasher and the objects to be washed will be affected.

In the cleaning method of the present invention, it is preferable that the average effective chlorine concentration in the cleaning liquid from the start of use of the cartridge cleaning agent to the end of use be two-thirds or less of the maximum available chlorine concentration.
By doing so, the damage given to the object to be cleaned can be further reduced.

Moreover, the average value of the effective chlorine concentration is preferably 3 ppm or more and 30 ppm or less.
The average value of effective chlorine concentration can be obtained as the average value of effective chlorine concentration at each measurement point when a graph is drawn with the measured effective chlorine concentration on the vertical axis and the usage amount of the cartridge cleaning agent on the horizontal axis.

In the cleaning method of the present invention, when repeatedly cleaning the 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 a section excluding the start and end of supply.
By doing so, the damage given to the object to be cleaned can be further reduced.

Contaminants accumulated on objects to be cleaned include composite contaminants in which components such as oils and fats, proteins, and starches are mixed. Objects to be cleaned include tableware, cutlery, cooking utensils, metal fittings, jigs, containers, trays, and the like.

By using the cartridge cleaning agent of the present invention, it is possible to clean with a cleaning solution having a high effective chlorine concentration and a high cleaning effect while suppressing damage to the cleaning object. Agglomerates can be preferably removed.
The method for sterilizing microorganisms or removing agglomerates of bacterial flora of the present invention is characterized by allowing the high-chlorine-concentrated cleaning solution used in the cleaning method of the present invention to act on bacteria and bacterial flora in an automatic washing machine.
According to the above-mentioned method, microorganisms or bacterial flora agglomerates can be preferably removed by allowing the cleaning liquid having a high chlorine concentration to act on the bacteria and bacterial flora formed in the automatic washing machine.

The bacterial flora agglomerate to be removed by the method for sterilizing microorganisms or the method for removing a bacterial flora agglomeration of the present invention is preferably a red-based or orange-based bacterial flora agglomerate. The cartridge cleaning agent of the present invention is useful for preventing the occurrence of red-colored or orange-colored bacterial flora coagulation or for eliminating bacteria.
An example of the flora clump includes a flora clump containing at least one microorganism selected from the group consisting of the genera Meiothermus and Tepidimonas. A lot of bacterial flora agglomerates containing at least one microorganism selected from the group consisting of the genera Meiothermus and the genera Tepidimonas tend to be red or orange. The cartridge cleaning agent of the present invention has sterilizing power against microorganisms belonging to the genus Meiothermus and Tepidimonas, and generates bacterial flora agglomerates containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepidimonas. It is preferably used for prevention or sterilization.
In one aspect, the cartridge cleaning agent of the present invention is used in a cleaning machine in which bacterial flora agglomerates containing at least one microorganism selected from the group consisting of the genus Meiothermus and the genus Tepidimonas are present, resulting in high detergency and high detergency. Demonstrates sterilization power against coagulum.

Examples of microorganisms belonging to the genus Meiothermus include Meiothermus ruber, Meiothermus taiwanensis, Meiothermus sylvanus, Meiothermus tyralophilus, Meiothermus cervereus, Meiothermus granatisius, Meiothermus rosaceus, Meiothermus rufus, and Meiothermus thymidus.
Microorganisms belonging to the genus Tepigimonas include Tepigimonas taiwanensis, Tepigimonas fonticardi, Tepigimonas aquatica, Tepigimonas ignava, Tepigimonas thermalum, and the like.
The number of microorganisms belonging to the genus Meiothermus and the number of microorganisms belonging to the genus Tepidimonas may each be one, or two or more. Meiothermus louvers, Meiothermus taiwanensis, and Meiothermus sylvanus are preferable as the microorganisms belonging to the genus Meiothermus, and Tepidimonas taiwanensis and Tepidimonas fonticardi are preferable as the microorganisms belonging to the genus Tepidimonas. In one aspect, the cartridge cleaner of the present invention is suitable for sterilization of at least one microorganism selected from the group consisting of Meiothermus louver, Meiothermus taiwanensis, Meiothermus sylvanus, Tepigimonas taiwanensis, and Tepigimonas fonticardi. is.

The cartridge cleaners of the present invention are also useful for disinfecting microorganisms of the genera Bacillus cereus (Bacillus cereus), Tepidiphilus, Licinibacillus and Diferisoma. The cartridge cleaning agent of the present invention can further be used for sterilization of at least one microorganism selected from the group consisting of Bacillus cereus species, Tepidiphilus, Licinibacillus and Diferisoma.
Microorganisms belonging to the genus Bacillus cereus, genus Tepidiphilus, genus Licinibacillus, and genus Diferisoma may each be one species or two or more species.
Microorganisms belonging to the genus Tepidiphilus include Tepidiphilus succinatemandens, Tepidiphilus thermophilus, and the like. As microorganisms belonging to the genus Licinibacillus, Licinibacillus fusiformis, Licinibacillus boronitoerans, Licinibacillus glesolivorans, Licinibacillus macroloides, Licinibacillus maciliensis, Licinibacillus odissei, Licinibacillus parvivoronicapiens, Licinibacillus sinduriensis, Licinibacillus su Felix, Licinibacillus sylanilyticus, and the like. Microorganisms belonging to the genus Diferisoma include Diferisoma camini, Diferisoma paleocoriens, and the like.

The bacterial flora coagulum may contain at least one microorganism selected from the group consisting of Bacillus cereus species, Tepidiphilus, Licinibacillus and Diferisoma. The cartridge cleaning agent of the present invention has sterilizing power against these microorganisms as well.
The cartridge cleaning agent of the present invention comprises at least one selected from the group consisting of the genera Meiothermus and Tepidimonas, and at least one selected from the group consisting of the genera Bacillus cereus, Tepidiphilus, Licinibacillus and Diferisoma. It is suitably used for preventing or eradicating bacterial flora agglomerates containing microorganisms.
Examples of microorganisms belonging to the genera Meiothermus, Tepidimonas, Bacillus cereus, Tepidiphilus, Licinibacillus, and Diferisoma include the microorganisms described above.
The presence of the above-mentioned microorganisms in the bacterial flora clump can be confirmed, for example, by DNA sequence analysis of 16S rDNA of the microbial group forming the bacterial flora clump. DNA sequence analysis of 16S rDNA can be performed by the method described in Examples.
In one aspect, the cartridge cleaners of the present invention are useful in the disinfection of microorganisms, such as Escherichia species bacteria, in addition to the microorganisms described above.

The method of applying the washing liquid to the microorganisms or the bacterial flora agglomerates containing them is not particularly limited, and the washing liquid is brought into contact with the microorganisms or the bacterial flora agglomerates containing the same. contacting the washing liquid of (1) with the microorganisms or the bacterial lawn coagulum containing the microorganisms. When objects to be washed such as dishes in an automatic washing machine are to be washed with the washing liquid, the washing liquid should be brought into contact with the objects to be washed in the automatic washing machine.

When objects to be washed such as tableware are washed with an automatic washing machine using the cartridge detergent of the present invention, the washing liquid obtained from the cartridge detergent and the tableware are brought into contact with each other in the automatic washing machine. good. When the cartridge cleaning agent of the present invention is used to remove bacterial flora clumps in an automatic washing machine, the cleaning liquid obtained from the cartridge cleaning agent may act on the bacterial flora agglomerates. In addition, in an automatic washing machine in which bacterial flora agglomerates containing microorganisms exist, in the case of sterilizing microorganisms, the washing liquid may be circulated in the automatic washing machine.

A method for producing the cartridge cleaning agent of the present invention will be described.
The method for preparing the solid detergent composition used in the cartridge detergent of the present invention is not particularly limited, but solids with a low chlorine agent content (for example, containing no chlorine agent) and solids with a high chlorine agent content are used. There is a method in which at least one type of each solid substance is produced, and the chlorine agent is unevenly distributed in at least one place in the upper half and at least one place in the lower half based on the volume of the cartridge cleaning agent. be done.

Instead of producing a solid material with a high chlorine content, the chlorine agent may be sprinkled and immobilized on a solid material with a low chlorine content during the solidification step. Alternatively, the bottom of the container may be sprinkled with a chlorine agent and then filled with a solid having a low chlorine agent content.
Alternatively, a solid chlorine agent may be used as the chlorine agent, and the solid substance having a low chlorine agent content and the solid chlorine agent may be alternately filled.

As the chlorine agent and other raw materials used for producing the solid, those mentioned above can be used.
In preparing raw materials for producing a solid material containing a large amount of chlorine agent, the chlorine agent and other raw material compositions are mixed with water (hot water) to prepare a mixed melt.
The water is mixed with the raw material composition as hot water, or mixed with the raw material composition as water and then heated to obtain hot water. The temperature of hot water for preparing the mixed melt is preferably 30 to 90°C.
In preparation of raw materials for producing a solid material containing no chlorine agent, a mixed melt may be prepared without using a chlorine agent and the same procedure as described above may be taken.

A solid can be produced by putting the mixed melt into a container and cooling and solidifying the mixed melt in the container.
Cooling may be performed at a temperature at which the components constituting the solid detergent composition are solidified, and may be simply left at room temperature (for example, 20 to 35°C). Also, such cooling may be omitted.

Further, a mixed melt containing a small amount of chlorine agent (for example, containing no chlorine agent) may be used in place of the solid matter containing a small amount of chlorine agent (for example, containing no chlorine agent).
A predetermined amount of a chlorine agent is sprinkled in a container, and a mixed melt of components of a solid detergent composition that does not contain a chlorine agent is placed thereon so that the position of the chlorine agent on the bottom of the container does not move much, A chlorine agent can be placed in the bottom of the container.
Alternatively, the chlorine agent can be immobilized on the supply port side of the container by placing a mixed melt of the components of the solid detergent composition containing no chlorine agent in a container and sprinkling the chlorine agent thereon.
After that, the mixed melt can be solidified to obtain a solid detergent composition.

In addition, in the present production method, the preferred mixing ratio of the chlorine agent and the other raw material composition can be the same as the ratio explained in the item of the solid detergent composition.
Further, it is preferable that the weight ratio of water (hot water) in the mixed melt is 5 to 20% by weight.

Furthermore, if necessary, a solid chlorine agent may be arranged in the inner lid and used together with a solid detergent composition containing a chlorine agent.

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

(Preparation of cartridge cleaning agent)
Cartridge cleaners for Examples 1-16 and Comparative Examples 1-4 were prepared.
Table 1 shows the chlorine agent powder and tablet used in each example.
Table 2 shows the overall formulation (composition) of the cartridge cleaning agents of Examples and Comparative Examples. Table 2 shows the proportion of each component in weight percent.

In the production of the solid detergent composition, each component is mixed in hot water to prepare a mixed melt, the mixed melt is placed in a water-insoluble container, and the mixed melt is cooled and solidified in the container. Thus, a solid detergent composition was produced. When the mixed melt was cooled and solidified, it was placed with the supply opening facing upward.

The operation of disposing the chlorine agent was performed as follows.
When the chlorine agent is placed on the "bottom of the container", a predetermined amount of powder of the chlorine agent is sprinkled on the container, and the mixed melt of the components of the solid detergent composition that does not contain the chlorine agent is added to the chlorine agent on the bottom of the container. The chlorine agent was arranged at the bottom of the container so that the position did not move too much.
When the chlorine agent is placed at "1/4 the height from the bottom of the container" or "1/2 the height from the bottom of the container", the components of the solid detergent composition that does not contain a chlorine agent are mixed and melted in the container. A liquid was put thereinto, powder of a chlorine agent was sprinkled thereon, and then a mixed melt of the components of a solid detergent composition containing no chlorine agent was put in such that the position of the chlorine agent did not move so much. The depth of the mixed melt of the components of the solid detergent composition that does not contain a chlorine agent is adjusted so that the chlorine agent is placed at "a quarter of the height from the bottom of the container" or "at the bottom of the container." Adjusted whether it is placed at 1/2 height from
When the chlorine agent is placed on the "surface of the solid detergent composition", a mixed melt of the components of the solid detergent composition that does not contain a chlorine agent is placed in a container, and the powder of the chlorine agent is sprinkled on the mixed melt and mixed. The chlorine agent was arranged on the surface of the solid detergent composition by solidifying the melt.
Also, in some examples, a solid chlorine tablet was placed in place of or in conjunction with the chlorine powder.
When the chlorine agent was placed in the "supply port inner lid", a solid chlorine agent tablet was placed in the inner lid.

(Measurement of effective chlorine concentration)
The cartridge detergent of each example and comparative example is installed in a supply device attached to an automatic dishwashing machine, and water is sprayed so as to obtain a washing liquid having a solid detergent composition concentration of 0.10% by weight. A washing liquid was obtained by adjusting the amount. The temperature of the jetted water was set at 35°C, and the available chlorine concentration was measured with 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 cleaning agent to the end of use.
(1) 100 g of the aqueous solution in the washing tank was weighed, 5 g of aluminum sulfate and 5 g of potassium iodide were added, and the mixture was sufficiently stirred.
(2) 10 mL of glacial acetic acid was added to the above aqueous solution.
(3) After uniformly mixing, titration was performed with an N/100 sodium thiosulfate aqueous solution.
(4) The end point was when the color of the solution changed from pale yellow to colorless.
(5) From the amount of sodium thiosulfate aqueous solution dropped at the end point, the effective chlorine concentration was calculated by the following formula (1).
Available chlorine concentration (ppm) = N/100 drop amount of sodium thiosulfate aqueous solution (mL) x 3.546 (1)

FIG. 9 is a graph showing the results of measurement of available chlorine concentrations for the cartridge cleaning agents of Examples 8 and 12 and Comparative Examples 1 and 4. FIG.
As shown in FIG. 9, in the cartridge cleaning agents of Examples 8 and 12, when measuring from the start of use of the cartridge cleaning agent to the end of use, the effective chlorine concentration in the cleaning solution peaked at 5 ppm or more and 100 ppm or less. However, one is present in the first half of the period from the start of use of the cartridge cleaning agent to the end of use, and one is present in the second half of the period.
On the other hand, in the cartridge cleaning agent of Comparative Example 1, the peak at which the available chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less does not exist in the second half period.
In the cartridge cleaning agent of Comparative Example 4, the effective chlorine concentration was as high as 5 ppm or more over the entire period, and it cannot be said that there is a peak at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less.

FIG. 9 shows a representative example of a graph showing the results of measuring the effective chlorine concentration. There is one peak in the first half period and one in the second half period of the period from the start of use of the cartridge cleaning agent to the end of use of the available chlorine concentration of 5 ppm or more and 100 ppm or less.
In Comparative Examples 2 and 3, since the chlorine agent was uniformly distributed in the solid detergent composition, the effective chlorine concentration was constant from the start of use of the cartridge detergent to the end of use, and the effective chlorine concentration was 5 ppm. There are no peaks above 100 ppm.

Table 2 shows the effective chlorine concentration peak concentrations in the first and second halves of each example and comparative example. For each comparative example in which there is no peak at which the available chlorine concentration is 5 ppm or more and 100 ppm or less, the maximum values of the available chlorine concentration in the first half and the second half are shown as peaks.
In addition, the average value of available chlorine concentration in each example and comparative example is also shown.
In addition, the following evaluations 1) to 3) were performed, and Table 2 summarizes the results.

1) Detergency evaluation (1) Add 70% water (80 mL) and 0.3 g of composite dirt to a glass container (115 mL) made of tempered glass, mix well, and tilt so that the wall surface is stained. and left in a 70° C. incubator overnight.
(2) Washing is performed using Hoshizaki 650 (manufactured by Hoshizaki Co., Ltd.) as an automatic dish washer with a detergent concentration of 0.1% by weight. , 0.3 g of composite soil (room temperature) was added, and after mixing well, it was tilted twice so that the wall surface was soiled in the same manner as above, and left in a 70° C. incubator for 10 minutes.
(3) The finish of the glass when (2) was repeated 10 times was evaluated according to the following evaluation criteria.
The evaluation was carried out using a cleaning solution having a composition in which the effective chlorine concentration was the smaller peak value.

<Evaluation Criteria>
◎: Few streaks and high transparency ○: Slightly high transparency with streaks △: Cloudy and many streaks ×: Significant dirt

2) Effect on melamine tableware Melamine tableware was washed repeatedly 10 times with a detergent concentration of 0.1% by weight. Hoshizaki 650 (manufactured by Hoshizaki Co., Ltd.) was used as an automatic dishwasher.
The evaluation was performed using a cleaning liquid having a composition that gave an average effective chlorine concentration.

<Evaluation Criteria>
◎: Same as before washing ○: Almost no yellowing ×: Yellowed

3) Sterilizing effect The bacteria to be tested were cultured at 60°C in a normal bouillon medium manufactured by Eiken Chemical Co., Ltd. for 24 hours to obtain a bacterial solution. Each sample (composition produced above) was diluted with deionized water to 0.1% and heated to 60 ° C., mixed with the bacterial solution at a ratio of 99 to 1 (volume ratio), and the sample added bacteria liquid. After reacting for 15 seconds, the sample-added bacterial solution was neutralized with a pH 7 buffer solution containing sterilized sodium thiosulfate, and the neutralized sample-added bacterial solution was serially diluted with physiological saline. 1000 μL of this diluted solution and 30 mL of standard agar medium manufactured by Nihon Pharmaceutical Co., Ltd. were added to the plate. Colony forming units (CFU) were counted after incubating the plates at 60° C. for 48 hours. From the difference in log ₁₀ CFU between the control and the sample (log ₁₀ CFU of the control - log ₁₀ CFU of the sample), the disinfecting power of the composition against the test bacteria was evaluated as follows. Ion-exchanged water at 60° C. was used as a control. The difference in log ₁₀ CFU between control and sample (log ₁₀ CFU of control minus log ₁₀ CFU of sample) is denoted as Δlog ₁₀ CFU.
The evaluation was carried out using a cleaning solution having a composition in which the effective chlorine concentration was the smaller peak value.

(Evaluation criteria for sterilization effect)
◎: Sterilization effect with Δlog ₁₀ CFU of 5 or more ○: Sterilization effect with Δlog ₁₀ CFU of 3 or more and less than 5 △: Sterilization effect of Δlog ₁₀ CFU of 1 or more and less than 3 ×: Δlog ₁₀ CFU is less than 1 sterilization effect of

From these evaluation results, there are at least one peak in the first half and at least one in the second half of 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 5 ppm or more and 100 ppm or less. It can be seen that the cartridge cleaning agents of Examples 1 to 16 can remove dirt and germs accumulated on the cleaning object with less damage to the cleaning object.
By using a cleaning liquid with a peak available chlorine concentration, it is possible to remove dirt and germs accumulated on the object to be cleaned.

On the other hand, in the cartridge cleaning agents of Comparative Examples 2 and 4, the effective chlorine concentration was high throughout the entire period from the start of use to the end of use of the cartridge cleaning agent, so the damage to the object to be cleaned was increased.
Further, in the cartridge cleaning agent of Comparative Example 1, there is no point where the effective chlorine concentration peaks in the second half period, and in the cartridge cleaning agent of Comparative Example 3, the effective chlorine concentration is over the entire period from the start to the end of use of the cartridge cleaning agent. There was no peak point.
As a result, dirt and germs accumulated on the object to be washed cannot be sufficiently removed.

1, 101, 201, 301, 401, 501 cartridge cleaning agent 10 container 11 supply port 20, 120, 220, 320, 420, 520 solid cleaning agent composition 21a, 21b, 221, 321b, 321c, 421a, 421b high Chlorine layers 22, 222, 322, 422, 522 Detergent layer 60 Jet water 61, 62, 63 Detergent solutions 121B, 121D Layers 122A, 122C, 122E of solid chlorine agent Layer 123 of detergent components other than solid chlorine agent , 223, 523a, 523b, 523c solid chlorine agent 210 container body 212 cylindrical member 212a screw 232 inner lid 232a opening 232b bottom 232c cylindrical portion 232d cylindrical member 232e inner cylinder 232f partitioning member 233 outer lid (film member)
233a Protruding portion 234 Cover portion 234a Cover portion opening 320a Screw

Claims (16)

A cartridge for an automatic dishwasher in which a water-insoluble container having a content supply port is installed with the supply port facing downward, and water is jetted to the supply port to dissolve the contents while supplying them. a cleaning agent,
The content is an alkaline agent (A) that is a silicate and/or carbonate, and at least one selected from the group consisting of ethylenediaminetetraacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, and salts thereof. A solid detergent composition comprising a chelating agent (B) and a chlorine agent (C) that is dichloroisocyanurate and/or trichloroisocyanuric acid , and optionally dichloroisocyanurate and/or trichloroisocyanuric acid A solid chlorine agent (c2) ,
With respect to the total amount of the solid detergent composition and the solid chlorine agent (c2), the content of the alkaline agent (A) is 10 to 60% by mass, and the content of the chelating agent (B) is 20 to 60% by mass. 50% by mass,
The chlorine agent (C) and, if desired, the solid chlorine agent (c2) are placed in two or three portions of the container bottom layer, the intermediate layer, the surface layer, and the inner lid of the solid detergent composition, respectively. It is dispersed and installed so that it is contained in an amount of 0.25 to 3% by mass with respect to the total amount of the solid detergent composition and the solid chlorine agent (c2),
The cartridge detergent is installed in a supply device attached to an automatic dishwashing machine, and the effective chlorine concentration of the washing solution obtained by dissolving the solid detergent composition in water at 35° C. is measured when the concentration of the solid detergent composition is 0. When measuring from the start of use of the cartridge cleaning agent to the end of use in the cleaning solution of 10% by weight, the peak at which the effective chlorine concentration in the cleaning solution is 5 ppm or more and 100 ppm or less is the peak from the start of use to the end of use of the cartridge cleaning agent. There is at least one in the first half of the cleaning period and at least one in the second half of the cleaning period, and the average value of the available chlorine concentration in the cleaning period is 3 ppm or more and 30 ppm or less, and during the cleaning period, at the start of use and at the time of use There is a period other than the end when the effective chlorine concentration is less than 1/3 of the maximum effective chlorine concentration measured during the use of the cartridge cleaning agent.
A cartridge cleaning agent characterized by: 2. The cartridge cleaning method according to claim 1, wherein the average effective chlorine concentration in the cleaning solution from the start of use of the cartridge cleaning agent to the end of use is two-thirds or less of the maximum available chlorine concentration measured during use of the cartridge cleaning agent. agent. 3. The cartridge cleaning agent according to claim 1, wherein the minimum effective chlorine concentration is 0 or more and less than 5 ppm in a section excluding the start and end of supply of the cleaning agent when repeatedly cleaning the object to be cleaned. 4. The cartridge cleaner according to any one of claims 1 to 3, wherein said chlorine agent (C) is a coated chlorine agent comprising a chlorine agent and a coating agent surrounding said chlorine agent. The coating agent contains 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. 5. The cartridge cleaner of claim 4, which is a salt. The solid detergent composition is in a solid form in which the contents are integrated, and the part where the chlorine agent (C) is unevenly distributed in the solid detergent composition is the upper half of the cartridge detergent based on the volume. 6. The cartridge cleaning agent according to any one of claims 1 to 5, which exists at least one location in the lower half and at least one location in the lower half. The chlorine agent (C) is a solid chlorine agent (c1),
The solid cleaning agent composition includes a layer of the solid chlorine agent (c1) and a layer of cleaning agent components other than the solid chlorine agent, and the layer of the solid chlorine agent (c1) is the volume of the cartridge cleaning agent. The cartridge cleaning agent according to any one of claims 1 to 5, which is present in at least one portion in the upper half and in at least one portion in the lower half. The container comprises a container body, an inner lid and an outer lid,
The container body contains the solid cleaning composition,
The inner lid contains a solid chlorine agent (c2) separately from the chlorine agent (C), and between the container body and the inner lid, the solid chlorine agent (c2) or A partition is provided to prevent movement of the solid detergent composition,
8. The cartridge cleaning agent according to any one of claims 1 to 7, wherein the peak occurring in the first half of the peaks at which the effective chlorine concentration in the cleaning liquid is 5 ppm or more and 100 ppm or less is caused by dissolution of the solid chlorine agent (c2). A cartridge for an automatic dishwasher in which a water-insoluble container having a content supply port is installed with the supply port facing downward, and water is jetted to the supply port to dissolve the contents while supplying them. A cleaning method for repeatedly cleaning an object to be cleaned using a cleaning agent,
The cartridge cleaning agent is the cartridge cleaning agent according to any one of claims 1 to 8, and is used from the start of use of the cartridge cleaning agent when repeatedly cleaning an object to be cleaned using the same cartridge cleaning agent. At least once in the first half of the cleaning period and at least once in the second half of the cleaning period until the end, cleaning is performed with a high chlorine concentration cleaning liquid having an effective chlorine concentration of 5 ppm or more and 100 ppm or less. remove accumulated dirt,
The average effective chlorine concentration during the cleaning period is 3 ppm or more and 30 ppm or less, and the effective chlorine concentration is the maximum available chlorine measured during the use of the cartridge cleaning agent during the cleaning period, except at the start and end of use. A cleaning method characterized in that there is a period of less than one-third of the concentration . 10. The cleaning method according to claim 9, wherein the average effective chlorine concentration in the cleaning liquid from the start of use of the cartridge cleaning agent to the end of use is two-thirds or less of the maximum available chlorine concentration measured during use of the cartridge cleaning agent. . 11. The cleaning method according to claim 9 or 10, wherein when the object to be cleaned is repeatedly cleaned, cleaning is performed with a cleaning liquid having a minimum effective chlorine concentration of 0 or more and less than 5 ppm in a section excluding the beginning and end of supply of the cleaning agent . A method for sterilizing microorganisms or agglomeration of bacterial flora, characterized in that the high chlorine concentration cleaning liquid used in the cleaning method according to any one of claims 9 to 11 is allowed to act on bacteria and bacterial flora in an automatic dishwasher . removal method. 13. The method for sterilizing microorganisms or removing clumps of bacterial flora according to claim 12, wherein the clumps of bacterial flora are red-colored or orange-colored clumps. 14. The method for sterilizing microorganisms or removing a clump of bacterial flora according to claim 12 or 13, wherein the clump of bacterial flora contains at least one microorganism selected from the group consisting of the genera Meiothermus and Tepidimonas. 15. The method of sterilizing microorganisms or concentrating the bacterial flora according to claim 14, wherein the bacterial flora further comprises at least one microorganism selected from the group consisting of Bacillus cereus, Tepidiphilus, Licinibacillus and Diferisoma. How to remove clumps. 16. The method for sterilizing microorganisms or the microbial flora aggregate according to any one of claims 12 to 15, wherein, in an automatic dishwashing machine in which the microbial flora agglomerate is present, the microbial flora agglomerate is sterilized while washing an object to be washed. How to remove clumps.

Images