JP6955746B2 - Powder detergent composition for automatic dishwasher and tableware cleaning method using it - Google Patents

Description

The present invention improves the fluidity of the powder detergent composition, suppresses the generation of scale, supplies the powder detergent quantitatively in small amounts, and has sufficient detergency even with a small amount of detergent. It relates to a powder detergent composition for a washing machine and a method for washing dishes using the same.

Conventionally, as a powder detergent composition for an automatic dishwasher, as shown in Patent Document 1, a polyacrylate, an acrylic acid copolymer, an alkaline agent, and an organic chelating agent are blended in a specific ratio, particularly in a plastic container or the like. It is known that the stains on hard articles can be effectively removed. Since this powder detergent composition for an automatic dishwasher contains a polyacrylate or an organic chelating agent, it is said that the polyacrylate or the chelating agent has a high scale adhesion suppressing effect.

However, although this product can suppress calcium carbonate and magnesium carbonate scales, it is insufficient to suppress silica scales. Therefore, there are hygienic problems caused by silica scales generated in automatic dishwashers and water distribution pipes. In addition, it was insufficient to solve the problem of poor cleaning due to clogging of the nozzle due to the silica scale. Further, even when the product is used at a concentration lower than the conventional concentration, there is a problem of poor cleaning, so that a compact design cannot be performed.

On the other hand, as shown in Patent Document 2, in order to improve the scale suppressing effect of spot stains, a powder for an automatic dishwasher containing an alkaline agent, an organic phosphorus-based chelating agent and a polymer water-soluble dispersant in a specific ratio. Detergent compositions have also been proposed. However, this product has a very high content of organic phosphorus-based chelating agent, and has a problem that it exceeds the standard value which is a guideline for eutrophication when the total phosphate is analyzed in the water quality analysis. There is.
Further, both Patent Document 1 and Patent Document 2 have a problem that the fluidity and stability (cakeing and the like), which are important for supplying the powder detergent, have not been studied.

On the other hand, automatic dishwashers are used for cleaning dirty dishes in kitchens such as homes, restaurants, and coffee shops, and the detergents used in this automatic dishwasher include powder cleaners and liquid cleaners. There is a drug. Cartridge-type powder cleaners have been particularly preferred because of their mass, size, and reduced transportation costs.

However, in space-saving areas such as food courts and small kitchens these days, it is difficult to install an automatic dishwasher using a cartridge because the installation space of the automatic dishwasher is limited. The automatic dishwasher used is often used.
However, considering the cleaning effect and running cost, although the cartridge type may be preferable to the liquid detergent, there is a problem that it cannot be installed in terms of size, so space saving such as a small kitchen is possible. There is a demand for a small cartridge type concentrated powder cleaning agent that can be used in areas.

Japanese Unexamined Patent Publication No. 2011-149001 Japanese Unexamined Patent Publication No. 10-226800

The present invention has been made in view of such circumstances, and in order to reduce the size of the cartridge that can be used in a space-saving area, the fluidity of the powder is improved and scale generation is suppressed, and the powder detergent is used. It is an object of the present invention to provide a powder detergent composition for an automatic dishwasher, which is quantitatively supplied in small amounts and has sufficient detergency even with a small amount of detergent. Another object of the present invention is to provide a method for cleaning tableware using the powder detergent composition for an automatic dishwasher.

The present invention has been made in view of such circumstances, and is a powder detergent composition for an automatic dishwasher containing the following components (A) to (G), and is the above-mentioned powder detergent composition. A powder detergent composition for an automatic dishwasher in which the component (A) is 0.5 to 10% by mass, the component (B) is 20% by mass or more, and the component (C) is 30% by mass or more, based on the whole. This is the first gist.
(A) Nonionic surfactant.
(B) Alkaline agent.
(C) A chelating agent excluding organophosphorus compounds.
(D) Polyelectrolyte polymer excluding acrylic acid-sulfonic acid-based copolymer.
(E) Organophosphorus chelating agent.
(F) Silica scale inhibitor.
(G) Amorphous silica.

Further, a method for cleaning dishes using the above-mentioned powder cleaning agent composition for an automatic dishwashing machine, wherein a solvent is injected by a solvent injection nozzle, and a step of dissolving the powder cleaning agent composition by the injection. The second gist is a method for washing dishes, which comprises a step of supplying the washing solution obtained by the dissolution to an automatic dishwasher.

That is, the present inventor is diligent in order to quantitatively supply the powder detergent little by little and obtain a high-concentration powder detergent composition for an automatic dishwasher having sufficient cleaning properties even with a small amount of detergent. Repeated research. In the process, in order to supply the powder detergent in a fixed amount in a fixed amount, when amorphous silica was added to improve the fluidity, there was a problem that the generation of silica scale was promoted. A powder detergent composition for an automatic dishwasher containing the components (A) to (G), wherein the component (A) is 0.5 to 10% by mass based on the entire powder detergent composition. When the component (B) is 20% by mass or more and the component (C) is 30% by mass or more, the generation of silica scale caused by silicate and silica is suppressed, and the cleaning component flows while having a high concentration. We have found that it has excellent properties and has a cleaning property that does not vary even with a low-concentration cleaning solution, and has reached the present invention.

As described above, the powder detergent composition for an automatic dishwasher of the present invention is a powder detergent composition for an automatic dishwasher containing the following components (A) to (G), and is described above. Since the component (A) is 0.5 to 10% by mass, the component (B) is 20% by mass or more, and the component (C) is 30% by mass or more with respect to the entire powder detergent composition, the cleaning component is Despite its high concentration, the fluidity of the powder is good and scale generation is suppressed. Therefore, the powder cleaning agent can be quantitatively supplied little by little, and sufficient cleaning performance can be exhibited even with a small amount of cleaning agent.
(A) Nonionic surfactant.
(B) Alkaline agent.
(C) A chelating agent excluding organophosphorus compounds.
(D) Polyelectrolyte polymer excluding acrylic acid-sulfonic acid-based copolymer.
(E) Organophosphorus chelating agent.
(F) Silica scale inhibitor.
(G) Amorphous silica.

Further, in the powder detergent composition for an automatic dishwasher of the present invention, when the (F) silica scale inhibitor is at least one of a glycine compound and an acrylic acid-sulfonic acid copolymer. Will be able to suppress scale generation more effectively.

Further, when the content of the (G) amorphous silica is 0.1 to 1% by mass, the fluidity of the powder is further improved.

Further, when the contents of the components (D) and (F) are 0.1 to 5% by mass and the total amount of the powder detergent composition is less than 500 ppm by total phosphate measurement, The supply of the powder detergent can be made more constant, and the cleaning property becomes better.

Then, a step of injecting a solvent by a solvent injection nozzle, a step of dissolving the powder detergent composition for an automatic dishwasher of the present invention by the injection, and a step of supplying the cleaning liquid obtained by the dissolution to the automatic dishwasher. According to the tableware cleaning method equipped with a process, the powder detergent has good fluidity and can be supplied quantitatively, so that even a small amount of detergent has sufficient cleaning property and scale generation is suppressed. Will be done. Therefore, it can be effectively used in space saving such as a small kitchen and a food court.

Then, in the step of dissolving the powder detergent composition by the injection, when a cleaning liquid containing 0.01 to 0.06% by mass of the powder detergent composition is prepared, the cleaning liquid is sufficient. Since it has detergency, it is possible to suppress an increase in the frequency of replacement that normally occurs.

Next, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

First, the powder detergent composition for an automatic dishwasher of the present invention (hereinafter, may be referred to as "detergent composition") is (A) a nonionic surfactant, (B) an alkaline agent, and (C). Detergents other than organic phosphorus-based, (D) Polyelectrolyte polymers (excluding acrylic acid-sulfonic acid-based copolymers), (E) Organic phosphorus-based chelating agents, (F) Silica scale inhibitors, and (G) ) Amorphous silica is contained, and the component (A) is 0.5 to 10% by mass, the component (B) is 20% by mass or more, and the component (C) is 30% by mass or more based on the entire detergent composition. It is set to be. Hereinafter, each component will be described.

<Ingredient (A)>
The nonionic surfactant which is the component (A) used in the cleaning agent composition is blended for the purpose of improving the cleaning property, the reattachment property of oil to the object to be cleaned, and the foam suppressing property. The nonionic surfactant is not particularly limited, but among them, polyoxyethylene polyoxypropylene alkyl ether, pluronic block polymer, reverse pluronic block polymer, and ethylene oxide of polyhydric alcohol. (EO), propylene oxide (PO) adduct, EO of glycerin, PO adduct, polyalkylene glycol, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester are preferable, among which polyoxyethylene polyoxypropylene alkyl ether, Ethylene oxide (EO) and propylene oxide (PO) adducts of polyhydric alcohols, EO and PO adducts of glycerin, and polyalkylene glycols are more preferably used. These can be used alone or in combination of two or more.

Examples of the polyoxyethylene polyoxypropylene alkyl ether include polyoxyethylene polyoxypropylene alkyl obtained by adding 1 to 40 mol of EO and 1 to 50 mol of PO to a linear or branched alcohol having 6 to 24 carbon atoms. Ether can be given. Among them, those in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the weight ratio of EO / PO is in the range of 0.5 to 5. Polyoxyethylene polyoxypropylene alkyl having an EO / PO weight ratio in the range of 0.05 to 1 by adding 1 to 15 mol of EO and 1 to 50 mol of PO to a linear or branched alcohol having 6 to 18 carbon atoms. Ether and the like are preferable.

As the pluronic block polymer, for example, a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO mass ratio in the range of 0.5 to 4.0 has an average molecular weight. Pluronic block polymer with an EO content in the range of 500 to 10,000 and an EO content in the range of 5 to 80% by mass of the total average molecular weight, a mass ratio of EO / PO with an average molecular weight in the range of 500 to 10,000. Examples thereof include a pluronic block polymer having a mass ratio in the range of 0.05 to 0.5.
In the present invention, the "average molecular weight" in the polymer compound means "weight average molecular weight", and unless otherwise specified, polyethylene glycol is used as a standard substance and measured by gel permeation chromatography (GPC). And converted.

Further, as the reverse pluronic block polymer, for example, a reverse pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO mass ratio in the range of 0.05 to 1 can be mentioned. ..

Further, examples of the EO and PO adducts of the polyhydric alcohol include those obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylolpropane.

Examples of the EO and PO adducts of glycerin include glycerin supplemented with 3 to 45 mol of EO and 15 to 120 mol of PO.

Examples of the glycerin fatty acid ester include glycerin monocaproic acid ester, glycerin monocaprylic acid ester, glycerin monocapric acid ester, glycerin monolauric acid ester, glycerin monomyristic acid ester, glycerin monopalmitic acid ester, and glycerin monostearic acid. Examples thereof include esters, glycerin monobechenic acid esters, glycerin monooleic acid esters, glycerin monoellaic acid esters, glycerin monolithinolic acid esters, and glycerin monocondensed ricinolic acid esters.

The polyglycerin fatty acid ester is a partial ester of a fatty acid having 6 to 22 carbon atoms and polyglycerin having an average degree of polymerization of glycerin of 2 to 10, specifically, diglycerin, triglycerin, and the like. Tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin, decaglycerin, etc., caproic acid, capric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, It is an ester with saturated or unsaturated fatty acids such as ellaidic acid, glycinolic acid, linoleic acid, and linoleic acid, or a mixture thereof. Examples of the ester with the saturated or unsaturated fatty acid or a mixture thereof include diglycerin monocaprelate, triglycerin monocaprelate, tetraglycerin monocaprelate, pentaglycerin monocaprelate, hexaglycerin monocaprelate, and hepta. Glycerin monocaprelate, octaglycerin monocaprelate, nonaglycerin monocaprelate, decaglycerin monocaprelate, tetraglycerin monolaurate, tetraglycerin monostearate, tetraglycerin monooleerate, hexaglycerin monolaurate, hexaglycerin Examples thereof include monostearate, hexaglycerin tristearate, hexaglycerin monooleate, decaglycerin monolaurate, and decaglycerin monooleate.

Examples of the sorbitan fatty acid ester include caproic acid sorbitan ester, capric acid sorbitan ester, capric acid sorbitan ester, lauric acid sorbitan ester, myristic acid sorbitan ester, palmitate sorbitan ester, stearate sorbitan ester, and behenic acid sorbitan ester. , Oleic acid sorbitan ester, eleidic acid sorbitan ester, ricinolic acid sorbitan ester, condensed ricinolic acid sorbitan ester, and EO 10 to 100 mol of them.

The blending amount of the nonionic surfactant as the component (A) is 0.5 to 10% by mass, and further 1 to 9% by mass, particularly 2 to 5% by mass, based on the entire detergent composition. Is preferable from the viewpoint of cleanability and cost. That is, if the amount of the component (A) is too small, the desired detergency is poor, and the cartridge for supplying the cleaning agent does not become compact and tends to be disadvantageous in terms of cost. A) If the amount of the component is too large, the balance as a whole is deteriorated, and there is a tendency that a synergistic effect with other components cannot be obtained any more.

Further, the nonionic surfactants are combined as in the combination of [1] to [6] below from the viewpoints of detergency, foam-suppressing property, and oil reattachment prevention property to the object to be cleaned. Is preferable.

[1] Polyoxy in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the mass ratio of EO / PO is in the range of 0.5 to 5. A combination of two types consisting of ethylene polyoxypropylene alkyl ether and EO and PO adducts of a polyhydric alcohol obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethylol propane.

[2] Polyoxy in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the mass ratio of EO / PO is in the range of 0.5 to 5. A combination of two types consisting of ethylene polyoxypropylene alkyl ether and EO and PO adducts of glycerin obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to glycerin.

[3] Polyoxy in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the mass ratio of EO / PO is in the range of 0.5 to 5. Ethylene polyoxypropylene alkyl ether and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO mass ratio in the range of 0.05 to 0.5 or having an average molecular weight of 500 to 10, A reverse pluronic block polymer in the range of 000 and a mass ratio of EO / PO in the range of 0.05 to 0.5, and a polymethylolpropane to which 3 to 45 mol of EO and 15 to 120 mol of PO are added. A combination of three types consisting of EO and PO adducts of valent alcohol.

[4] Polyoxy in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the mass ratio of EO / PO is in the range of 0.5 to 5. Ethylene polyoxypropylene alkyl ether, EO and PO adducts of polyhydric alcohol with 3 to 45 mol of EO and 15 to 120 mol of PO added to trimethylolpropane, and 3 to 45 mol of EO and PO15 to 120 to glycerin. A combination of three types consisting of EO and PO adducts of glycerin added with mol.

[5] Polyoxy in which 1 to 20 mol of EO and 1 to 20 mol of PO are added to a linear or branched alcohol having 6 to 18 carbon atoms and the mass ratio of EO / PO is in the range of 0.5 to 5. Ethylene polyoxypropylene alkyl ether, EO and PO adducts of polyhydric alcohols obtained by adding 3 to 45 mol of EO and 15 to 120 mol of PO to trimethyl propane, sorbitan fatty acid ester, polyglycerin fatty acid ester, and glycerin fatty acid. A combination of 3 types consisting of at least 1 type selected from esters.

[6] Polyoxyethylene poly having an EO / PO weight ratio in the range of 0.05 to 1 by adding 1 to 15 mol of EO and 1 to 50 mol of PO to a linear or branched alcohol having 6 to 18 carbon atoms. A combination of two types consisting of an oxypropylene alkyl ether and a pluronic block polymer having an average molecular weight in the range of 500 to 10,000 and an EO / PO mass ratio in the range of 0.05 to 0.5.

<Ingredient (B)>
Next, examples of the alkaline agent as the component (B) include alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide, silicates such as sodium silicate and potassium silicate, and carbonates such as sodium carbonate and potassium carbonate. Examples include salts and alkanolamines. Of these, alkali metal hydroxide salts such as sodium hydroxide and potassium hydroxide are preferably used from the viewpoint of storage stability and cost. These can be used alone or in combination of two or more.

The blending amount of the alkaline agent as the component (B) is 20% by mass or more, more preferably 22 to 45% by mass, based on the entire detergent composition. If the amount of the component (B) is too small, the desired detergency tends not to be exhibited, and conversely, if the amount of the component (B) is too large, the rinsing property when used in a dishwasher deteriorates. At the same time, the balance of each performance of the cleaning agent composition becomes poor, and in particular, the cleaning property due to the synergistic effect with other components becomes saturated, and the storage stability tends to decrease.

<Ingredient (C)>
As the chelating agent excluding the organic phosphorus-based chelating agent which is the component (C), either a phosphorus-based chelating agent or a phosphorus-free chelating agent can be used, but it means a chelating agent excluding the organic phosphorus-based chelating agent which is the component (E). .. Examples of the phosphorus-based chelating agent include alkali metal phosphates, and examples of the phosphoric acid include orthophosphoric acid, polyphosphoric acid, pyrophosphoric acid, metaphosphoric acid, and hexametaphosphoric acid. Examples of the alkali metal to be combined with these phosphoric acids include sodium and potassium. In particular, among the above alkali metal phosphates, sodium tripolyphosphate is preferable. Examples of phosphorus-free chelating agents include ethylenediaminetetraacetic acid, nitrilotriacetic acid, iminodiacetic acid, diethylenetriaminepentacetic acid, N-hydroxyethylethylenediamineacetic acid, ethylenediaminetetrapropionacetic acid, methylglycinediacetic acid (MGDA), and triethylenetetraacetic acid. Aminhexaacetic acid, ethylene glycol dietherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, cyclohexane-1,2-diaminetetraacetic acid, diencoric acid, dicarboxymethylglutaric acid, hydroxyethylethylenediaminetriacetic acid, ethylenediaminediaminedicate (EDDS) , L-Glutamic Acid Diacetic Acid (GLDA), 3-Hydroxy-2,2'-Iminodisuccinic Acid (HIDS), L-Aspartic Acid-N, N-Diacetic Acid (ASDA), Heptogluconic Acid (GH-NA), Taurine- Examples thereof include water-soluble alkali metal salts such as N, N-diacetic acid, gluconic acid, citric acid and their sodium salts and potassium salts, ethanolamine salts, ammonium salts and the like. Among the phosphorus-free chelating agents, ethylenediaminetetraacetic acid, nitrilotriacetic acid, L-glutamate diacetic acid, methylglycine diacetic acid, and water-soluble alkali metal salts such as sodium salts and potassium salts, ethanolamine salts, etc. Ammonium salt and methylglycindiacetic acid are preferable, and sodium salt is particularly preferable in terms of cleanability and cost. These can be used alone or in combination of two or more.

The blending amount of the chelating agent excluding the organic phosphorus-based component (C) is 30% by mass or more, preferably 45 to 65% by mass, based on the entire detergent composition. If the amount of the component (C) is too small, not only the cleaning property of oil and fat stains becomes poor due to the balance with other components, but also it causes scale generation. On the contrary, if the amount of the component (C) is too large. , Not only the storage stability is reduced, but also the cost tends to be disadvantageous.

<Ingredient (D)>
The polyelectrolyte polymer as the component (D) is blended for the purpose of improving metal ion blocking ability, threshold effect, dispersion performance of water-insoluble substances, reattachment prevention property and detergency, and is acrylic. It is a polyelectrolyte polymer excluding acid-sulfonic acid-based copolymers. For example, acrylic acid polymer and its salt, maleic acid polymer and its salt, acrylic acid-maleic acid copolymer and its salt, poly-α-hydroxyacrylic acid and its salt, acrylic acid-maleic acid system-polyethylene glycol. Examples thereof include copolymers and salts thereof, olefin-maleic acid copolymers and salts thereof. These can be used alone or in combination of two or more.

Examples of these salts include sodium salt, potassium salt, ammonium salt and ethanolamine salt, and among them, sodium salt and potassium salt are preferable. In particular, from the viewpoint of metal ion blocking ability, anti-reattachment property and detergency, sodium polymaleate, sodium polyacrylate, sodium salt of acrylate-maleic acid copolymer, sodium poly-α-hydroxyacrylate, acrylic acid. -Sodium salts of maleic acid-based-polyethylene glycol copolymers and olefin-maleic acid copolymers are preferably used.

Further, as the salt of the acrylic acid polymer, the maleic acid polymer, and the copolymer of maleic acid and acrylic acid, a commercially available product may be used, but when sodium polymaleate is used, for example, polymaleic acid is previously added. , Sodium hydroxide can be added (neutralization reaction) to appropriately prepare and use sodium polymerate. Similarly, in the above neutralization reaction, when sodium hydroxide and potassium hydroxide are used instead of sodium hydroxide, a mixture containing sodium polymaleate and potassium polymaleate in an arbitrary ratio can be obtained. Can be used.

The average molecular weight of the acrylic acid polymer, the maleic acid polymer and the salt thereof is preferably 600 to 15,000, and particularly preferably 1,000 to 15,000. The average molecular weight of the maleic acid-acrylic acid copolymer and its salt is preferably 1,000 to 100,000, and particularly preferably 3,000 to 80,000. .. The salt of the polymer and the copolymer may be a salt that is completely neutralized or a salt that is partially neutralized.
The average molecular weight is measured and converted by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance.

The content of the polyelectrolyte polymer as the component (D) is preferably set in the range of 0.1 to 5% by mass with respect to the entire cleaning agent composition, and further 0.5 to 4% by mass. It is preferable to set it in the range of% in terms of metal ion blocking ability, threshold effect, dispersion performance of water-insoluble substances, recontamination prevention effect and detergency in balance with other components. That is, if the amount of the component (D) is too small, the scale prevention performance tends to be poor, and if the amount of the component (D) is too large, the balance as a whole is deteriorated, the storage stability is lowered, and the storage stability is lowered. This is because there is a tendency that a synergistic effect with other components cannot be obtained any more.

<Ingredient (E)>
The organic phosphorus-based chelating agent as the component (E) is a chelating agent containing organic phosphorus, and is preferably excellent in scale prevention performance from the viewpoint of further enhancing the effect of suppressing scale generation and adhesion. Examples of the organic phosphorus-based chelating agent include ethane-1,1-diphosphonate, ethane-1,1,2-triphosphonate, ethane-1-hydroxy-1,1-diphosphonate and its derivatives, and ethane. Phosphonic acid compounds such as hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, or alkali metal salts and alkaline earth metal salts thereof, Ammonium salt, or ethanolamine salt, phosphonocarboxylic acid compounds such as 2-phosphonobustane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid, or phosphonocarboxylic acid compounds thereof. Examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and ethanolamine salts. Of these, alkali metal salts are preferable. These can be used alone or in combination of two or more.

The content of the organic phosphorus-based chelating agent as the component (E) is preferably 0.1 to 5% by mass, more preferably 0.5 to 1.5% by mass, based on the entire detergent composition. Is. If the amount of the component (E) is too small, the anti-scaling performance tends to be poor, and if the component (E) is too large, the total phosphate value, which is a guideline for eutrophication, exceeds the standard. Because there is a tendency.

<(F) component>
The silica scale inhibitor which is the component (F) suppresses the generation of silica scale, and it is preferable to use at least one of a glycine compound and an acrylic acid-sulfonic acid copolymer.
Examples of the glycine-based compound include dihydroxyethylglycine and a salt thereof. Examples of these salts include sodium salt, potassium salt, ammonium salt and ethanolamine salt, and among them, the sodium salt of dihydroxyethylglycine is preferable.
The acrylic acid-sulfonic acid-based copolymer refers to an acrylic acid-sulfonic acid-based copolymer and a salt thereof. Examples of these salts include sodium salt, potassium salt, ammonium salt and ethanolamine salt, and among them, sodium salt and potassium salt are preferable.
The component (F) is particularly preferably a sodium salt of an acrylic acid-sulfonic acid-based copolymer.
These can be used alone or in combination of two or more.

The content of the silica scale inhibitor, which is the component (F), is preferably 0.1 to 5% by mass, more preferably 0.5 to 3.5% by mass, based on the entire detergent composition. be. If the content of the component (F) is too small, the desired silica scale suppression performance tends to be poor, and if the content of the component (F) is too large, the balance as a whole becomes poor, and storage stability and fluidity are deteriorated. This is because the filling property tends to be inferior.

<(G) component>
The detergent composition of the present invention contains amorphous silica, which is the component (G), as an essential component in addition to the components (A) to (F).

Here, the amorphous silica as the component (G) means a silica having a network structure of Si—O and does not have a constant crystal structure, and commercially available amorphous silica can be used. can. Examples of commercially available amorphous silica products include CAB-O-SIL M-5 (manufactured by Cabot Corporation), Neosil GP (manufactured by PQ Corporation), Toxil NR, and Toxil NP (manufactured by Oriental Silicon Corporation). .. These can be used alone or in combination of two or more.

The content of amorphous silica as the component (G) is preferably 0.1 to 1% by mass, more preferably 0.2 to 0.7% by mass, based on the entire detergent composition. be. If the content of the component (G) is too small, the fluidity of the cleaning agent composition tends to be inferior, and conversely, if the content of the component (G) is too large, the bulk density becomes large and the filling property deteriorates. This is also because it tends to promote the generation of silica scale.

In the detergent composition of the present invention, as optional components other than the above components (A) to (G), for example, an bulking agent such as sodium sulfate, a pH adjuster, a dye, a fragrance, and a metal corrosion inhibitor (rust preventive agent). ), Bactericides, deodorants, antistatic agents, etc.

As described above, the detergent composition of the present invention is a powdery detergent composition containing the above-mentioned components (A) to (G) and, if necessary, an arbitrary component.

Further, all of the above components do not have to be powders, and some components may contain a liquid, but the detergent composition as a whole is in the form of powder.

The entire powder detergent composition preferably has a total phosphate measurement of less than 500 ppm, mainly by adjusting the content of the organophosphorus chelating agent (E) and, in some cases, the component (C). , Can be less than this value.

The above-mentioned total phosphate measurement method is an absorptiometry according to JIS K 3362-7.10.1, in which the phosphate contained in the sample is hydrolyzed with nitric acid, and then a molybdvanazine salt solution is used. The absorbance of the yellow complex salt produced by adding the above is measured at a wavelength of 400 nm, and the total phosphate is determined from the following formula (1).
〔formula〕
C = A x (200 / B) x (200/2) x 100 / (S x 1000)
= (A × 2000) / (S × B)… (1)
C: Total phosphate (as P ₂ O ₅ ) (mass fraction%)
A: Mass (mg) of _{P 2} O ₅ obtained from the calibration curve (absorbance)
B: Amount of ethanol-insoluble aqueous solution (mL)
S: Sample mass (g)

<How to wash tableware>
As a method for cleaning tableware using the detergent composition of the present invention,
[I] A step of injecting a solvent by a solvent injection nozzle,
[II] a step of dissolving the powder detergent composition by the injection, and [III] a step of supplying the cleaning liquid obtained by the dissolution to the automatic dishwasher.
It has.

Specifically, for example, first, the cartridge case for an automatic dishwasher is filled with the detergent composition. Then, in the above step [I] of injecting the solvent with the solvent injection nozzle, water (or hot water) as the solvent is injected by the injection nozzle for injecting the solvent provided inside the cleaning agent dissolving device upward, and the cartridge case is used. It is introduced into the case through the slit of the above, and the powdery cleaning agent in the case is dissolved to prepare a cleaning liquid. Then, by supplying this cleaning agent to the automatic dishwasher, the dishes are washed.

In the step [II] of dissolving the powder detergent composition by the above injection, the concentration of the detergent diluted with a solvent such as water is 0.01 to 0.01 to the above powder detergent composition from the viewpoint of detergency. It is preferably contained in an amount of 0.06% by mass, more preferably 0.02 to 0.05% by mass. That is, if the content of the detergent composition is too small, it tends to be difficult to obtain the desired effect, and conversely, if it is too large, the rinsing property tends to decrease.

As described above, since the cleaning agent composition of the present invention can be compactly designed to have concentration performance, the installation space of the automatic dishwasher has been limited so far, and the cartridge type cleaning agent cannot be used. It is a cleaning agent composition that enables the use of a small cartridge type even in a space-saving environment. In addition, it is also possible to suppress an increase in the frequency of replacement, which usually occurs due to the miniaturization of the cartridge.

The detergent composition of the present invention is suitable for cleaning dishes having a hard surface such as glass, ceramics, metal, and plastic. In the present invention, the "tableware" means an object having a hardness sufficient to maintain a predetermined shape by itself and can be used for serving food and drink, for example, a fiber. The product is not included, but the elastic resin surface is included.
Further, the "tableware" in the present invention includes "tableware" as the wording, as well as cleaning targets related to food manufacturing and food processing such as plastic containers used for food processing and distribution in restaurants, restaurants, etc. Things are also included.

The "automatic dishwasher" in the present invention is a machine that automatically cleans dishes and the like, and examples thereof include a door type, an under counter type, a rack conveyor type, and a flight conveyor type. In particular, when space saving is required, it is preferable to use the cleaning agent composition of the present invention for a door type, an under counter type, or the like.

Next, Examples will be described together with Comparative Examples, but the present invention is not limited thereto.

Prior to Examples and Comparative Examples, the following components were prepared. The details of each prepared component and its effective net content (%) are as follows, and the numerical values in Tables 1 to 3 indicate each component in pure content. Unless otherwise specified, "%" means a mass standard. Unless otherwise specified, ion-exchanged water is used as the water.

<Nonionic surfactant (A)>
-A-1: Polyoxyethylene (p = 15) Polyoxypropylene (q = 9) Linear alkyl (C = 14,15) ether, EO / PO mass ratio = 1.26, Seabayes prototype-A- 2: Polyoxyethylene (p = 5) polyoxypropylene (q = 6) linear alkyl (C = 12, 13) ether, EO / PO mass ratio = 0.63, trade name: Pepol AS-053X (Toho Kagaku) Made by Kogyo Co., Ltd.)
-A-3: Trimethylolpropane EO, PO adduct represented by the following chemical formula (1), average molecular weight = 4,500, EO / PO mass ratio = 0.21, Seabayes prototype

-A-4: Glycerin EO, PO adduct represented by the following chemical formula (2), Seabayes prototype

-A-5: Polyoxyethylene polyoxypropylene block polymer (Pluronic block polymer), EO / PO mass ratio = 0.67, average molecular weight: 3,300, trade name: Epan 740 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
-A-6: Polyoxyethylene polyoxypropylene block polymer (reverse pluronic block polymer), EO / PO mass ratio = 0.67, average molecular weight: 2,800, trade name: Pluronic RPE1740 (manufactured by BASF)
-A-7: Sorbitan fatty acid ester, trade name: Sunsoft No. 81S (manufactured by Taiyo Kagaku Co., Ltd.)

<Alkaline agent (B)>
-B-1: Pearly sodium hydroxide (pure 99%), trade name: Toso Pearl (manufactured by Tosoh)
-B-2: Sodium orthosilicate (pure content 80%), Product name: Neo-Ortho 80 (manufactured by Koei Chemical Industry Co., Ltd.)
-B-3: Anhydrous sodium metasilicate (pure content 96%), trade name: anhydrous sodium metasilicate (manufactured by Nippon Chemical Industrial Co., Ltd.)
-B-4: Sodium carbonate (pure 99%), Product name: Soda ash (Dense) (manufactured by Tokuyama Chemical Co., Ltd.)

<Chelating agent (C) excluding organophosphorus compounds>
-C-1: Ethylenediaminetetraacetic acid tetrasodium (pure content 87%), trade name: Trilon B Powder (manufactured by BASF)
-C-2: Sodium nitrilotriacetic acid (pure content 92%), trade name: Clewat PC-C3 (manufactured by Nagase ChemteX)
-C-3: Sodium methylglycine diacetate (pure content 76%), trade name: Trilon M Granules SG (manufactured by BASF)

<Polyelectrolyte polymer (D)>
-D-1: Sodium polyacrylate (pure content 92%), trade name: Acusol 445NG (manufactured by Dow Chemical Co., Ltd.)
-D-2: Sodium salt of acrylic acid-maleic acid copolymer (pure content 92%), trade name: Acusol 497NG (manufactured by Dow Chemical Co., Ltd.)

<Organophosphorus chelating agent (E)>
E-1: 1-Hydroxyethylidene-1,1-diphosphonic acid tetrasodium salt (pure 85%), trade name: Dequest 2016D (manufactured by Italmatch Japan)

<Silica scale inhibitor (F)>
-F-1: Sodium salt of carboxylic acid-sulfonic acid-based copolymer (pure content 45%), trade name: Acusol 500 (manufactured by Dow Chemical Co., Ltd.)
-F-2: Sodium dihydroxyethylglycine (pure content 50%), Product name: Chelest G-50 (manufactured by Chelest)

<Amorphous silica (G)>
-G-1: Fumed silica (100% pure), trade name: Neosil GP (manufactured by FITZ CHEM)

<Arbitrary ingredient>
-Sodium sulfate (100% pure), trade name: Neutral anhydrous Glauber's salt (manufactured by Nippon Chemical Industrial Co., Ltd.)

[Examples 1 to 24, Comparative Examples 1 to 12]
Prepare a cleaning agent composition having the composition shown in Table 1 below (the unit of the numerical value in each table is "mass%"), measure the total phosphate, and store stability and detergency (for commercial use). The cleanability of pseudo-dirt using an automatic dishwasher), anti-scale property (scale suppression test using artificial hard water), and fluidity (measurement of rest angle) were evaluated. The total phosphate measurement is carried out by the method described above, and the test methods and evaluation methods for other items are as shown below.

[Storage stability]
-Test method 400 g of the prepared detergent composition is placed in a polyethylene bottle having a volume of 500 ml, placed in a constant temperature bath (SLI-4S, manufactured by Sunaka Rika Kogyo Co., Ltd.) in an atmosphere of 40 ° C., and stored in that state for 1 month. bottom. Then, the appearance was visually observed and evaluated according to the following evaluation criteria.
-Evaluation criteria ○: No discoloration or consolidation was observed after 1 month.
Δ: After 1 month, some discoloration, solidification, etc. were observed.
X: After 1 month, remarkable discoloration and consolidation were observed.

[Cleanability]
-Test method The prepared detergent composition was put into a commercial automatic dishwasher (DW-DR61, manufactured by Sanyo Electric Co., Ltd.) and operated under the following operating conditions. Then, the following porcelain dishes or bowls, which are the objects to be cleaned, were washed as a set of 10 pieces, and the cleanability was evaluated according to the evaluation criteria described later. Two types of stains, beef tallow stain and egg yolk stain, were prepared, and cleaning evaluation was performed for each stain.
* Operating conditions Detergent concentration: 0.05% by mass
Cleaning temperature: 60 ° C
Rinse temperature: 80 ° C
Cleaning course: Standard cleaning cycle (cleaning: 43 seconds, rinsing: 15 seconds)
Tank capacity: 50L
Tap water hardness: 60 mg / L _{(as CaCO 3)}
Oil stains: A porcelain dish having a diameter of 25 cm to which refined beef tallow was attached so as to be 4 g / sheet was used.
Protein stains: Egg yolks of chicken eggs were attached to a porcelain dish having a diameter of 25 cm so as to be 4 g / sheet, dried at room temperature for 1 hour, and soaked in hot water at 40 ° C. for 30 minutes immediately before washing.
-Evaluation criteria For oil stains, oil red liquid was applied to the cleaned porcelain dish, and for protein stains, the degree of stain removal was visually judged as follows.
⊚: 90% or more dirt removal.
◯: Removes dirt of 70% or more and less than 90%.
Δ: 50% or more and less than 70% dirt removal.
X: Removes less than 50% of dirt.

[Scale prevention: Scale suppression test using artificial hard water]
-Test method The detergent composition was diluted with artificial hard water (hardness 150 ppm) to a concentration of 0.05% by mass to prepare a test solution. 50 mL of this test solution is poured into a colorimetric tube having a capacity of 100 mL, held in an incubator (IS800, manufactured by Yamato Kagaku Co., Ltd.) at 60 ° C. for 4 hours, and then the test solution and the colorimetric tube are visually observed. Scale generation suppression was evaluated according to. There are scales that float in the test solution and those that adhere to the bottom and sides of the colorimetric tube, both of which were evaluated.
-Evaluation criteria ◎: Very good (no scale was generated).
◯: Good (almost no scale was generated).
Δ: Yes (scale was generated).
×: Bad (scale adhesion was remarkable).

〔Liquidity〕
-Test method The static angle of repose (θ) was measured as the fluidity of the detergent composition using a rest angle measuring device (manufactured by Seishin Enterprise Co., Ltd., model number: Multitester MT-1000).
-Evaluation criteria ○: Good (angle of repose was less than 36 °).
Δ: Yes (the angle of repose was 36 ° or more and less than 46 °).
×: Bad (angle of repose was 46 ° or more)

From Table 3 above, a comparative example product in which the content of at least one of the components (A) to (C) is less than the amount specified in the present invention, or at least one of the components (D) to (G) is missing. Was inferior in detergency, anti-scale property, and fluidity.
On the other hand, from Tables 1 and 2 above, the product of Example had good powder fluidity and suppressed scale generation.
Further, when the method for cleaning tableware of the present invention was carried out (water was sprayed from an injection nozzle to dissolve the powder detergent composition into a cleaning liquid and then washed with an automatic dishwasher), the example product was sufficient. It had excellent detergency and suppressed the generation of scale.

As described above, it can be seen that the detergent composition of the present invention can improve the fluidity of the powder and effectively suppress the generation of scale even though the cleaning component has a high concentration. Therefore, the cleaning agent composition of the present invention quantitatively supplies the powder cleaning agent and has sufficient cleaning property even with a small amount of cleaning agent, so that the cartridge can be miniaturized and the frequency of cartridge replacement can be reduced. It turned out to be a thing.

Since the detergent composition of the present invention can improve the fluidity of the powder and effectively suppress the generation of scale, it can be used as a small cartridge type detergent, and the frequency of cartridge replacement can be reduced. Suitable for use as a concentrated detergent. Therefore, it is more suitable as a small cartridge type cleaning agent for automatic dishwashers in space-saving areas such as food courts and small kitchens.

Claims (3)

A powder detergent composition for an automatic dishwasher, which comprises the following components (A) to (G) based on the total amount of the composition.
(A) 0.5 to 10% by mass of nonionic surfactant.
(B) At least one inorganic alkaline agent selected from the group consisting of alkali metal hydroxide salts, silicates, and carbonates in an amount of 20 to 45% by mass.
(C) At least one aminocarboxylic acid-based chelating agent selected from the group consisting of ethylenediaminetetraacetic acid, nitrilotriacetic acid, L-glutamate diacetic acid, methylglycine diacetic acid and alkali metal salts thereof in an amount of 30 to 65% by mass.
(D) 0.1 to 5% by mass of acrylic acid-based polyelectrolyte polymer excluding acrylic acid-sulfonic acid-based copolymer.
(E) 0.5 to 5% by mass of an organophosphorus chelating agent.
(F) At least one silica scale inhibitor selected from the group consisting of 0.1 to 5% by mass of dihydroxyethylglycine, acrylic acid-sulfonic acid-based copolymers, and salts thereof.
(G) Amorphous silica of 0.1 to 1% by mass. A method for cleaning dishes using an automatic dishwasher powder detergent composition according to claim 1 Symbol placing, the step of injecting the solvent by solvent injection nozzle, dissolving a powder detergent composition by the injection A method for washing tableware, which comprises a step of performing the washing process and a step of supplying the washing liquid obtained by the dissolution to an automatic dishwashing machine. The method for cleaning tableware according to claim 2, wherein a cleaning liquid containing 0.01 to 0.06% by mass of the powder detergent composition is prepared in the step of dissolving the powder detergent composition by the injection.