JP7347782B2 - Cleaning composition for washing machines, cartridge cleaning agent, and cleaning method - Google Patents

Description

The present invention relates to a cleaning composition for a washing machine, a cartridge cleaning agent, and a cleaning method.

2. Description of the Related Art In hotels, restaurants, etc., washing machines such as automatic dishwashers are used to wash tableware or cooking utensils after use in order to improve work efficiency and maintain hygiene. Automatic washing machines have become rapidly popular in ordinary households in recent years.
Furthermore, in recent years, resin containers have come into use that have excellent impact resistance and are resistant to breakage even when subjected to strong impacts such as drops or collisions. Under these circumstances, cleaning compositions used in cleaning machines are used to remove oil stains, protein stains, starch stains, etc. from various objects to be cleaned, including glass containers, ceramics, and resin containers. Not only does it remove stains that occur, but it also removes stubborn accumulated stains from food. Accumulated stains include dull stains, astringent stains, and slimy stains that cannot be removed by regular automatic dishwashing, which requires soaking and cleaning with bleach or alkaline detergents, which is time-consuming and time-consuming. Therefore, there is a need for cleaning compositions for automatic washing machines to remove or reduce accumulated dirt.

U.S. Pat. No. 5,002,000 describes a concentrated polymer system comprising a polymer system comprising at least one polycarboxylic acid polymer, copolymer, or terpolymer, an alkali source comprising an alkali metal carbonate, a nonionic surfactant, and water. A concentrated detergent is disclosed, the detergent having an alkaline pH.

Furthermore, Patent Document 2 describes 3 to 25% by mass of an alkaline agent as the (A) component, ethylenediaminetetraacetic acid and its alkali metal salt, nitrilotriacetic acid and its alkali metal salt, methylglycinediacetic acid and its alkali as the (B) component. 10 to 35% by mass of at least one sequestering agent selected from metal salts, glutamic acid diacetic acid and its alkali metal salts, 0.1 to 10% by mass of a polycarboxylic acid type polymer or its salt as component (C), Contains water as component (D), the total ratio of component (A) and component (B) is (A) + (B) = 33 to 60% by mass, and component (A) and (B) A concentrated liquid detergent composition for automatic dishwashers is described, characterized in that the mass ratio of components (A)/(B) is from 1 to 1.25.

Special table 2016-538412 publication JP 2019-35099 Publication

The detergent described in Patent Document 1 and the cleaning composition described in Patent Document 2 are effective for more fully removing or reducing accumulated dirt in various objects to be cleaned such as glass containers, ceramics, and resin containers. There was room for improvement.

The present invention has been made to solve the above-mentioned problems, and is capable of more fully removing or reducing accumulated dirt in various objects to be cleaned such as glass containers, ceramics, and resin containers. An object of the present invention is to provide a cleaning composition for a washing machine.

The cleaning composition for washing machines of the present invention includes polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, and maleic acid (salt)-olefin copolymer. Features.

The detergent composition for washing machines of the present invention uses polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, and maleic acid (salt)-olefin copolymer in combination. As a result, the effect of removing or reducing accumulated dirt on various objects to be cleaned becomes remarkable.

The neutralization rate of each of the polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, and maleic acid (salt)-olefin copolymer is not particularly limited.
For example, polyacrylic acid (salt) may be unneutralized polyacrylic acid, or polyacrylic acid with some or all of its acid groups neutralized; It may be a mixture. Further, the maleic acid (salt)-acrylic acid (salt) copolymer may be an unneutralized maleic acid-acrylic acid copolymer, and one of the acid groups of the maleic acid-acrylic acid copolymer may be It may be partially or completely neutralized, or it may be a mixture thereof. Furthermore, the maleic acid (salt)-olefin copolymer may be an unneutralized maleic acid-olefin copolymer, in which some or all of the acid groups of the maleic acid-olefin copolymer are neutralized. or a mixture thereof.

The cleaning composition for a washing machine of the present invention contains 1 to 8% by mass of the polyacrylic acid (salt) and 0.1 to 5% by mass of the maleic acid (salt)-acrylic acid (salt) copolymer. The maleic acid (salt)-olefin copolymer is preferably contained in an amount of 0.01 to 4% by mass.
Thereby, the effect of removing or reducing accumulated dirt becomes more excellent.
In this specification, the content (mass %) of each component in the cleaning composition is the content of pure components in the cleaning composition unless otherwise specified.

In the cleaning composition for washing machines of the present invention, the polyacrylic acid (salt) has a mass average molecular weight of 1,000 to 100,000, and the maleic acid (salt)-acrylic acid (salt) copolymer has a mass average molecular weight of 1,000 to 100,000. The maleic acid (salt)-olefin copolymer preferably has a mass average molecular weight of 5,000 to 100,000.
Thereby, the effect of removing or reducing accumulated dirt becomes more excellent.

It is preferable that the cleaning composition for a washing machine of the present invention further contains a silicate and/or an alkali metal hydroxide.
It is preferable that the cleaning composition for a washing machine of the present invention further contains a chelating agent.
It is preferable that the cleaning composition for a washing machine of the present invention further contains a surfactant.
It is preferable that the cleaning composition for a washing machine of the present invention further contains a chlorine bleach.

The cleaning composition for washing machines of the present invention is preferably solid or powder at 20°C.
It is also preferred that the washing machine cleaning composition of the present invention is liquid at 20°C.

The present invention provides an automatic washing machine in which a water-insoluble container having a supply opening for contents is installed with the supply opening facing downward, and water is sprayed into the supply opening to dissolve the contents and supply the contents. The cartridge cleaning agent is also characterized in that the above-mentioned contents are the cleaning composition for cleaning machines of the present invention.
By repeatedly cleaning various objects to be cleaned using the cartridge cleaning agent of the present invention, it is possible to fully demonstrate the effect of removing or reducing dirt accumulated on various objects to be cleaned, and to clean the objects to be cleaned. It can be conveniently washed.

The present invention further provides a cleaning method using the detergent composition for a washer of the present invention, which comprises cleaning with a cleaning liquid obtained by diluting or dissolving the above-mentioned detergent composition for a washer with water. It is also a cleaning method characterized by removing or reducing dirt attached or accumulated on the object to be cleaned.
In the above method, by cleaning with a cleaning liquid obtained by diluting or dissolving the cleaning composition for cleaning machines of the present invention with water, it is possible to not only remove stains that occur every time, but also to clean various objects to be cleaned. Accumulated dirt can be removed or reduced.
Note that the water for diluting or dissolving the washing machine cleaning composition of the present invention may be not only room temperature water but also warm water (hot water). That is, the temperature of the water is not particularly limited, and can be, for example, room temperature to 90°C.

Note that the term "cleaning liquid" refers to an aqueous detergent solution obtained by diluting or dissolving a detergent composition for a washing machine with water.
The detergent composition for washing machines of the present invention is particularly suitable as a detergent composition for automatic dishwashers.

The cleaning composition for washing machines of the present invention can sufficiently remove or reduce dirt accumulated on various objects to be cleaned, such as glass containers, ceramics, and resin containers.

FIG. 1 is a cross-sectional view schematically showing an example of a cartridge cleaning agent. FIG. 2 is a cross-sectional view schematically showing how water is injected into the supply port of the cartridge cleaning agent and the washing machine cleaning composition of the present invention is dissolved in water to obtain a cleaning liquid. FIG. 3 is an explanatory diagram schematically showing an example of a container constituting a cartridge cleaning agent according to an embodiment of the present invention. 4(a), FIG. 4(b), and FIG. 4(c) are conceptual diagrams schematically showing an example of an inner lid and an outer lid that constitute the cartridge cleaning agent shown in FIG. 3.

Embodiments of the present invention will be specifically described below. However, the present invention is not limited to the following embodiments, and can be modified and applied as appropriate without changing the gist of the present invention.

The cleaning composition for washing machines of the present invention includes polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, and maleic acid (salt)-olefin copolymer. Features.

The polyacrylic acid (salt) is a polymer composed of structural units derived from acrylic acid (salt).
In this specification, acrylic acid (salt) is acrylic acid and/or acrylate.
The term "composed of structural units derived from acrylic acid (salt)" may be used as long as it contains 90 mol% or more of structural units derived from acrylic acid (salt), and other copolymerizable units other than acrylic acid (salt) may be used. Although it may contain structural units derived from monomers, it is preferable that the polyacrylic acid (salt) contains 100 mol% of structural units derived from acrylic acid (salt).

Among these, the polyacrylic acid (salt) is preferably sodium polyacrylate or potassium polyacrylate, and more preferably sodium polyacrylate.

The weight average molecular weight of the polyacrylic acid (salt) is preferably 1,000 to 100,000. The mass average molecular weight is more preferably 30,000 or less, even more preferably 10,000 or less, and particularly preferably 4,700 or less.
Further, the mass average molecular weight is more preferably 2,000 or more, and even more preferably 3,000 or more.
The above mass average molecular weight is determined by gel permeation chromatography using N,N-dimethylformamide (DMF) as a developing solvent and polyethylene glycol (PEG) as a standard substance.

The washing machine cleaning composition of the present invention preferably contains 1 to 8% by mass of the polyacrylic acid (salt).
The content of the polyacrylic acid (salt) is more preferably 5% by mass or less.
The content of the above polyacrylic acid (salt) is, when two or more types of polyacrylic acids (salts) (for example, two or more types of polyacrylic acids (salts) with different mass average molecular weights) are mixed in the composition. , is the total amount.

The maleic acid (salt)-acrylic acid (salt) copolymer is a polymer composed of a structural unit derived from maleic acid (salt) and a structural unit derived from acrylic acid (salt).
In this specification, maleic acid (salt) is maleic acid and/or maleate salt. Note that maleic acid may be maleic anhydride. In addition, maleate is a product in which some or all of the acid groups of maleic acid have been neutralized.
Consisting of structural units derived from maleic acid (salts) and structural units derived from acrylic acid (salts) means containing 5 mol% or more of structural units derived from maleic acid (salts) and derived from acrylic acid (salts). It is sufficient that it contains 10 mol% or more of the structural unit, and may contain structural units derived from copolymerizable monomers other than maleic acid (salt) and acrylic acid (salt).

In the maleic acid (salt)-acrylic acid (salt) copolymer, the content of the structural unit derived from the maleic acid (salt) is preferably 7 mol% or more, and preferably 10 mol% or more. More preferred. Further, the content of the structural unit derived from maleic acid (salt) is preferably 60 mol% or less, more preferably 55 mol% or less. It is more preferable that the content of the structural unit derived from maleic acid (salt) is 20 mol%.
Further, in the maleic acid (salt)-acrylic acid (salt) copolymer, the content of the structural unit derived from the acrylic acid (salt) is preferably 15 mol% or more, and preferably 20 mol% or more. is more preferable. Further, the content of the structural unit derived from the acrylic acid (salt) is preferably 95 mol% or less, more preferably 90 mol% or less. It is more preferable that the content of the structural unit derived from acrylic acid (salt) is 80 mol%.

In the maleic acid (salt)-acrylic acid (salt) copolymer, the molar ratio of the structural units derived from the maleic acid (salt) and the structural units derived from the acrylic acid (salt) is 10/90 to 40/60. The ratio is preferably 15/85 to 35/55, and even more preferably 20/80.

The mass average molecular weight of the maleic acid (salt)-acrylic acid (salt) copolymer is preferably 5,000 to 100,000. The mass average molecular weight is more preferably 10,000 or more, and even more preferably 60,000 or more.
Further, the mass average molecular weight is more preferably 90,000 or less, and even more preferably 80,000 or less.
The above-mentioned mass average molecular weight is determined by gel permeation chromatography using N,N-dimethylformamide (DMF) as a developing solvent and polyethylene glycol (PEG) as a standard substance in the same manner as described above.

The detergent composition for washing machines of the present invention preferably contains 0.1 to 5% by mass of the maleic acid (salt)-acrylic acid (salt) copolymer.
The content of the maleic acid (salt)-acrylic acid (salt) copolymer is more preferably 4% by mass or less.
When two or more types of maleic acid (salt)-acrylic acid (salt) copolymers are mixed in the composition, the content of the above maleic acid (salt)-acrylic acid (salt) copolymer is the total amount It's the amount.

The maleic acid (salt)-olefin copolymer is a polymer composed of structural units derived from maleic acid (salt) and structural units derived from olefin.
In this specification, olefin is an unsaturated hydrocarbon having a carbon-carbon double bond, and examples thereof include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, etc. One or more of these can be used. Among these, heptene, octene, and nonene are preferred.
Composed of structural units derived from maleic acid (salt) and structural units derived from olefins means containing 5 mol% or more of structural units derived from maleic acid (salt) and 10 mol% or more of olefin-derived structural units. It may contain structural units derived from copolymerizable monomers other than maleic acid (salt) and olefin.

In the maleic acid (salt)-olefin copolymer, the content of the structural unit derived from the maleic acid (salt) is preferably 7 mol% or more, more preferably 10 mol% or more. Further, the content of the structural unit derived from maleic acid (salt) is preferably 40 mol% or less, more preferably 35 mol% or less. It is more preferable that the content of the structural unit derived from maleic acid (salt) is 20 mol%.
Further, in the maleic acid (salt)-olefin copolymer, the content of the structural unit derived from the olefin is preferably 10 mol% or more, more preferably 20 mol% or more. Further, the content of the structural unit derived from the olefin is preferably 90 mol% or less, more preferably 85 mol% or less. It is more preferable that the content of the above-mentioned olefin-derived structural units is 80 mol%.

In the maleic acid (salt)-olefin copolymer, the molar ratio of the structural units derived from the maleic acid (salt) to the structural units derived from the olefin is preferably 10/90 to 40/60, and 15/ The ratio is more preferably 85 to 35/55, and even more preferably 20/80.

The mass average molecular weight of the maleic acid (salt)-olefin copolymer is preferably 5,000 to 100,000. The mass average molecular weight is more preferably 7,000 or more, and even more preferably 8,000 or more.
The mass average molecular weight is more preferably 50,000 or less, even more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 11,000 or less.
The above-mentioned mass average molecular weight is determined by gel permeation chromatography using N,N-dimethylformamide (DMF) as a developing solvent and polyethylene glycol (PEG) as a standard substance in the same manner as described above.

The detergent composition for a washing machine of the present invention preferably contains 0.01 to 4% by mass of the maleic acid (salt)-olefin copolymer.
The content of the maleic acid (salt)-olefin copolymer is more preferably 3% by mass or less, and even more preferably 2% by mass or less.
The content of the maleic acid (salt)-olefin copolymer is the total amount when two or more types of maleic acid (salt)-olefin copolymers are mixed in the composition.

In the detergent composition for a washing machine of the present invention, the content ratio of the polyacrylic acid (salt), the maleic acid (salt)-acrylic acid (salt) copolymer, and the maleic acid (salt)-olefin copolymer (mass%) is preferably 10-99/0.5-85/0.5-80, more preferably 15-98/1-80/1-75, and 20-97/1 More preferably, the ratio is .5 to 75/1.5 to 65. The total content of the polyacrylic acid (salt), the maleic acid (salt)-acrylic acid (salt) copolymer, and the maleic acid (salt)-olefin copolymer is 100% by mass. Thereby, the effects of the present invention can be made even more excellent.

It is preferable that the cleaning composition for a washing machine of the present invention further contains a silicate and/or an alkali metal hydroxide.
Examples of the silicates include sodium silicate (sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4), Examples include alkali metal salts of silicic acid such as potassium silicate (potassium metasilicate, potassium sesquisilicate, potassium orthosilicate).
Examples of the alkali metal hydroxides include sodium hydroxide (caustic soda) and potassium hydroxide (caustic potash).
When the cleaning composition of the present invention contains a silicate and/or an alkali metal hydroxide, the content thereof is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, and 10 to 50% by mass. % by weight is more preferable, and 15 to 45% by weight is particularly preferable. When two or more types of compounds are included as silicates and/or alkali metal hydroxides, the above content is defined as the sum of them.

It is preferable that the cleaning composition for a washing machine of the present invention further contains a chelating agent.
The above-mentioned chelating agents are not particularly limited, but include hydroxycarboxylic acid-based, aminocarboxylic acid-based, phosphonic acid-based, phosphoric acid-based, etc., and these may be used in combination.

Examples of the hydroxycarboxylic acid-based chelating agent include malic acid, citric acid, lactic acid, tartaric acid, gluconic acid, or salts thereof, and one or more of these can be used.

Examples of aminocarboxylic acid chelating agents include ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), methylglycinediacetic acid (MGDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), and triethylene. Tetraminehexaacetic acid (TTHA), glutamic acid diacetic acid (GLDA), hydroxyethyliminodiacetic acid (HIDA), dihydroxyethylglycine (DHEG), 1,3-propanediaminetetraacetic acid (PDTA), 1,3-diamino-2- Examples include hydroxypropane hexaacetic acid (DPTA-OH), aspartic acid diacetic acid (ASDA), ethylenediaminesuccinic acid (EDDS), or salts thereof, and one or more of these can be used.

Phosphonic acid-based chelating agents include hydroxyethylidene diphosphonic acid (HEDP), nitrilotrimethylenephosphonic acid (NTMP), phosphonobutanetricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonic acid (EDTMP), etc. One type or two or more types can be used.
In the chelating agent, at least a part of the phosphonic acid moiety may be a salt.

Examples of the phosphoric acid-based chelating agent include tripolyphosphoric acid, hexametaphosphoric acid, or salts thereof, and one or more of these can be used.

Among the above chelating agents, aminocarboxylic acid-based chelating agents are preferred.

Examples of the salt in the chelating agent include salts of alkali metals such as potassium and sodium; salts of alkaline earth metals such as magnesium and calcium. Among these, alkali metal salts are preferred, and sodium salts or potassium salts are more preferred.
In addition, the chelating agent and the salt of the chelating agent may be mixed in the alkaline cleaning agent composition, and when the chelating agent is included in the alkaline cleaning agent composition, sodium ions etc. may be added afterwards. It may be salt.

The content of the chelating agent is not particularly limited, but is preferably 1 to 60% by mass, more preferably 5 to 55% by mass, even more preferably 10 to 50% by mass, and even more preferably 20 to 45% by mass. % is particularly preferred. When multiple types of chelating agents are included, the content of the chelating agents is determined as the total amount.

It is preferable that the cleaning composition for a washing machine of the present invention further contains a surfactant.
The type of surfactant is not particularly limited, but examples include anionic surfactants, amphoteric surfactants, and nonionic surfactants.
Examples of anionic surfactants include fatty acid salts, alkyl ether carboxylates (AES), alkanesulfonates, α-olefin sulfonates, α-sulfomethyl ester salts, alkylbenzenesulfonates (LAS), and alkyl succinic acids. Examples include salts, alkyl sulfate salts, alkyl ether sulfate salts, and the like.
Examples of the amphoteric surfactant include alkylaminobetaine, alkylamidobetaine, alkylaminosulfobetaine, and the like.
Examples of nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, alkyl Examples include polyglucoside, polyoxyethylene methyl ether fatty acid ester, fatty acid alkanolamide, polyoxyalkylene alkylamine, and alkylamine oxide.
When the surfactant is a salt, the salt is not particularly limited, but suitable examples include sodium salt, potassium salt, magnesium salt, and the like.
As the surfactant, a nonionic surfactant is preferable.
Two or more of these various surfactants may be used in combination.

The content of the surfactant is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight.
When multiple types of surfactants are included, the content of surfactants is determined as the total amount.

It is preferable that the cleaning composition for a washing machine of the present invention further contains a chlorine bleach.
The type of chlorine bleach is not particularly limited, but examples include sodium dichloroisocyanurate, trichloroisocyanuric acid, and calcium hypochlorite. The shape of the chlorine bleach may be any shape such as spherical, cylindrical, conical, other polyhedral, needle-like, etc., or a mixture thereof. Further, processing such as crushing, tableting, granulation, coating, and encapsulation may be performed. In particular, coating with sodium benzoate, etc., which has low solubility in water, or dry-coated tableting is preferred because the stability of the chlorine bleach in the product is improved.

The detergent composition for washing machines of the present invention contains, as other components, alkaline agents other than those mentioned above (sodium carbonate, sodium bicarbonate, etc.), fillers (sodium sulfate (mirabilite), powdered silica, etc.), and antioxidants. , a solubilizer, a dye, a fragrance, a preservative, etc.

The cleaning composition for washing machines of the present invention is preferably solid (solid cleaning composition) at 20°C.
When the washing machine cleaning composition of the present invention is solid at 20°C, the washing machine cleaning composition of the present invention usually does not contain water or has a total water content of 40°C in the raw materials. % by mass or less.

It is also preferable that the cleaning composition for a washing machine of the present invention is liquid (liquid cleaning composition) at 20°C.
When the detergent composition for a washing machine of the present invention is liquid at 20°C, the detergent composition for a washing machine of the present invention usually has a total water content of 25% by mass or more in the raw materials, It is preferably 30% by mass or more.
Further, the content of water is preferably 90% by mass or less, more preferably 80% by mass or less.

The method for producing the cleaning composition of the present invention is not particularly limited, and includes polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, maleic acid (salt)-olefin copolymer, and , other components blended as desired, or hydrates thereof, and can be produced by mixing or stirring. The order of mixing each component, the method of mixing or stirring, etc. are not particularly limited.

The washing machine in which the washing machine cleaning composition of the present invention is used is not particularly limited, and examples include spray-type automatic washing machines. Examples of the spray-type automatic washing machine include automatic dishwashing machines, container washing machines, and the like. Examples of containers include plastic containers used for transporting foods and the like. Among these, the detergent composition for a washing machine of the present invention is preferably used as a detergent composition for an automatic dishwasher or a container washer, and more preferably used as a detergent composition for an automatic dishwasher. Ru.
The detergent composition for washing machines of the present invention is suitably used for commercial or domestic automatic washing machines, but is more suitable for commercial automatic washing machines, and is more suitable for commercial automatic dishwashing machines. It is particularly suitable as a cleaning composition.

With a cleaning liquid containing the cleaning composition of the present invention, objects to be cleaned, such as tableware and containers, can be cleaned using an automatic washing machine. As the cleaning liquid, a cleaning liquid prepared by dissolving the cleaning composition of the present invention in water such as tap water, or a cleaning liquid prepared by appropriately diluting the cleaning composition with water is used. The concentration of the cleaning composition of the present invention in the cleaning liquid can be appropriately set depending on the condition of the object to be cleaned. For example, the concentration of the cleaning composition for washing machines of the present invention in the cleaning liquid is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.3% by mass. A cleaning liquid containing the cleaning composition for washing machines of the present invention at the above concentration can more fully remove or reduce accumulated dirt in various objects to be cleaned such as glass containers, ceramics, and resin containers.

The detergent composition for washing machines of the present invention can be used in various types of containers such as glass containers, ceramics, and resin containers that can be cleaned by automatic washing machines by adding a small amount (for example, 0.01 to 0.5% by mass) into a cleaning liquid. When cleaning objects to be cleaned, accumulated dirt can be sufficiently removed or reduced. Further, the cleaning composition for cleaning machines of the present invention has an effect of removing or reducing accumulated dirt even when used in combination with a cleaning composition for cleaning machines (detergent for cleaning machines) other than the cleaning composition for cleaning machines. It is possible to demonstrate the Therefore, the detergent composition for washing machines of the present invention is suitably used as an auxiliary detergent composition that is added when using a detergent for washing machines (main detergent composition). The detergent composition for washing machines of the present invention, which is used in combination with detergents for automatic washing machines, is an example of a preferred embodiment of the present invention.

Furthermore, by using a cartridge cleaning agent comprising the solid cleaning agent composition of the present invention, dirt accumulated on various objects to be cleaned can be more fully removed or reduced.

In the cartridge cleaning agent of the present invention, for example, a water-insoluble container having a supply port for the contents is installed with the supply port facing downward, and water is jetted to the supply port to dissolve the contents and supply the contents. The present invention is a cartridge cleaning agent for an automatic cleaning machine, characterized in that the above-mentioned contents are the cleaning agent composition for a cleaning machine of the present invention.

FIG. 1 is a cross-sectional view schematically showing an example of a cartridge cleaning agent.
In the cartridge cleaning agent 1 shown in FIG. 1, a water-insoluble container 10 contains the cleaning machine cleaning composition (solid cleaning agent composition 2) of the present invention as its contents.
In this example, the solid cleaning composition 2 is solidified in the shape of a container 10.
The container 10 has a supply opening 11 . The supply port 11 serves as an inlet through which water is injected into the container 10, and serves as an outlet from which the cleaning liquid produced by dissolving the solid cleaning agent composition 2 exits the container 10.
Water is injected into the supply port 11 to dissolve the solid detergent composition 2 as the contents while supplying the cleaning liquid to the automatic cleaning machine.

FIG. 2 is a cross-sectional view schematically showing how water is injected into the supply port of the cartridge cleaning agent and the washing machine cleaning composition (solid cleaning composition 2) of the present invention is dissolved in water to obtain a cleaning liquid. It is a diagram.
As shown in FIG. 2, when using the cartridge cleaning agent 1, the jet water 60 passes through the supply port 11, reaches the solid cleaning agent composition 2 housed in the container 10, and the solid cleaning agent A cleaning liquid 61 in which the composition 2 is dissolved is generated.
This cleaning liquid 61 falls down from the supply port 11, flows into the cleaning tank of the automatic cleaning machine, and is introduced into the automatic cleaning machine.

The cartridge cleaning agent of the present invention is a cartridge cleaning agent for automatic cleaning machines.
The automatic cleaning machine in which the cartridge cleaning agent of the present invention is used is not particularly limited, and examples thereof include spray-type automatic cleaning machines. Examples of the spray-type automatic washing machine include automatic dishwashing machines, container washing machines, and the like. Among these, the cartridge cleaning agent of the present invention is suitably used for automatic dishwashers.
Further, the cartridge cleaning agent of the present invention is suitably used for commercial or domestic automatic washing machines, but is more suitable for commercial automatic washing machines, and is suitable for use in commercial automatic dishwashing machines. It is particularly suitable as a germ-cleaning composition.

Further, as another form of the cartridge cleaning agent of the present invention, the container is composed of a container body, an inner lid body, and an outer lid body, and the container body is provided with a cleaning agent composition for cleaning machines of the present invention (solid). The solid chlorine agent is contained in the inner lid, and the solid chlorine agent or the solid cleaning agent is contained between the container body and the inner lid. Examples include cleaning agents in which a partition is provided to prevent movement of the composition.

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

The container 10 constituting the cartridge cleaning agent according to the present embodiment includes a container body 10a, an inner lid 32, an outer lid 33, and a cover portion 34.
The container main body 10a has a so-called funnel shape in which the diameter of the lower part of the cylindrical container gradually decreases. There is a cylindrical member 12 at the bottom.
The cylindrical member 12 is formed with a screw 12a into which the inner lid body 32 is screwed. Although not shown in the drawings, the cylindrical member may be configured to fix the inner lid body not by screwing but by fitting with a claw structure.

The inner lid body 32 shown in FIG. 4(a) has a cylindrical shape with a bottom, and a bottom portion 32b includes a cylindrical member 32d for passing the jet water, a solid cleaning agent composition, and a solid chlorine agent if necessary. 23 (see FIG. 4(b)) is provided in the inner wall of the cylindrical portion 32c of the inner lid body 32 for screwing into the cylindrical member 12 shown in FIG. A screw 320a is provided.
The part on which the solid chlorine agent 23 is placed, including the opening 32a and the bottom 32b, is the placement part of the inner lid 32.
The bottom portion 32b has a mesh shape and has a large number of openings 32a formed therein. When the bottom 32b has a mesh shape and has a large number of openings 32a, there is an advantage that the cleaning liquid can easily pass through the bottom of the inner lid and be discharged uniformly.

Moreover, this inner lid body 32 is further provided with an inner cylinder 32e, and is configured to accommodate the solid chlorine agent 23 inside the inner cylinder 32e (see FIG. 4(b)).
It is desirable that the solid chlorine agent 23 housed in the inner lid body 32 is large enough to prevent it from falling through the mesh-shaped opening 32a of the bottom portion 32b.
Further, within the inner cylinder 32e of the inner lid body 32, partition members 32f for regulating the movement of the solid chlorine agent 23 are provided at a plurality of locations, and the space within the inner cylinder 32e is partitioned. It is desirable that the intervals between the partitioning members 32f be determined such that the solid chlorine agent 23 is inserted between the partitioning members 32f. By regulating the movement of the solid chlorine agent 23 in this manner, each solid chlorine agent can be uniformly dissolved.

Further, it is preferable that the space within the inner tube 32e is not completely partitioned by the partitioning member 32f, but is partitioned loosely. "Loosely" means that the space inside the inner cylinder 32e is divided to such an extent that the movement of the solid solid chlorine agent 23 is restricted by the partition member 32f, while the space between the partition member 32f and the inner wall of the inner cylinder 32e is , and/or a space is provided between the partition member 32f and the outer wall of the cylindrical member 32d, so that liquid such as water or cleaning liquid can freely move between the inner cylinders 32e. In such a state, even if liquid such as water or cleaning liquid is sprayed to a specific area, the liquid will not be concentrated in the inner cylinder 32e, so that only the specific solid chlorine agent 23 will dissolve. is prevented.

Further, as shown in FIG. 4(b), an annular cover portion 34 is provided to hold the solid chlorine agent 23 housed inside the inner cylinder 32e.
The cover part is provided between the container body and the inner lid body, and is a partition that prevents the solid chlorine agent or the solid cleaning composition from moving.

FIG. 4(c) shows a state in which a film member 33 serving 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 body 32 with an adhesive that can be peeled off when using the cartridge cleaning agent. The film member 33 can be peeled off by grasping the protrusion 33a to which no adhesive is applied by hand. Alternatively, the film member may be a water-soluble film so that the film member dissolves and disappears when exposed to water.

When using such a cartridge cleaning agent, the film member 33, which is the outer lid, is peeled off from the inner lid 32.
The jetted water passes through the space between the cylindrical members 32d and reaches the solid cleaning composition contained in the container body 10a, producing a cleaning liquid in which the solid cleaning composition is dissolved.
The cleaning liquid enters the inner lid body 32 through the opening 34a of the cover part 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 falls down from the opening 32a at the bottom of the inner lid 32 and flows into the cleaning tank of the automatic cleaning machine, and the cleaning liquid containing the chlorine agent derived from the coated chlorine agent and the solid chlorine agent is introduced into the automatic cleaning machine.
In this embodiment of the cartridge cleaning agent, the cylindrical member 32d and the opening 32a at the bottom of the inner lid 32 correspond to the supply port 11.

A chlorine agent derived from a solid chlorine agent is supplied to the cleaning liquid produced by the above method. Therefore, a cleaning liquid with a high concentration of available chlorine can be obtained.

As the chlorine agent used in the solid chlorine agent, one obtained by adding a binding aid to the chlorine agent and solidifying it can be suitably used.
In the same cartridge cleaning agent, it is preferable that the chlorine agent used in the solid chlorine agent and the chlorine agent contained in the cleaning composition for a washing machine of the present invention are of the same type.

Further, the cleaning method of the present invention is a cleaning method using the cleaning machine cleaning composition of the present invention (which may be solid or liquid), which comprises: The feature is that dirt accumulated on the object to be cleaned is removed or reduced by cleaning with a cleaning liquid obtained by diluting or dissolving it with water.
With the above method, dirt accumulated on the object to be cleaned can be removed or reduced by cleaning with a cleaning liquid containing a specific combination of polymers.

Note that the water used to obtain a cleaning liquid by dissolving or diluting the cleaning composition for cleaning machines of the present invention may be not only room temperature water but also warm water (hot water). That is, the temperature of the water is not particularly limited, and can be, for example, room temperature to 90°C.

Examples for explaining the present invention more specifically are shown below. Note that the present invention is not limited only to these examples.
Molecular weight means number average molecular weight measured by the method described herein.

<Examples 1 to 11>
The components shown in Table 1 were blended and mixed in the proportions shown in Table 1 to produce cleaning compositions for washing machines in Examples 1 to 11. The washing machine cleaning compositions of Examples 1 and 4 were both solid. Furthermore, all of the washing machine cleaning compositions of Examples 2, 3, and 5 to 11 were in liquid form. The numerical values in Table 1 are the proportions (% by mass) of the pure components of each component to the cleaning composition.

<Comparative Examples 1 to 11>
The components shown in Table 2 were blended and mixed in the proportions shown in Table 2 to produce cleaning compositions for washing machines in Comparative Examples 1 to 11. The washing machine cleaning compositions of Comparative Examples 1 and 8 were both solid. Further, the cleaning compositions for washing machines of Comparative Examples 2 to 7 and 9 to 11 were all in liquid form. The numerical values in Table 2 are the pure proportions (% by mass) of each component to the cleaning composition.

The detergent compositions produced in Examples 1 to 11 and Comparative Examples 1 to 11 were evaluated for appearance, detergency, and foam control properties using the following methods.

<Evaluation of accumulated dirt removal or reduction effect>
(Test method)
1.0 g of composite dirt was spread on a container made of each material, stored at 60° C. overnight, and washed once using a washing machine.
The container after being washed once was dried, further spread with 0.3 g of composite dirt, stored at 60° C. for 10 minutes, and washed under the following washing conditions. From the second time onward, this operation was repeated for a total of 10 times, and the amount of accumulated dirt adhering was visually evaluated.
Washing conditions: Washing machine: Hoshizaki UF680, washing temperature 60°C, rinsing temperature 80°C, washing time 50 seconds, rinsing time 10 seconds as one washing cycle.

(Evaluation criteria)
◎: No accumulated dirt ○: Almost no accumulated dirt △: Some dirt accumulated ×: Accumulated dirt is more than half of the container surface

The compositions and evaluation results of each cleaning composition produced in Examples and Comparative Examples are shown in Tables 1 and 2.

From Tables 1 and 2, the washing machine cleaning compositions of Examples 1 to 11 can sufficiently remove or reduce dirt accumulated on glass containers, ceramics, and resin containers.

1 Cartridge cleaning agent 10 Container 10a Container body 11 Supply port 12 Cylindrical member 12a Screw 2 Solid cleaning composition 23 Solid chlorine agent 32 Inner lid 32a Opening 32b Bottom 32c Cylindrical portion 32d Cylindrical member 32e Inner tube 32f Partitioning member 33 Outer lid body (film member)
33a Projection 34 Cover part 34a Cover part opening 320a Screw 60 Water jet 61 Cleaning liquid

Claims (10)

Including polyacrylic acid (salt), maleic acid (salt)-acrylic acid (salt) copolymer, and maleic acid (salt)-olefin copolymer,
A detergent composition for a washing machine , further comprising a total of 15 to 60% by mass of a silicate and an alkali metal hydroxide . Contains 1 to 8% by mass of the polyacrylic acid (salt), 0.1 to 5% by mass of the maleic acid (salt)-acrylic acid (salt) copolymer, and contains the maleic acid (salt)-olefin copolymer. The detergent composition for a washing machine according to claim 1, which contains 0.01 to 4% by mass of coalescent. The polyacrylic acid (salt) has a mass average molecular weight of 1,000 to 100,000, the maleic acid (salt)-acrylic acid (salt) copolymer has a mass average molecular weight of 5,000 to 100,000, and the maleic acid (salt) - The cleaning composition for a washing machine according to claim 1 or 2, wherein the olefin copolymer has a mass average molecular weight of 5,000 to 100,000. The cleaning composition for a washing machine according to any one of claims 1 to 3 , further comprising a chelating agent. The cleaning composition for a washing machine according to any one of claims 1 to 4 , further comprising a surfactant. The cleaning composition for a washing machine according to any one of claims 1 to 5 , further comprising a chlorine bleach. The detergent composition for a washing machine according to any one of claims 1 to 6 , which is solid or powder at 20°C. The detergent composition for a washing machine according to any one of claims 1 to 6 , which is liquid at 20°C. 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 and supply the content. A drug,
A cartridge cleaning agent, wherein the content is the cleaning machine cleaning composition according to claim 7 . A cleaning method using the cleaning composition for a cleaning machine according to any one of claims 1 to 8 , comprising:
A cleaning method, characterized in that dirt adhering to or accumulating on an object to be cleaned is removed or reduced by cleaning with a cleaning liquid obtained by diluting or dissolving the cleaning composition for a washing machine with water.

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