JP7287635B2 - Cartridge detergent, method for sterilizing microorganisms or method for removing coagulum of bacterial flora, and method for producing cartridge detergent - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cartridge cleaning agent, a method for sterilizing microorganisms or removing agglomerates of bacterial flora, and a method for producing a cleaning agent for cartridges.

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 describes a molten solid detergent composition.
Further, Patent Document 2 discloses a cartridge cleaning agent in which a solid cleaning agent composition can be used. Patent Literature 2 describes that water is injected into a cartridge cleaning agent to obtain a cleaning liquid, and the cleaning liquid is introduced into an automatic dishwasher.

JP 2017-186549 A JP 2017-8267 A

Patent Document 1 discloses a melt-solid cleaning composition obtained by cooling and solidifying a melt-mixed cleaning composition.
In paragraph [0021] of Patent Document 1, a molten solid type detergent composition is generally prepared by melting and mixing each component under heating, filling the molten mixture into a container such as a plastic container, and cooling and solidifying in the container. It is stated that it will be commercialized.

In Patent Document 1, as one aspect of a molten solid detergent composition, a slurry containing a chlorine bleach coated with a coating agent is prepared and solidified by cooling to obtain a molten solid detergent composition. Are listed.

When a molten solid cleaning composition as described in Patent Document 1 is used as a solid cleaning composition in a cartridge cleaning agent as described in Patent Document 2, the cartridge cleaning agent is used from the start to the end of use. It is desirable that the composition of the components constituting the cleaning composition remain constant over the entire period.
This is because if the composition of the components constituting the detergent composition changes between the start and end of use, the detergency, sterilization properties, etc. will also change.

Regarding this point, in Patent Document 1, in paragraph [0047], as a component uniformity test, the cooled solid matter at the top and bottom of the container is collected and the chelating force is measured. It discloses that less is preferred.

Here, the present inventors produced a molten solid type cleaning composition as described in Patent Document 1, and measured the effective chlorine concentration of the cleaning solution, which is an index affecting the sterilization power, of the cartridge cleaning agent. Observations were made continuously from the start of use to the end of use.
As a result, it was found that although the effective chlorine concentration exceeded 10 ppm at the start of use, the effective chlorine concentration immediately decreased and remained almost constant at a low value of about 3 ppm until the end of use.
Although it is preferable to have an effective chlorine concentration of 5 ppm or more in order to exhibit the sterilization power, it was found that the use of this cartridge cleaning agent does not provide sufficient sterilization power except immediately after the start of use.

The reason for this was thought to be that the particles of the chlorine bleaching agent were concentrated near the surface of the container when the produced molten solid detergent composition was observed.
Upon further investigation by the present inventors, it was found that the particles of the chlorine bleach used in Patent Document 1 are light and tend to float on the surface when the molten mixture is allowed to stand still.
Therefore, in the molten solid detergent composition obtained by filling the molten mixture in a container and solidifying it by cooling, the concentration of the chlorine bleach near the surface of the container (the surface of the solid matter) is high, The concentration of chlorine bleach in the area other than the area was low.

The present invention was made to solve the above problems, and when the cartridge cleaning agent is used continuously, the effective chlorine concentration of the cleaning solution is maintained at a stable high value from the start of use to the end of use of the cartridge cleaning agent. It is an object of the present invention to provide a cartridge cleaning agent that can

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. The cartridge cleaning agent for an automatic cleaning machine of , wherein the contents are a solid cleaning agent composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated chlorine agent (C) The cartridge cleaning agent is installed in 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 at 25°C. It is characterized in that the effective chlorine concentration in the cleaning liquid is 5 ppm or more from the start of use to the end of use in the cleaning liquid at which the concentration of the solid detergent composition is 0.05% by weight.

The cartridge detergent of the present invention contains a surface-coated chlorine agent as a chlorine agent in the solid detergent composition. Since the coated chlorine agent has low reactivity with the coexisting alkali agent and chelating agent in the solid detergent composition, it is possible to suppress the decrease in the effective chlorine concentration.
In addition, when the cartridge detergent of the present invention is installed in an automatic dishwashing machine and used, the effective chlorine concentration in the cleaning liquid is 5 ppm from the start of use of the cartridge detergent to the end of use (when the detergent is consumed and used up). As described above, the effective chlorine concentration of the cleaning liquid can be stably maintained at a high value from the start of use of the cartridge cleaning agent to the end of use.
The 0.05% by weight indicated as the concentration of the solid detergent composition in the cleaning liquid indicates the lower limit of the concentration of the detergent composition required for cleaning.

When the cartridge cleaning agent of the present invention is installed in 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 at 25°C, It is preferable that the variation in the effective chlorine concentration in the cleaning solution from the start of use of the cartridge cleaning agent to the end of use is within ±8 ppm of the average value in the cleaning solution in which the concentration of the solid cleaning composition is 0.05% by weight.

A small variation in available chlorine concentration is preferable because the variation in detergency and sterilization performance is also small. If the variation is large, the effective chlorine concentration may become too high, which is not preferable from the viewpoint of odor.

In the cartridge cleaning agent of the present invention, the absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the solid cleaning composition is 0.8 g. /cm ³ or less.

When the difference between the specific gravity of the coated chlorine agent and the specific gravity of the components other than the coated chlorine agent is small, the concentration of the coated chlorine agent on the surface or bottom of the container is prevented. The effective chlorine concentration of the cleaning liquid can be stably maintained at a high value until the end of use.

In the cartridge cleaning agent of the present invention, the specific gravity of the coating chlorine agent (C) is preferably 1.0 to 2.0 g/cm ³ .
It is preferable to use a material having a specific gravity of this level as the coating chlorine agent, since the difference in specific gravity from components other than the coating chlorine agent does not become large.

In the cartridge cleaning agent of the present invention, the coating chlorine agent (C) comprises a chlorine agent and a coating agent that coats the periphery of the chlorine agent, and the coating agent includes benzoic acid, o-phthalic acid, m- Salts of one or more aromatic carboxylic acids selected from the group consisting of phthalic acid, p-phthalic acid, trimellitic acid and pt-butylbenzoic acid are preferred.

In the cartridge cleaning agent of the present invention, the content of the alkaline agent (A) in the solid cleaning composition is 10 to 60% by weight, and the content of the chelating agent (B) is 8 to 60% by weight. and the content of the coating chlorine agent (C) is preferably 1 to 10% by weight.

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 detergent composition, and the inner lid contains the solid detergent composition. , the solid chlorine agent (c) is accommodated separately from the coating chlorine agent (C), and the solid chlorine agent (c) or the solid cleaning agent composition is placed between the container body and the inner lid. A partition is preferably provided to prevent movement of objects.

When only the covering chlorine agent contained in the solid detergent composition is used as the chlorine source, there is a limit to the amount of the agent to be blended, so there is a limit to increasing the chlorine concentration in the cleaning liquid.
If a solid chlorine agent is used separately from the covering chlorine agent, the chlorine agent can be supplied in addition to the covering chlorine agent. In addition, since the solid chlorine agent is stored in the cartridge detergent in a form that does not come into contact with other components of the solid detergent composition, it does not react with the alkaline agent or chelating agent contained in the solid detergent composition and is effective. A decrease in chlorine concentration can be suppressed.

The method for sterilizing microorganisms or the method for removing agglomerates of bacterial flora of the present invention comprises installing the cartridge cleaning agent of the present invention in an automatic cleaning machine, and dissolving the solid cleaning composition in water to obtain a cleaning solution for automatic cleaning. It is characterized by acting on bacteria and bacterial flora in the cabin.

When the cartridge cleaning agent of the present invention is used, the effective chlorine concentration in the cleaning liquid can be kept at 5 ppm or more from the start of use to the end of use of the cartridge cleaning agent, so it acts on the bacteria and bacterial flora formed in the automatic cleaning machine. Microorganisms or bacterial flora agglomerates can be preferably removed by allowing the

In the method for producing the cartridge cleaning agent of the present invention, a raw material composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated chlorine agent (C) is mixed in hot water. make a liquid,
Prepare a water-insoluble container having a content supply port,
A method for producing a cartridge cleaning agent by putting a liquid mixture in the container and cooling and solidifying the liquid mixture in the container,
The absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the mixed liquid is 0.8 g/cm ³ or less. Characterized by

In the method for producing the cartridge cleaning agent of the present invention, the mixed liquid is prepared so that the absolute value of the difference between the specific gravity of the coating chlorine agent and the specific gravity of the components other than the coating chlorine agent becomes small, and the mixed liquid is cooled and solidified to obtain a cartridge. Make a cleaning agent.
In this way, the coated chlorine agent is prevented from concentrating on the surface or bottom of the container in the process of cooling and solidifying the mixed liquid, so that the distribution of the coated chlorine agent in the solid detergent composition is uneven. can be prevented to manufacture the cartridge cleaning agent.

According to the present invention, it is possible to provide a cartridge cleaning agent that can stably maintain the effective chlorine concentration of the cleaning liquid at a high value from the start to the end of use of the cartridge cleaning agent.

FIG. 1 is a cross-sectional view schematically showing an example of a cartridge cleaning agent. FIGS. 2(a), 2(b), and 2(c) schematically 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 liquid. It is a sectional view showing. FIG. 3 is an explanatory diagram schematically showing an example of a container that constitutes the cartridge cleaning agent according to the embodiment of the present invention. FIGS. 4(a), 4(b) and 4(c) are conceptual diagrams schematically showing an embodiment of the inner lid and the outer lid constituting the cartridge cleaning agent shown in FIG. FIG. 5 is a schematic diagram showing an example of how the solid detergent composition is collected from the supply port side of the container and from the bottom side of the container. FIG. 6 is a graph showing the results of measurement of effective chlorine concentration for the cartridge cleaning agents of Examples and Comparative Examples.

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. The cartridge cleaning agent for an automatic cleaning machine of , wherein the contents are a solid cleaning agent composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated chlorine agent (C) The cartridge cleaning agent is installed in 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 at 25°C. It is characterized in that the effective chlorine concentration in the cleaning liquid is 5 ppm or more from the start of use to the end of use in the cleaning liquid at which the concentration of the solid detergent composition is 0.05% by weight.

FIG. 1 is a cross-sectional view schematically showing an example of a 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 is an inlet through which water is injected into the container 10 and an outlet through which the cleaning liquid generated by dissolving the solid cleaning composition 20 exits the container 10 . The solid detergent composition 20 contains a coating chlorine agent 21 .
Water is jetted into the supply port 11 to dissolve the solid detergent composition 20, which is the content, while supplying the washing liquid to the automatic washing machine.

The solid detergent composition contained in the cartridge detergent will be described below.
The solid detergent composition contains an alkali agent (A), a chelating agent (B) and a coating chlorine agent (C).
In addition, in this specification, the content (% by weight) of each component of the solid detergent composition is the content of the pure component in the solid detergent composition unless otherwise specified.

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 one or more compounds selected from the group consisting of alkali metal salts of silicic acid, alkali metal hydroxides, alkali metal carbonates and alkali metal phosphates. Sodium (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, potassium sesquisilicate , potassium orthosilicate); alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate alkali metal phosphates such as trisodium phosphate are preferred. These alkaline agents may be hydrates. Among them, alkali metal salts of silicic acid, alkali metal hydroxides, and alkali metal carbonates are more preferable from the viewpoint of improving detergency and disinfecting power, and alkali metal salts of silicic acid and alkali metal hydroxides are more preferable. More preferred are sodium silicate, potassium silicate, sodium hydroxide and potassium hydroxide. Compounds exemplified as the chelating agent (B) described later are not included in the alkali agent (A) in the present invention.

The content of the alkaline agent (A) is preferably 10 to 60% by weight in the solid detergent composition. If the content of the alkaline agent (A) is less than 10% by weight, the detergency may be insufficient, and if it exceeds 60% by weight, the items to be washed may deteriorate. From the viewpoint of improving detergency, etc., the content of the alkaline agent (A) in the solid detergent composition is more preferably 10 to 55% by weight, more preferably 10 to 50% by weight.
When two or more alkaline agents (A) are contained, the above content is defined as the total content of each alkaline agent.

Examples of the chelating agent (B) include aminocarboxylic acid-based, phosphonic acid-based, phosphoric acid-based, and ether carboxylate-based chelating agents, and these may be used in combination. Compounds exemplified as acid agents and compounds exemplified as builders described later are not included in the chelating agent (B) in the present invention.

Aminocarboxylic acid-based chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylene Tetraminehexaacetic 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 acid diacetic acid (ASDA), ethylenediaminesuccinic acid (EDDS), salts thereof, and the like.

Phosphonic acid-based chelating agents include hydroxyethylidenephosphonic acid (HEDP), nitrilotrimethylenephosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), salts thereof, and the like. . Phosphoric acid-based chelating agents include tripolyphosphoric acid, hexametaphosphoric acid, salts thereof, and the like.

Examples of the salt in the chelating agent include salts of alkali metals such as potassium and sodium, and 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.
Moreover, the chelating agent and the salt of the chelating agent may be mixed in the solid detergent composition. It may be salt.

The chelating agent is at least one selected from the group consisting of nitrilotriacetic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, ethylenediaminetetramethylenephosphonic acid, phosphonobutanetricarboxylic acid and salts thereof, from the viewpoint of improving detergency. is more preferable.

The content of the chelating agent (B) is preferably 8-60% by weight in the solid detergent composition. If the content of the chelating agent (B) is less than 8% by weight, the detergency-enhancing effect resulting from the addition of the chelating agent will be insufficient. When the content of the chelating agent (B) exceeds 60% by weight, the metal tends to be eluted. For this reason, for example, there is a possibility that the washing machine and the objects to be washed are likely to deteriorate. The content of the chelating agent is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, from the viewpoint of improving detergency. When two or more chelating agents are contained, the above content is defined as the total content of each chelating agent.

The coated chlorine agent (C) is obtained by coating the periphery of the chlorine agent with a coating agent.
By coating the surroundings of the chlorine agent with a coating agent, it is possible to prevent the chlorine agent from reacting with other components contained in the solid detergent composition, particularly the chelating agent and the alkaline agent, and deactivating the chlorine agent. can. 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 (C) include dichloroisocyanuric acid (chlorinated isocyanuric acid) salts (sodium dichloroisocyanurate (chlorinated sodium isocyanurate), potassium dichloroisocyanurate (chlorinated potassium isocyanurate), etc.). , trichloroisocyanuric acid, and hypochlorites (sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc.). 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.

Coating agents include carboxylates.
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- Mandelic acid, L-mandelic acid, trimellitic acid, pyromellitic acid, 2-methoxyphenylacetic acid, 3-methoxyphenylacetic acid, salts of aromatic carboxylic acids such as 4-methoxyphenylacetic acid, one of these It can be used alone or in combination of two or more.
Among them, benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid and pt- Salts of one or more aromatic carboxylic acids selected from the group consisting of butylbenzoic acid are preferred, with benzoates being more preferred. Benzoates have good stability against chlorine agents, so if a coated chlorine agent coated with a coating agent containing benzoate is used, the decomposition of the chlorine agent, etc. during storage of the cleaning composition is effective. It is possible to effectively prevent it, and it is possible to suppress the decrease in the effective chlorine amount and the decrease in the detergency and the sterilization power. Moreover, since the benzoate is excellent in quick solubility, it can exhibit good detergency and sterilization power when washing with the detergent composition. In addition, benzoates are less foamy and less likely to reduce cleaning efficiency when used in automatic cleaning machines, for example.
The benzoate includes sodium benzoate, potassium benzoate, calcium benzoate, magnesium benzoate, etc. From the viewpoint of solubility, sodium benzoate is preferred.
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 salts in the chlorine agent and coating agent include alkali metal salts such as potassium and sodium, and alkaline earth metal salts such as magnesium and calcium. Among them, alkali metal salts are preferable, and sodium salts or potassium salts are more preferable.

The coating chlorine agent (C) includes a chlorine agent and benzoic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, trimellitic acid and pt- Preferred are salts of one or more aromatic carboxylic acids selected from the group consisting of butylbenzoic acid. 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.

As for the weight ratio of the coating agent and the chlorine agent, for example, the weight ratio of chlorine agent/coating agent is preferably 1 to 9, more preferably 1.5 to 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 (C) preferably has a specific gravity of 1.0 to 2.0 g/cm ³ .
It is preferable to use a material having a specific gravity of this level as the coating chlorine agent, since the difference in specific gravity from components other than the coating chlorine agent does not become large.

The content of the coating chlorine agent (C) is preferably 1 to 10% by weight in the solid detergent composition.
When the content of the coating chlorine agent (C) is within the above range, the detergency and sterilization power are improved. Also, the risk of generating chlorine gas can be suppressed. From the viewpoint of sterilization power, detergency and safety improvement, the content of the coating chlorine agent (C) is more preferably 2 to 9% by weight in the solid detergent composition. When two or more chlorine agents are contained, the above content is defined as the total content of each chlorine agent.

In addition, regarding the contents of the alkaline agent (A), the chelating agent (B) and the coating chlorine agent (C) in the solid detergent composition, the content of the alkaline agent (A) in the solid detergent composition is It is preferable that the content is 10 to 60% by weight, the content of the chelating agent (B) is 8 to 60% by weight, and the content of the coating chlorine agent (C) is 1 to 10% by weight.
When the contents of the alkali agent (A), the chelating agent (B) and the coating chlorine agent (C) in the solid detergent composition are within the above ranges, respectively, the sterilizing power and the detergency are well balanced.

The solid detergent composition may contain components other than the above components as long as the effects of the present invention are not impaired. For example, the solid detergent composition can contain surfactant (D), anticorrosion agent (E), and other ingredients.
Other components include one or more of acid agents, builders, enzymes, solvents, bulking agents (bulking agents), antifoaming agents, scrubbing agents, fragrances, deodorants, and the like.

If the solid detergent composition contains a surfactant (D), the detergency will be improved. Surfactants (D) include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants and the like, preferably nonionic surfactants.
Examples of nonionic surfactants include polyoxyalkylene dialkyl ethers, pluronic block polymers, reverse pluronic block polymers, tetronic block polymers, reverse tetronic block polymers, polyoxyalkylene alkylphenyl ethers, fatty acid alkanolamides, Polyoxyalkylene fatty acid alkanolamide, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl polyglycoside, polyoxyethylene methyl ether fatty acid ester, polyoxyalkylene alkyl Amine etc. are mentioned.

When the solid detergent composition contains the surfactant (D), the content of the surfactant (D) is preferably 0.01 to 10% by weight in the solid detergent composition from the viewpoint of improving detergency. , 2 to 8% by weight is more preferred. When two or more surfactants are included, the above content is defined as the total content of each surfactant.

When the solid detergent composition contains the anticorrosive agent (E), the anticorrosion action (anticorrosion action) of the solid detergent composition is improved. As the anticorrosive agent, for example, at least one selected from the group consisting of triazole or its derivatives, benzimidazole or its derivatives, and benzothiazole or its derivatives is preferred.

Examples of triazoles or derivatives thereof include triazole, benzotriazole, tolyltriazole, 5-dodecylbenzotriazole, 5-octylbenzotriazole, 5-hexylbenzotriazole, 5-butylbenzotriazole, 5-methylbenzotriazole, carboxybenzotriazole ( 4-carboxybenzotriazole, 5-carboxybenzotriazole), carboxybenzotriazole methyl ester, carboxybenzotriazole butyl ester, carboxybenzotriazole hexyl ester, benzotriazole octyl ester, dicarboxypropylbenzotriazole and the like.
Benzimidazole or derivatives thereof such as benzimidazole, 2-hydroxybenzimidazole, 1-isopropenylbenzimidazol-2-one, 1-(2-propenyl)benzimidazol-2-one, 2-methylbenzimidazole, 2 - mercaptobenzimidazole, thiazolylbenzimidazole, thiabendazole and the like.
Examples of benzothiazole or derivatives thereof include benzothiazole, 2-methylbenzothiazole, 2-aminobenzothiazole, 2-mercaptobenzothiazole and the like.

When the solid detergent composition contains the anticorrosive agent (E), the content of the anticorrosive agent (E) is 0.05 to 5% by weight in the solid detergent composition from the viewpoint of corrosion prevention and odor prevention. and more preferably 0.1 to 2% by weight.
When two or more anticorrosive agents are contained, the above content is defined as the total content of each anticorrosive agent.

If the solid detergent composition contains an acid agent as another component, it is preferable because the sterilizing power is improved. Acid agents include citric acid, succinic acid, lactic acid, formic acid, oxalic acid, acetic acid, propionic acid, malonic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, glycolic acid, salicylic acid, tartaric acid, malic acid, hydrochloric acid, Sulfuric acid, nitric acid, sulfamic acid and the like can be mentioned.

When the solid detergent composition contains an acid agent, the content of the acid agent in the solid detergent composition is preferably 0.01 to 10% by weight, more preferably 2 to 8% by weight. When two or more kinds of acid agents are contained, the above content is defined as the total content of each acid agent.

When the solid detergent composition contains a builder as another component, it is preferable because the detergency is improved. Builders include polymeric dispersants. As the polymeric dispersant, for example, a polymeric dispersant having a weight average molecular weight of 3,000 to 300,000 is preferred.
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. , maleic acid-olefin 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 acid 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, maleic acid-olefin copolymers or salts thereof are preferable, and sodium polyacrylate, maleic acid-olefin copolymers or sodium salts thereof are more preferable.
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 builder, its content is preferably 2 to 20% by weight, more preferably 3 to 20% by weight, in the solid detergent composition. When two or more types of builders are included, the above content is defined as the sum of them.

When the solid detergent composition contains enzymes as other components, the detergency is improved. Enzymes include, for example, proteases, esterases, lipases, nucleases, cellulases, amylases and pectinases. If these enzymes are included, the detergency will be improved due to the function of the enzymes. Among them, protease, amylase and lipase are preferred.

When the solid detergent composition contains an enzyme, the content of the enzyme is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, in terms of enzyme protein weight in the solid detergent composition. When two or more enzymes are contained, the above content is defined as the total content of each enzyme.

Water, an organic solvent, etc. are mentioned as a solvent. As the organic solvent, monohydric to trihydric alcohols can be suitably used, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methoxyethanol and 2-ethoxyethanol. monohydric alcohols such as; ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, and dihydric or trihydric polyhydric alcohols such as polyethylene glycol. .
Examples of bulking agents include sodium sulfate (mirabilite) and the like.
Defoamers include end-capped nonionic surfactants, silicone oils, polydimethylsiloxane, and the like.

When the cartridge cleaning agent of the present invention is installed in 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 at 25°C, the use of the cartridge cleaning agent is started. The effective chlorine concentration in the cleaning liquid is 5 ppm or more in the cleaning liquid in which the concentration of the solid cleaning composition is 0.05% by weight from the time of use to the end of use.
The measurement of the effective chlorine concentration of the cleaning liquid will be described below.

FIGS. 2(a), 2(b), and 2(c) schematically 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 liquid. It is a sectional view showing.
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 cleaning liquid 61 in which the solid cleaning composition 20 is dissolved is produced.
This cleaning liquid 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.
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. . Each drawing schematically shows that the densities of the particles of the coating chlorine agent 21 included in the arrows of the cleaning liquid 61 are approximately the same. That is, the effective chlorine concentration in the cleaning liquid is maintained at a predetermined value from the start of use of the cartridge cleaning agent to the end of use.

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, at the start of using the cartridge cleaning agent (when using 0-5% of the total amount), when using about half of the cartridge cleaning agent (when using 45-55% of the total amount), and when using the cartridge cleaning agent ( The washing liquid is sampled so as to include at least three points (when 95 to 100% of the total amount is used).
If the concentration of available chlorine in the sampled cleaning liquid is 5 ppm or more in all of the measurements at the above three points, it is determined that the concentration of available chlorine in the cleaning liquid is 5 ppm or more from the start to the end of use of the cartridge cleaning agent.

When measuring the available chlorine concentration, the amount of water to be sprayed is adjusted so as to obtain a cleaning liquid with a solid cleaning composition concentration of 0.05% by weight. Also, the temperature of the cleaning liquid is set to 35°C.
The temperature of the cleaning solution of 35° C. and the concentration of the solid cleaning composition of 0.05% by weight are the conditions necessary for measuring the effective chlorine concentration defined in the present invention. The concentration of the cleaning liquid and the temperature 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).
Effective chlorine concentration (ppm) = N/100 dropwise 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. For example, measurements are taken every 30 minutes.

In the cartridge cleaning agent of the present invention, it is preferable that the variation in available chlorine concentration measured by the above method is within ±8 ppm of the average value.
The variation in effective chlorine concentration is determined by calculating the average value of the effective chlorine concentration measured in each sampled cleaning liquid and determining the difference between the maximum value and the minimum value with respect to the average value.
If the effective chlorine concentration is maintained at a high concentration of 5 ppm or more and the variation in the effective chlorine concentration is within a predetermined range, the variation in detergency and sterilization performance is also reduced, which is preferable.

In the cartridge detergent of the present invention, the absolute value of the difference between the specific gravity of the coated chlorine agent (C) and the specific gravity of the components other than the coated chlorine agent (C) contained in the solid cleaning composition is 0.8 g/cm ³ . The following are preferable.
The "specific gravity of components other than the coating chlorine agent (C) contained in the solid detergent composition" is the specific gravity calculated including the water contained in the solid detergent composition.
When the difference between the specific gravity of the coated chlorine agent and the specific gravity of the components other than the coated chlorine agent is small, the concentration of the coated chlorine agent on the surface or bottom of the container is prevented. The effective chlorine concentration of the cleaning liquid can be stably maintained at a high value until the end of use.
The absolute value of the difference in specific gravity may be 0 (zero) g/cm ³ or may be a value exceeding 0 (zero) g/cm ³ .

The specific gravity of the coating chlorine agent may be larger or smaller than the specific gravity of the components other than the coating chlorine agent.
The specific gravity of the coating chlorine agent is preferably 1.0 to 2.0 g/cm ³ .
Further, the specific gravity of components other than the coating chlorine agent is preferably 1.5 to 2.5 g/cm ³ .

The specific gravity of components other than the coating chlorine agent can be obtained from the specific gravity of the coating chlorine agent and the specific gravity of the entire solid detergent composition.

The cartridge cleaning agent of the present invention is a cartridge cleaning agent for automatic cleaning machines.
The automatic washing machine using the cartridge cleaning agent of the present invention is not particularly limited, and examples thereof include spray-type automatic washing machines. Examples of automatic spray washing machines include automatic dishwashers and container washing machines. Among others, the cartridge detergent of the present invention is preferably used for automatic dishwashers.
Further, the cartridge detergent of the present invention is preferably used for commercial or household automatic washing machines, but it is more suitable for commercial automatic washing machines, and is more suitable for commercial automatic dishwashing machines. It is particularly suitable as a disinfectant composition.
Further, as the automatic washing machine, an automatic washing machine equipped with a microbubble applying mechanism for applying microbubbles having a diameter of 100 μm or less to the washing liquid or rinse water can be used. An automatic washing machine equipped with the microbubble applying mechanism is described, for example, in JP-A-2017-209302.

Further, as another embodiment of the cartridge cleaning agent of the present invention, the container comprises a container body, an inner lid and an outer lid, and the container body contains the solid cleaning composition, The inner lid contains a solid chlorine agent (c) separately from the coated chlorine agent (C), and the solid chlorine agent (c) is placed between the container body and the inner lid. Alternatively, a cleaning agent having a partition for preventing movement of the solid cleaning composition may be used.

FIG. 3 is an explanatory diagram schematically showing an example of a container that constitutes the cartridge cleaning agent according to the embodiment of the present invention. FIGS. 4(a), 4(b) and 4(c) are conceptual diagrams schematically showing an embodiment of the inner lid and the outer lid constituting the cartridge cleaning agent shown in FIG.

The container 10 constituting the cartridge cleaning agent according to this embodiment comprises a container body 10a, an inner lid 32 and an outer lid 33. As shown in FIG.
The container body 10a 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 12 at the bottom.
A screw 12a for screwing the inner lid 32 is formed in the cylindrical member 12. As shown in FIG. 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 32 shown in FIG. 4(a) has a cylindrical shape with a bottom, and the bottom 32b includes a cylindrical member 32d for allowing jetted water to pass therethrough, a solid detergent composition and a solid chlorine agent 23 (see FIG. 4). (b)) is provided for passing the cleaning liquid dissolved therein, and the inner wall of the cylindrical portion 32c of the inner lid 32 is provided with a screw 320a for screwing into the cylindrical member 12. .
A portion for placing the solid chlorine agent 23 , including the opening 32 a and the bottom 32 b , is the placement portion of the inner lid 32 .
The bottom portion 32b has a mesh shape and is formed with a large number of openings 32a. When the bottom portion 32b has a mesh shape and a large number of openings 32a are formed, there is an advantage that the cleaning liquid can easily pass through the bottom portion of the inner lid and is discharged uniformly.

Further, the inner lid 32 is provided with an inner cylinder 32e, which is configured to accommodate the solid chlorine agent 23 (see FIG. 4(b)).
The solid chlorine agent 23 contained in the inner lid 32 is desirably a solid solid chlorine agent 23 of a size that does not fall from the mesh-shaped opening 32a of the bottom 32b.
In addition, partitioning members 32f for restricting the movement of the solid chlorine agent 23 are provided at a plurality of locations in the inner cylinder 32e of the inner lid 32 to partition the space in the inner cylinder 32e. It is desirable to set the interval between the partitioning members 32f so that the solid chlorine agent 23 enters between the partitioning members 32f. By restricting the movement of the solid chlorine agent 23 in this way, each solid chlorine agent can be uniformly dissolved.

Moreover, it is desirable that the partitioning by the partitioning member 32f does not completely partition the space in the inner cylinder 32e but loosely partitions it. "Loosely" means that the space in the inner cylinder 32e is divided by the dividing member 32f to such an extent that the movement of the solid solid chlorine agent 23 is restricted, while the space between the dividing member 32f and the inner wall of the inner cylinder 32e and/or a state in which a space is provided between the partition member 32f and the outer wall of the cylindrical member 32d so that liquids such as water and cleaning liquid can freely move between the inner cylinders 32e. In such a state, even if a liquid such as water or cleaning liquid is sprayed to a specific portion, the liquid is not biased in the inner cylinder 32e, so that only the specific solid chlorine agent 23 is dissolved. is prevented.

Further, as shown in FIG. 4(b), a ring-shaped cover portion 34 is provided to hold the solid chlorine agent 23 in the inner cylinder 32e.
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. 4(c) shows a state in which a film member 33 as an outer lid is adhered to the back surface of the inner lid 32 shown in FIG. 4(a).
The film member 33 may be adhered to the inner lid 32 with an adhesive that can be peeled off when using the cartridge cleaning agent. The film member 33 can be peeled off by manually grasping the projecting portion 33a 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 33 that is the outer cover is peeled off from the inner cover 32 .
The jetted water passes through the space between the cylindrical members 32d and reaches the solid detergent composition contained in the container body 10a, generating a cleaning liquid in which the solid detergent composition is dissolved.
The cleaning liquid enters the inner lid 32 through the opening 34a of the cover 34, dissolves the solid chlorine agent 23, and produces a solid cleaning composition containing the coated chlorine agent and a cleaning liquid containing the solid chlorine agent.
This cleaning liquid drops downward from the opening 32a at the bottom of the inner lid 32 and flows into the cleaning tank of the automatic washing machine, and the cleaning liquid containing the coated chlorine agent and the chlorine agent derived from the solid chlorine agent is introduced into the automatic washing machine.
In the cartridge detergent of this form, the cylindrical member 32 d and the opening 32 a at the bottom of the inner lid 32 correspond to the supply port 11 .

In addition to the chlorine agent derived from the coated chlorine agent, the chlorine agent derived from the solid chlorine agent is further supplied to the cleaning liquid generated by the above method. Therefore, a cleaning liquid having a higher available chlorine concentration can be obtained.

As the chlorine agent used for the solid chlorine agent (c), the chlorine agents exemplified as the chlorine agents constituting the coating chlorine agent (C) can be used. A solidified product obtained by adding a binding aid to a chlorine agent can be preferably used.
The chlorine agent used in the solid chlorine agent (c) and the chlorine agent constituting the coated chlorine agent (C) in the same cartridge cleaning agent are preferably of the same type.

A cartridge cleaning agent according to another aspect of the present invention is provided by installing a water-insoluble container having a supply port for contents with the supply port facing downward, and water being sprayed into the supply port to remove the contents. A cartridge cleaning agent for an automatic cleaning machine that feeds while dissolving,
The content is a solid detergent composition containing an alkali agent (A), a chelating agent (B), and a surface-coated chlorine agent (C),
The solid detergent composition is sampled from the supply port side of the container and the bottom side of the container, and when the effective chlorine concentration of the detergent composition taken out from each part is measured, the effective chlorine concentration is 5 ppm or more. It is characterized by

FIG. 5 is a schematic diagram showing an example of how the solid detergent composition is collected from the supply port side of the container and from the bottom side of the container.
FIG. 5 shows a cleaning composition 20a collected from the supply port side of the container and a cleaning composition 20b collected from the bottom side of the container of the solid cleaning composition 20 constituting the cartridge cleaning composition 1. there is
It also shows how the cleaning composition 20a and the cleaning composition 20b are diluted for measuring the effective chlorine concentration.
The supply port side of the container means an area of up to 5% in the thickness direction from the surface of the solid detergent composition in the container. The bottom side of the container means an area of up to 5% in the thickness direction from the bottom of the solid detergent composition in the container (an area of 95 to 100% in the thickness direction from the surface of the solid detergent composition). .
The available chlorine concentration is measured by the following method for the cleaning composition sampled in each region.

The effective chlorine concentration of the detergent composition is measured as follows.
The effective chlorine concentration is measured using an aqueous solution at 25°C.
(1) 100 g of an aqueous solution of a sample (collected detergent composition) diluted with pure water to a 0.1% aqueous solution is weighed, 5 g of potassium iodide is added, and the mixture is sufficiently 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).
Effective chlorine concentration (ppm) = N/100 dropwise amount of sodium thiosulfate aqueous solution (mL) x 3.546 (1)

In addition to collecting the solid detergent composition from the supply port side of the container and the bottom side of the container, the collection position of the solid detergent composition is changed to the part in the thickness direction of the solid detergent composition. When the effective chlorine concentration of the solid detergent composition taken out from each site is measured by adding differently, it is more preferable that all effective chlorine concentrations are 5 ppm or more.
In addition to the two positions on the supply port side of the container and the bottom side of the container, the measurement positions are the center of the solid detergent composition in the thickness direction (45 to 55 in the thickness direction from the surface of the solid detergent composition). %) is also preferable.
In addition to the above three locations, between the supply port side of the container and the central portion in the thickness direction of the solid detergent composition (20 to 30% in the thickness direction from the surface of the solid detergent composition), and the center of the solid detergent composition in the thickness direction (70 to 80% in the thickness direction from the surface of the solid detergent composition).
If the effective chlorine concentrations measured at these sites are all 5 ppm or more, it is considered that a stable high effective chlorine concentration can be exhibited from the start of use to the end of use of the cartridge cleaning agent.

INDUSTRIAL APPLICABILITY The cartridge cleaning agent of the present invention can maintain a high effective chlorine concentration in the cleaning liquid, and therefore can be used for a method for sterilizing microorganisms or a method for removing agglomerates of bacterial flora.
The method for sterilizing microorganisms or the method for removing agglomerates of bacterial flora of the present invention comprises installing the cartridge cleaning agent of the present invention in an automatic cleaning machine, and dissolving the solid cleaning composition in water to obtain a cleaning solution for automatic cleaning. It is characterized by acting on bacteria and bacterial flora in the cabin.
Further, the cartridge detergent of the present invention is used as a disinfecting detergent composition for automatic washing machines for removing bacterial flora agglomerates containing microorganisms, for removing bacterial flora agglomerates formed inside automatic washing machines and the like. is preferably used for Further, the cartridge cleaning agent of the present invention is preferably used for sterilization of microorganisms in automatic cleaning machines. The cartridge detergent of the present invention is also suitably used as a detergent composition for bleaching. The cartridge cleaning agent of the present invention is also suitably used as a cleaning agent composition for removing accumulated dirt. Accumulated stains are stains that have accumulated on the items to be washed, and examples thereof include composite stains in which components such as oils and fats, proteins, and starches are mixed. Items to be washed include tableware, cutlery, cooking utensils, metal fittings, jigs, containers, trays, and the like.

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 the objects to be washed in the 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 washing objects such as tableware with an automatic washing machine using the cartridge detergent of the present invention, contact the washing liquid obtained from the cartridge detergent with the tableware 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 solution 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.
From the viewpoint of detergency and sterilization power, the concentration of the detergent composition in the cleaning solution is preferably 0.01 to 0.7% by weight, more preferably 0.05 to 0.5% by weight.

A method for producing the cartridge cleaning agent of the present invention will be described.
In the method for producing the cartridge cleaning agent of the present invention, a raw material composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated chlorine agent (C) is mixed in hot water. make a liquid,
Prepare a water-insoluble container having a content supply port,
A method for producing a cartridge cleaning agent by putting a liquid mixture in the container and cooling and solidifying the liquid mixture in the container,
The absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the mixed liquid is 0.8 g/cm ³ or less. Characterized by

As the alkali agent (A), chelating agent (B), coating chlorine agent (C) and other raw materials used in the production of the cartridge cleaning agent, those mentioned above can be used.
Also, as the water-insoluble container having a supply port for contents, the above-mentioned container can be used.
In preparing the raw materials, the specific gravity of the coating chlorine agent (C) is measured, and the specific gravity of the raw materials other than the coating chlorine agent (C) is measured. The specific gravity of the raw materials other than the covering chlorine agent (C) is obtained from the weight and volume of the mixed liquid excluding the covering chlorine agent (C), including the water used for preparing the mixed liquid.
Then, the absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the mixed solution is set to 0.8 g/cm ³ or less.

The alkaline agent (A), the chelating agent (B), the coating chlorine agent (C) and other raw material compositions having the specific gravities thus calculated are mixed with water (hot water) to prepare a mixed solution.
Water is mixed as hot water with the raw material composition, or mixed as water with the raw material composition and then heated to obtain hot water. The temperature of hot water for preparing the mixture is preferably 30 to 90°C.

The cartridge cleaning agent can be produced by putting the liquid mixture into the container and allowing the liquid mixture to cool and solidify in the container.
In the above method, the absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the mixed solution is set to 0.8 g/cm ³ or less. Therefore, the coated chlorine agent is prevented from concentrating on the surface or bottom of the container in the process of cooling and solidifying the mixed liquid, so that uneven distribution of the coated chlorine agent in the solid detergent composition can be prevented. Cartridge cleaners can be manufactured with prevention.
The 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).
It does not necessarily imply cooling in a device such as a refrigerator.

In this production method, the preferred mixing ratios of the alkali agent (A), chelating agent (B), coating chlorine agent (C) and other raw material compositions are the same as those described in the cartridge cleaning agent section. be able to.
Further, it is preferable that the weight ratio of water (hot water) in the mixed liquid is 5 to 20% by weight.

EXAMPLES The present invention will be described below in more detail with examples, but the present invention is not limited to these examples. In the examples, "%" means "% by weight" unless otherwise specified.

(Examples 1 and 2 and Comparative Examples 1 and 2)
As shown in Table 1, each component was mixed in hot water to prepare a mixed solution, the mixed solution was put into a water-insoluble container, and the mixed solution was allowed to cool and solidify in the container, thereby forming a cartridge cleaning agent. manufactured. When the liquid mixture was cooled and solidified, it was placed with the supply port facing upward.
In addition, when using a coating chlorine agent, either of the following two types was used.
Coating chlorine agent 1: The chlorine agent is sodium dichloroisocyanurate, the coating agent is sodium benzoate, and the specific gravity is 1.2 g/cm ³ Coating chlorine agent 2: The chlorine agent is sodium dichloroisocyanurate, and the coating agent is sodium benzoate and has a specific gravity of 0.8 g/cm ³ (used as G-1 in Patent Document 1).
The specific gravity of the components other than the coating chlorine agent contained in the mixed solution was adjusted to 1.7 g/cm ³ .
Table 1 shows the proportion of each component in weight percent.
The amount of the solid chlorine agent used is shown in parts by weight (3 parts by weight) with respect to 100 parts by weight of the solid detergent composition.

For Example 1 and Comparative Example 1, a cartridge cleaning agent capable of using a solid chlorine agent as shown in FIG. .
Solid chlorine agent 1: Cylindrical chlorine agent tablet containing sodium dichloroisocyanurate Example 1 and Example 2 have the same composition of the solid detergent composition, and are cartridge detergents further comprising a solid chlorine agent. is Example 1, and the cartridge cleaner without a solid chlorine agent is Example 2.
Comparative Example 1 is a cartridge cleaning agent using only a solid chlorine agent without using a coated chlorine agent as the chlorine agent.

(Measurement of effective chlorine concentration)
The cartridge detergent of each example and comparative example was installed in an automatic dishwashing machine, and the amount of sprayed water was adjusted so as to obtain a washing liquid with a solid detergent composition concentration of 0.05% by weight. A washing solution was obtained. 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 uniform 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).
Effective chlorine concentration (ppm) = N/100 dropwise amount of sodium thiosulfate aqueous solution (mL) x 3.546 (1)

FIG. 6 is a graph showing the results of measurement of effective chlorine concentration for the cartridge cleaning agents of Examples and Comparative Examples.
As shown in FIG. 6, in the cartridge cleaning agents of Examples 1 and 2, the effective chlorine concentration in the cleaning liquid was 5 ppm or more from the start of use of the cartridge cleaning agent to the end of use. Since the cartridge cleaning agent of Example 1 uses a solid chlorine agent in combination, the effective chlorine concentration is stable at a high value from the start of use of the cartridge cleaning agent until the amount used is about 2500 g (about half of the total amount). Was. It is presumed that the effective chlorine concentration became slightly lower after that because the solid chlorine agent was completely dissolved first.
In the cartridge cleaning agent of Example 2, although the variation in the effective chlorine concentration was somewhat large, the effective chlorine concentration in the cleaning liquid was maintained at 5 ppm or more from the start of use of the cartridge cleaning agent to the end of use.

The cartridge cleaning agent of Comparative Example 1 uses only a solid chlorine agent as the chlorine agent. The concentration of available chlorine decreased as the use of the cartridge cleaning agent started and progressed, and was below 5 ppm after the amount used was approximately 2000 g (approximately half of the total amount). It is presumed that the effective chlorine concentration decreases as the solid chlorine agent dissolves.
The cartridge detergent of Comparative Example 2 was produced by simulating the molten solid type detergent composition described in Patent Document 1, and although the effective chlorine concentration was as high as over 10 ppm when the detergent was first used, it soon After that, the available chlorine concentration decreased, and remained almost constant at a low value of about 3 ppm until the end of use. This is probably because the specific gravity of the coated chlorine agent was small and the coated chlorine agent was concentrated near the surface of the solid detergent composition.

In addition, the solid detergent compositions constituting the cartridge detergents produced in Examples 1 and 2 were sampled from the supply port side of the container and the bottom side of the container, and the solid detergent compositions taken out from the respective portions were collected. When the effective chlorine concentration was measured, all effective chlorine concentrations were 5 ppm or more.
In this case, the effective chlorine concentration was measured using a 25° C. aqueous solution as follows.
(1) 100 g of an aqueous solution of a sample (collected detergent composition) diluted with pure water to a 0.1% aqueous solution was weighed, 5 g of potassium iodide was added, and the mixture was sufficiently stirred.
(2) 10 mL of glacial acetic acid was added to the above aqueous solution.
(3) After uniform 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).
Effective chlorine concentration (ppm) = N/100 dropwise amount of sodium thiosulfate aqueous solution (mL) x 3.546 (1)

In addition, the solid detergent composition constituting the cartridge detergent produced in Comparative Example 2 was sampled from the supply port side of the container and the bottom side of the container, and the effective chlorine concentration of the detergent composition taken out from each part was was measured, the effective chlorine concentration was 5 ppm or more for the cleaning composition taken out from the supply port side of the container, but the effective chlorine concentration for the cleaning composition taken out from the bottom side of the container was The concentration was below 5 ppm.
The method for measuring the effective chlorine concentration is as described above.

1 Cartridge detergent 10 Container 10a Container body 11 Supply port 12 Cylindrical member 12a Screw 20 Solid detergent composition 20a, 20b Cleaning composition 21 Coated chlorine agent 23 Solid chlorine agent 32 Inner lid 32a Opening 32b Bottom 32c Cylindrical Portion 32d Cylindrical member 32e Inner cylinder 32f Partitioning member 33 Outer cover 33a Protrusion 34 Cover 34a Opening 60 Jet water 61 Cleaning liquid 320a Screw

Claims (7)

Cartridge cleaning for an automatic washing machine 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. is an agent
The content is a solid detergent composition containing an alkaline agent (A), a chelating agent (B), and a surface-coated chlorine agent (C),
The cartridge cleaning agent is installed in an automatic cleaning machine, and when the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid cleaning composition in water at 35°C is measured at 25°C, the use of the cartridge cleaning agent from the start of use The effective chlorine concentration in the cleaning liquid is 5 ppm or more in the cleaning liquid in which the concentration of the solid cleaning composition is 0.05% by weight until the end;
The specific gravity of the coating chlorine agent (C) is 1.0 to 2.0 g/cm ³ ,
The absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the solid detergent composition is 0.8 g/cm ³ or less. A cartridge cleaner characterized by: The cartridge cleaning agent is installed in an automatic cleaning machine, and when the effective chlorine concentration of the cleaning liquid obtained by dissolving the solid cleaning composition in water at 35°C is measured at 25°C, the use of the cartridge cleaning agent from the start of use 2. The cartridge cleaning agent according to claim 1, wherein the variation in the effective chlorine concentration in the cleaning solution until completion is within the average value ±8 ppm in the cleaning solution with a solid cleaning composition concentration of 0.05% by weight. The coated chlorine agent (C) consists of a chlorine agent and a coating agent that coats the circumference of the 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. 3. The cartridge cleaning agent according to claim 1 , which is a salt. In the solid detergent composition, the content of the alkaline agent (A) is 10 to 60% by weight, the content of the chelating agent (B) is 8 to 60% by weight, and the coating chlorine agent ( The cartridge cleaning agent according to any one of claims 1 to 3 , wherein the content of C) is 1 to 10% by weight. 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 (c) separately from the coated chlorine agent (C), and between the container body and the inner lid, the solid chlorine agent (c) Alternatively, the cartridge cleaning agent according to any one of claims 1 to 4 , further comprising a partition for preventing movement of the solid cleaning agent composition. The cartridge cleaning agent according to any one of claims 1 to 5 is installed in an automatic cleaning machine, and a cleaning liquid obtained by dissolving the solid cleaning composition in water is allowed to act on bacteria and bacterial flora in the automatic cleaning machine. A method for sterilizing microorganisms or removing clumps of bacterial flora, characterized by: A raw material composition containing an alkali agent (A), a chelating agent (B), and a surface-coated chlorine agent (C) is mixed in warm water to prepare a mixed solution,
Prepare a water-insoluble container having a content supply port,
A method for producing a cartridge cleaning agent by putting a liquid mixture in the container and cooling and solidifying the liquid mixture in the container,
The specific gravity of the coating chlorine agent (C) is 1.0 to 2.0 g/cm ³ ,
The absolute value of the difference between the specific gravity of the coating chlorine agent (C) and the specific gravity of the components other than the coating chlorine agent (C) contained in the mixed solution is set to 0.8 g/cm ³ or less. A method of manufacturing a cartridge cleaning material.

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