JP2024032791A - Foaming cleaning agent and its usage method - Google Patents

Abstract

An object of the present invention is to provide a foaming detergent with increased foaming amount and a method for using the same. Specifically, it is an object of the present invention to provide a foaming detergent that increases the amount of foaming without increasing the total amount of foaming detergent used, and a method for using the foaming detergent. [Solution] Foaming property comprising a combination of a tablet containing a foaming agent and a powder containing a foaming agent, a method for producing the foaming detergent, and an object to be cleaned using the foaming detergent. Concerning how to clean. [Selection diagram] None

Description

TECHNICAL FIELD The present invention relates to a foaming detergent that can be suitably used for cleaning hard surfaces around water such as kitchens, washrooms, toilets, etc. that have puddles or drain pipes, and a method for using the same.

BACKGROUND OF THE INVENTION Foaming detergent compositions containing bleaches, surfactants, etc. are used to clean hard surfaces around water such as kitchens, washrooms, and toilets where water accumulates or has drain pipes. Such a foaming detergent composition foams when it comes into contact with water, and exerts its cleaning effect by spreading detergent components such as bleach and surfactants to the object to be cleaned along with the foam.
Conventionally, in order to efficiently remove stains using foaming detergent compositions, we have focused mainly on the formulation of foaming detergent compositions from the viewpoint of improving the bleaching effect and increasing the amount of foaming. Studies have been carried out (for example, see Patent Document 1 and Patent Document 2). For example, in foaming detergent compositions, efforts have been made to increase as much as possible the amount of carbonate, etc., which is a source of carbon dioxide gas. However, in order to increase the amount of foaming of carbon dioxide gas, etc., it is necessary to make the aqueous solution acidic, so it is necessary to increase the amount of acids such as organic acids in addition to the amount of carbonates, etc. . Further, in order to enhance the cleaning effect, it is necessary to incorporate cleaning agent components such as bleach and surfactant. That is, in order to achieve both foaming power and cleaning effect, it has been necessary to incorporate various compounds in addition to the foaming component into the foaming detergent composition.
Therefore, in order to further increase the amount of foaming, a choice was made to increase the total amount of foaming detergent compositions used, and even components that were not directly related to the amount of foaming were used in excess. , there was a problem of economic inefficiency.

In this way, conventional attempts to increase the amount of foaming by focusing on optimizing the formulation composition had limitations, so it is possible to increase the amount of foaming without increasing the total amount of foaming detergents. There was a need for a foaming cleaning agent and method for using the same.

Japanese Patent Application Publication No. 2018-024875 Japanese Patent Application Publication No. 2008-013611

An object of the present invention is to provide a foaming detergent with increased foaming amount and a method for using the same. Specifically, it is an object of the present invention to provide a foaming detergent that increases the amount of foaming without increasing the total amount of foaming detergent used, and a method for using the foaming detergent.

In view of the problems of the prior art, the present inventor focused on the dosage form and method of use of cleaning compositions, and as a result of intensive studies on techniques for increasing the amount of foaming, the inventors discovered that tablets containing a foaming agent and It has been found that by using a foaming detergent in combination with a powder containing a foaming agent, the amount of foaming can be increased compared to when a powder detergent containing a foaming agent is used alone. Based on this knowledge, the present invention was completed after further study. The present invention relates to the following foaming detergent and method of using the same.

Item 1. A foaming cleaning agent comprising a combination of a tablet containing a foaming agent and a powder containing a foaming agent.

Item 2. Item 2. The foaming detergent according to item 1, wherein the mass ratio of tablet to powder (tablet/powder) is 0.14 to 7.

Item 3: The foaming detergent according to item 1 or 2, wherein the total content of foaming agents contained in the tablet and powder is 10% by mass to 99% by mass.

Item 4. Item 4. The foaming detergent according to any one of Items 1 to 3, wherein the foaming agent is one or more selected from the group consisting of a foaming agent that generates oxygen and a foaming agent that generates carbon dioxide.

Item 5. Item 1, wherein the tablets and powders each contain, either the same or different, a foaming agent consisting of a hypochlorous acid source and a hydrogen peroxide source, and a foaming agent consisting of an organic acid and a carbonate, or both. The foaming detergent according to any one of 4 to 4.

Item 6. Item 6. The foaming detergent according to any one of Items 1 to 5, wherein the tablet and the powder each contain a foaming agent that is the same or different and consists of a hypochlorous acid generating source and a hydrogen peroxide generating source.

Section 7. The hypochlorous acid source is one or more selected from the group consisting of halogenated isocyanuric acid, halogenated hydantoin, and calcium hypochlorite, and the hydrogen peroxide source is sodium percarbonate and sodium perborate. 7. The foaming detergent according to item 5 or 6, which is one or more selected from the group consisting of , and organic peroxides.

Section 8. Item 8. The foaming cleaning agent according to any one of Items 1 to 7, comprising a mixture of a tablet containing a foaming agent and a powder containing a foaming agent.

Item 9. Item 8. The foaming detergent according to any one of Items 1 to 7, wherein the tablet containing the foaming agent and the powder containing the foaming agent are respectively housed in different containers.

Item 10. Item 9. A method for producing a foaming detergent according to item 8, which includes the step of mixing a tablet containing a foaming agent and a powder containing a foaming agent.

Item 11. Item 9. A method for producing a foaming detergent according to Item 9, which includes the step of accommodating a foaming agent-containing tablet and a foaming agent-containing powder in different containers.

Item 12. A method of using a foaming detergent, which comprises washing powder containing a foaming agent and tablets containing a foaming agent contained in the foaming detergent according to any one of items 1 to 9 to which water is attached. A method of use that includes the step of bringing it into contact with an object (inserting it into an object to be cleaned that has a puddle).

Item 13. A method for cleaning an object to be cleaned, wherein a powder containing a foaming agent and a tablet containing a foaming agent contained in the foaming detergent according to any one of Items 1 to 9 are used to clean an object to be cleaned to which water has adhered. A cleaning method that includes the step of bringing the cleaning agent into contact with the cleaning object (inserting it into an object to be cleaned that has a puddle of water).

The present invention is characterized in that it is a foaming detergent that combines a tablet containing a foaming agent and a powder containing a foaming agent. By bringing this foaming detergent into contact with water, the amount of foaming increases dramatically compared to conventional foaming detergents made only of powder and foaming detergents made only of tablets. This effect was evaluated for a foaming detergent consisting of a combination of tablets and powder, a foaming detergent consisting only of powder, and a foaming detergent consisting only of tablets, all having the same composition (ingredients and content). This is clear from the results of Examples and Comparative Examples.

The foaming cleaning agent of the present invention can be suitably used for cleaning hard surfaces around water such as kitchens, washrooms, baths, toilets, etc., which have water puddles, drain ports, and drain pipes.

In this specification, "the amount of foaming increases" means that when compared with a foaming detergent consisting only of powder or tablets, the foaming detergent is added to water and the amount of foaming increases to a certain level from the start of foaming. When the maximum amount of foaming increases within a period until the foaming decreases after a certain amount of time has elapsed, and when the predetermined time required for cleaning has elapsed from the start of foaming after adding the foaming cleaning agent to water. This refers to one or both of the cases where the amount of foaming increases.

By increasing the maximum foaming amount, the foaming cleaning agent of the present invention can foam over a wide range of areas where dirt has adhered, such as the draft surface of water pools, the vicinity of drain ports, and the inside of drain pipes. Since the foam containing the generated cleaning agent components can be delivered, efficient cleaning can be achieved.
In addition, by increasing the amount of foam after the predetermined time required for cleaning has passed from the start of foaming, the foam containing the foaming detergent can act on the cleaning object for a long time, resulting in a high cleaning effect. can be obtained. In other words, the amount of foaming can be maintained for the time required to clean the object to be cleaned.
Furthermore, the maximum amount of foaming increases within the period from when the foaming detergent is added to water until the foam decreases after a predetermined period of time has elapsed from the start of foaming, and when the foaming detergent is added to water. If the amount of foam increases after the predetermined period of time required for cleaning has elapsed after the foaming starts, the object to be cleaned can be efficiently cleaned over a wide range, and the foam containing the cleaning agent components will remain for a long time. This method is more preferable because both of the effects of being able to act on the object to be cleaned can be obtained.

Generally speaking, when comparing a foaming detergent in the form of a powder and a foaming detergent in the form of a tablet, if the compositions (ingredients and their contents) of the two are the same, the powder is more resistant to water than the tablet. Since it dissolves quickly and foams, the maximum amount of foaming increases. On the other hand, since tablets have a smaller surface area per unit mass in contact with water than powders, they dissolve slowly and the maximum amount of foaming is usually smaller than that of powders. Therefore, the maximum foaming amount of a foaming detergent that combines powder and tablets is predicted to be about halfway between the maximum foaming amount when using only powder and the maximum foaming amount when using only tablets. Ta. However, contrary to this prediction, it was found that by creating a foaming detergent that combines powder and tablets, the maximum amount of foaming increases compared to a foaming detergent that uses only powder, and that It was confirmed that the amount of foaming increased at later time points.

(foaming cleaning agent)
The foaming cleaning agent of the present invention can be suitably used for cleaning hard surfaces around water such as kitchens, washrooms, baths, toilets, etc., which have water puddles, drain ports, and drain pipes.

As used herein, the term "foaming detergent" refers to a combination of a tablet containing a foaming agent and a powder containing a foaming agent, and unless otherwise specified, the term "foaming detergent" refers to a combination of a tablet containing a foaming agent and a powder containing a foaming agent. It also includes any form in which the tablet and powder are separated and come together so that they can be used in combination, and also includes forms containing ingredients other than the tablet and powder.
Since the foaming detergent of the present invention is used in combination of tablets and powder, the amount of foaming can be increased without increasing the total amount of the detergent composition used. The tablets and powders used in the present invention are each compositions containing multiple ingredients, and the tablets and powders may be prepared separately.
The powder can be prepared by mixing powder raw materials of multiple components using a mixer or the like. A tablet can be formed by blending a plurality of ingredients and then performing a compression process (hereinafter sometimes referred to as tableting).
Since the foaming detergent of the present invention is a combination of tablets and powder, the foaming amount is increased compared to detergents containing only tablets and detergents containing only powder. The tablet and powder may have the same composition or different compositions.
Also, using a combination of tablets and powder means that the tablets are first put into water and then the powder is used, or the powder is first put into water and then the tablets are used. This includes both the use of tablets and powder in water at the same time. A foaming detergent in which a mixture of tablets and powder is packaged in the same packaging container is preferred because the tablets and powder can be used at the same time during cleaning, making the operation easier.

(tablet)
As used herein, the term "tablet" refers to a molded product obtained by compression molding a tablet component containing a foaming agent. The form of the tablet component before tableting may be any form suitable for tableting, such as powder, granules, briquettes, etc. For tabletting, a widely known tableting machine such as a rotary tabletting machine or a reciprocating tabletting machine can be used. The tableting pressure is preferably about 5 to 100 MPa from the viewpoint of productivity and moldability. The hardness of the obtained tablet is usually preferably about 200 to 800 N from the viewpoint of shape stability.
The shape of the tablet is not particularly limited. Examples include cylindrical shape; strawberry shape; Go stone shape; polygonal prism shape including triangular, square, and star shapes; and corner shape. A cylindrical shape is preferable from the viewpoint of ease of processing and handling.

The size of the tablet used in the present invention is determined by the length of the longest line on the bottom of the tablet (for example, the length of the longest line on the bottom of the tablet) It is preferable that the sum of the diameter (if the shape is a circle, the length of the longest side if the shape is a triangle, the length of the diagonal line if the shape is a rectangle) and the height of the tablet is within a predetermined range. Here, the total length of the longest line segment on the tablet bottom and the tablet height means the sum of the diameter of the circle on the tablet bottom and the tablet height if the tablet is cylindrical; In the case of a square prism, it means the sum of the length of the longest side of the triangle on the bottom of the tablet and the tablet height; in the case of a square prism, it means the sum of the length of the diagonal of the rectangle on the bottom of the tablet and the tablet height (for square prisms other than rectangular parallelepipeds) In the case of a Go stone type or a bale type, the sum of the maximum vertical thickness and the maximum horizontal width. means.
In the present invention, it is preferable that the total length of the longest line segment on the bottom of the tablet and the height of the tablet is larger than the average particle diameter of the powder. The total length of the longest line segment on the bottom of the tablet and the tablet height is preferably 5 mm to 400 mm, more preferably 10 mm to 200 mm, from the viewpoint of ease of processing and handling. Moreover, in addition to the foaming agent, the tablet can be formulated with a combination of various compounds useful for cleaning to form a composition.

When the tablet is cylindrical, the diameter of the bottom of the cylinder is usually 3 to 200 mm, preferably 5 to 100 mm, and more preferably 10 to 50 mm. The height of the cylinder is usually 3 to 200 mm, preferably 5 to 100 mm, and more preferably 10 to 50 mm. The total length of the diameter of the tablet bottom and the height of the tablet is usually 6 to 400 mm, preferably 10 to 200 mm, and more preferably 20 to 100 mm.
In addition, when the tablet is cylindrical, if the value obtained by dividing the tablet diameter (mm) by the tablet height (mm) is within a specified range, the tablet will not easily break or chip. The value obtained by dividing the diameter (mm) by the height (mm) of the tablet is preferably 1 to 10, more preferably 1.5 to 6, and even more preferably 1.5 to 3.5. .

(powder)
Powder as used herein means a collection of particles containing a foaming agent. The shape of the particles is not particularly limited, and examples thereof include amorphous, spherical, and spheroidal shapes. The powder of the present invention may be produced by processing fine powder by a conventionally known method such as fluidized bed granulation, or by pulverizing it after compression molding by a conventionally known method such as in a chilsonator. It also includes cases in which it is secondarily processed into granules. The raw material compounds may be mixed in advance and then subjected to secondary processing such as granulation, or the raw materials may be prepared by mixing raw materials that have been previously subjected to secondary processing such as granulation. In addition to the foaming agent, the powder can also be blended with particles of various compounds useful for cleaning to form a composition.

The average particle diameter of the powder is, for example, preferably 1 to 5000 μm, more preferably 10 to 3000 μm, and even more preferably 100 to 1500 μm. When the average particle diameter is 5000 μm or less, the particles are not too large and are easy to handle, when the average particle diameter is 3000 μm or less, the handleability is better, and when the average particle diameter is 1500 μm or less, the handleability is even better. In addition, when the average particle size is 5000 μm or less, it is easy to use when directly used for cleaning or bleaching because it can be poured directly into a drain with a small opening, and when it is 3000 μm or less, it is easier to use, and 1500 μm or less It's even easier to use. On the other hand, if the average particle diameter is 1 μm or more, it is easy to use because it is unlikely to be scattered by a slight wind or static electricity during handling, if it is 10 μm or more, it is easier to use, and if it is 100 μm or more, it is even easier to use.

The average particle size of the powder can be measured as follows. Using 13 tiers of sieves with openings of 75 μm, 106 μm, 150 μm, 250 μm, 425 μm, 600 μm, 710 μm, 850 μm, 1000 μm, 1180 μm, 1400 μm, 1700 μm, and 2000 μm and a saucer, the sieve with the larger opening was placed on the top of the tray. Stack them up so that they become the same. Pour the sample onto the top sieve with a 2000 μm opening, and stack the sieve with the larger opening on top of the tray. Set the stacked sieves on a sieve shaker and shake for 10 minutes to separate the sieves. A sieve shaker may be used at a frequency of 3600 times/min and an amplitude of 1 mm. For measuring the particle size distribution, methods and instruments (sieves) described in JIS Z 8815 and JIS Z 8801 may be used.

As the sieve shaker, for example, "AS200CONTROL" manufactured by Lecce can be used, but it is not limited thereto. If you cannot use a sieve shaker, support the stack of sieves with one hand and tap the sieve frame at a rate of about 120 times per minute. Occasionally, place the sieve horizontally and tap the sieve frame several times. Repeat this operation to ensure sufficient sieving. If the sample is agglomerated or if fine powder is attached to the inside or back of the sieve, gently loosen the sample with a brush and repeat the sieving operation, and place the material that passed through the sieve net under the sieve. . Note that "under the sieve" refers to the test sample that has passed through the sieve net before the sieving is completed.

If the sample contains particles with a particle size of more than 2000 μm, a plurality of sieves having apertures of more than 2000 μm and having different openings may be added. For example, a sieve with a mesh opening of 2360 μm, 2800 μm, 3350 μm, 4000 μm, 4750 μm, 5600 μm, or more may be added. If there are many particles with a particle size of 75 μm or less, a plurality of sieves with mesh sizes of less than 75 μm may be added. For example, a sieve with a mesh opening of 63 μm, 53 μm, 45 μm, 38 μm, or smaller may be added. You can also select sieves with other openings.

The mass of particles remaining on each sieve and saucer is measured, and the mass percentage (%) of particles on each sieve is calculated. It is integrated by adding up the mass percentages of the particles on the sieves with small openings, starting from the receiving tray. The opening of the first sieve with an integrated mass ratio of 50% or more is aμm, the opening of the sieve one step larger than aμm is bμm, and the integrated mass ratio from the saucer to the sieve with an opening of aμm is c%, Further, when the mass percentage on a sieve having apertures of a μm is defined as d%, the average particle diameter can be obtained from the following equation 1.

(Formula 1)

The mass ratio of powder to tablet contained in the foaming detergent of the present invention is preferably within a predetermined range. For example, when the foaming detergent is in the form of a mixture of powder and tablets, it is desirable that the mass ratio of the tablets to the powder in the mixture is within a predetermined range. Furthermore, when the foaming detergent is in the form of separated powder and tablets, it is desirable that the mass ratio of the tablets to the powder to be added is within a predetermined range.
Specifically, the mass ratio of the tablet to the powder in the foaming detergent (the value obtained by dividing the mass of the tablet by the mass of the powder; tablet/powder) is preferably 0.14 to 7, and 0.14 to 7. It is more preferably from 14 to 5, and even more preferably from 0.3 to 2.5. If the mass ratio of tablet to powder is 0.14 to 7, an excellent effect of increasing the amount of foaming can be expected; ~2.5, an even more excellent effect of increasing the amount of foaming can be expected.

The foaming detergent may contain one or more tablets. As mentioned above, it is preferable to prepare the foaming detergent so that the mass ratio of the tablet to the powder is within a desired range, and one or more tablets may be used within that range. . The number of tablets may be adjusted by using tablets whose mass has been adjusted in advance.

(foaming agent)
Both the tablet and the powder contained in the foaming detergent of the present invention contain a foaming agent. A foaming agent is one that can generate gas when added to water. The foaming agent may include a foaming agent that generates carbon dioxide gas, a foaming agent that generates oxygen gas, or a mixture thereof. The tablet and the powder each contain one or both of a foaming agent that generates carbon dioxide gas and a foaming agent that generates oxygen gas. In order to obtain the effect of increasing the amount of foaming, it is preferable that both the tablet and the powder contained in the foaming cleaning agent of the present invention contain a foaming agent that generates oxygen gas.

In this specification, when simply referring to "amount of foaming agent blended", it refers to the total of the foaming agent that generates carbon dioxide gas and the foaming agent that generates oxygen gas in the foaming cleaning agent. Refers to the amount of . When distinguishing between a foaming agent that generates carbon dioxide gas and a foaming agent that generates oxygen gas, which foaming agent is used shall be specified.

The blending ratio of the foaming agent contained in the tablet and powder in the foaming detergent is preferably 10% by mass or more, more preferably 20% by mass or more, and 50% by mass or more, based on the total mass of the tablet and powder. is even more preferable. By setting the content to 10% by mass or more, a sufficient amount of gas generation is ensured, so by combining tablets and powder, the amount of foaming tends to increase, and by setting the content to 20% by mass or more, the amount of foaming increases further. If the amount is 50% by mass or more, the amount of foaming tends to further increase. In addition, since other components are blended into the foaming detergent to enhance the cleaning effect, the blending ratio of the foaming agent is preferably 99% by mass or less, and 90% by mass based on the total mass of the tablet and powder. The following is more preferable, and 85% mass or less is still more preferable. The foaming cleaning agent may contain a combination of a foaming agent that generates carbon dioxide gas and a foaming agent that generates oxygen gas.

(Foaming agent that generates carbon dioxide gas)
Examples of foaming agents that generate carbon dioxide gas include a combination of carbonate and acid.
Examples of carbonates include sodium carbonate (hereinafter sometimes referred to as soda ash), sodium hydrogen carbonate (hereinafter sometimes referred to as baking soda), potassium carbonate, potassium hydrogen carbonate, ammonium carbonate, sodium sesquicarbonate, and mixtures thereof. One or more selected from the group consisting of are preferable, and one or more selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, and a mixture thereof is more preferable because of easy availability and low cost. These carbonates generate carbonate ions when dissolved in water, and under acidic conditions, the carbonate ions turn into carbon dioxide and foam.
Examples of acids for making the pH acidic include inorganic acids and organic acids. The inorganic acid is not particularly limited as long as it exhibits acidity when dissolved in water, such as hydrochloric acid, sulfuric acid, nitric acid, and acid salt (sodium sulfate). Among these, those that are solid at room temperature and normal pressure are suitable for blending with other detergent components as a foaming detergent, such as acidic sulfate (sodium sulfate) and the like. The organic acid is not particularly limited as long as it exhibits acidity when dissolved in water. For example, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid, D-aspartic acid, L-aspartic acid, glutaric acid, D- Glutamic acid, L-glutamic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, myristic acid, stearic acid, palmitic acid, citric acid , and a mixture thereof. As organic acids, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, D-tartaric acid, L-tartaric acid, D-malic acid, L-malic acid are easy to handle as they are solid at room temperature and normal pressure. , D-aspartic acid, L-aspartic acid, glutaric acid, D-glutamic acid, L-glutamic acid, citric acid, and mixtures thereof.
The acid is selected from succinic acid, fumaric acid, and mixtures thereof from the viewpoint of excellent blending stability with hypochlorous acid generating sources (chlorine bleach) such as sodium dichloroisocyanurate, which is an oxidizing agent. More preferably, one or more of the following are preferred.

When the powder and/or tablet contained in the foaming cleaning agent of the present invention contains a foaming agent that generates carbon dioxide gas, the blending ratio of acid to carbonate (acid/carbonate) is the reaction equivalent ratio. The value is preferably 0.5 to 1.4 for efficient foaming, 0.7 to 1.4 is preferred for more efficient foaming, and 0.7 to 1.3 is more efficient. It is preferred because it foams well. Here, the reaction equivalent ratio is the ratio of the reaction equivalent of the organic acid to the reaction equivalent of the carbonate, and the reaction equivalent of the carbonate and the organic acid are each calculated using the following formula 2.

(Formula 2)
Reaction equivalent = (100g x blending ratio (mass%)) / (1 gram equivalent)
However, 1 gram equivalent is calculated by 1 gram equivalent=(molecular weight)/(valence of acid or base). Note that the valence means the valence as an acid or the valence as a base.

In this specification, containing a foaming agent that generates carbon dioxide gas means containing an acid (especially an organic acid) and a carbonate, and the amount of the foaming agent that generates carbon dioxide gas. means the total amount of organic acid and carbonate in the foaming detergent.

The blending ratio of the foaming agent that generates carbon dioxide gas is preferably 10 to 99% by mass, more preferably 20 to 90% by mass, and more preferably 30 to 99% by mass based on the total mass of the tablet and powder (in the foaming detergent). 80% by mass is more preferred.

(Foaming agent that generates oxygen gas)
As a foaming agent that generates oxygen gas, an oxidizing agent (hereinafter referred to as an oxidizing agent in this specification,
Compounds that cause hydrogen peroxide generation will be removed. ) can be used in combination with a compound that generates hydrogen peroxide.
It is preferable to use a compound that generates hypochlorous acid as the oxidizing agent, such as trichloroisocyanuric acid, sodium dichloroisocyanurate, sodium dichloroisocyanurate hydrate, potassium dichloroisocyanurate, dichlorohydantoin, and chlorobromohydantoin. , dibromohydantoin, calcium hypochlorite, and a mixture thereof.From the viewpoint of solubility in water and ease of handling, sodium dichloroisocyanurate and hydration of sodium dichloroisocyanurate are preferred. One or more selected from the group consisting of: and mixtures thereof are preferred. In addition, potassium monopersulfate double salt and the like can be used as an oxidizing agent other than the compound that generates hypochlorous acid.
Examples of compounds that generate hydrogen peroxide include one or more selected from the group consisting of sodium percarbonate, sodium perborate, organic peroxides such as peracetic acid and benzoic acid peroxide, and mixtures thereof. Preferably, one or more selected from the group consisting of sodium percarbonate, sodium perborate, and a mixture thereof, from the viewpoint of excellent formulation stability and good solubility in water, ease of availability, and ease of handling. preferable.
The compositions of the tablet and powder may be the same or different.

By using a combination of an oxidizing agent and a compound that serves as a hydrogen peroxide generating source, it acts as a foaming agent by generating oxygen gas. For example, 1 mole of sodium dichloroisocyanurate, which is an oxidizing agent and a source of hypochlorous acid, generates 2 moles of hypochlorous acid when dissolved in water. On the other hand, for example, 1 mole of sodium percarbonate, which is a source of hydrogen peroxide, has 1.5 moles of hydrogen peroxide added to 1 mole of sodium carbonate, and when dissolved in water, 1.5 moles of hydrogen peroxide are added to 1 mole of sodium carbonate. Generates hydrogen peroxide. Hypochlorous acid and hydrogen peroxide in water produce hydrochloric acid, water, and oxygen according to the following reaction formula (I). That is, 4 moles of sodium percarbonate are required to obtain 6 moles of hydrogen peroxide equivalent to 6 moles of hypochlorous acid produced from 3 moles of sodium dichloroisocyanurate.
HClO+ _H2O2 → HCl+ _{H2O + O2} ...(I)
The molecular weight of sodium dichloroisocyanurate is 220, and the molecular weight of sodium percarbonate, which is calculated by adding 1.5 mol of hydrogen peroxide to 1 mol of sodium carbonate, is 157, so 3 mol (660 g) of dichloroisocyanurate 4 moles (628 g) of sodium percarbonate are required to release hydrogen peroxide so as to react with hypochlorous acid produced from sodium hydroxide in just the right amount. In this case, the mass ratio of sodium dichloroisocyanurate and sodium percarbonate can be considered to be 1.05:1 in order to obtain hypochlorous acid and hydrogen peroxide that react in just the right amount. Note that hypochlorous acid can take the form of hypochlorite ions or chlorine gas in water depending on the influence of pH, etc., but it can react with hydrogen peroxide in either form.

When both the oxidizing agent and the compound serving as a hydrogen peroxide generation source are blended in a ratio that allows the reaction shown by formula (I) to be carried out in just the right amount, the amount of the foaming agent to be blended is equal to that of the oxidizing agent and hydrogen peroxide. Equal to the total amount of source compounds. On the other hand, if either the oxidizing agent or the compound that is a hydrogen peroxide generation source is blended in an amount exceeding the amount necessary to react in just the right amount, the excess amount of the oxidizing agent or hydrogen peroxide generation source will be used. The compound acts as a bleaching agent. Therefore, in this specification, when referring to the blending amount of a foaming agent that generates oxygen gas, it refers to the total amount of the oxidizing agent and the compound that becomes a hydrogen peroxide generation source within a range that can react in just the right amount. Compounds that are oxidizing agents or sources of hydrogen peroxide are classified as bleaching agents. Therefore, the same compound that is a source of oxidizing agents and hydrogen peroxide may be distinguished as foaming agents or bleaching agents.

Generally available sodium percarbonate often has 1.5 moles of hydrogen peroxide added to 1 mole of sodium carbonate. However, for safety reasons, there is sodium percarbonate with a high content ratio of sodium carbonate (relatively small number of added hydrogen peroxides). In this specification, sodium percarbonate includes those to which 1.5 moles or less of hydrogen peroxide is added to 1 mole of sodium carbonate. In other words, sodium percarbonate includes a mixture of sodium carbonate to which hydrogen peroxide has been added and sodium carbonate to which hydrogen peroxide has not been added.

In this specification, "contains a foaming agent that generates oxygen gas" means that it contains both the hypochlorous acid generation source and the hydrogen peroxide generation source, and "contains a foaming agent that generates oxygen gas" "Amount of foaming agent that generates foaming agent" means the amount of hypochlorous acid generating source and hydrogen peroxide generating source within the range where the hypochlorous acid generating source and hydrogen peroxide generating source react in just the right amount. means the total amount. The excess amount of hypochlorous acid generating source or hydrogen peroxide generating source that does not contribute to the oxygen gas generating reaction is not included in the amount of foaming agent blended.

The blending ratio of the foaming agent that generates oxygen gas is preferably 10 to 99% by mass, more preferably 15 to 95% by mass, and 20 to 90% by mass based on the total mass of the tablet and powder (in the foaming detergent). Mass % is more preferred.

(Other additives)
The tablets and powders of the present invention can be formulated into a combination of various cleaning beneficial compounds. In addition to foaming agents, the tablets and powders of the present invention may contain bleach, surfactants, chelating agents (metal ion scavengers), organic polymers, fragrances, and pigments, as long as they do not impair the effects of the present invention. , enzymes, inorganic substances, and other additives may be added. Not only solid additives but also liquid additives can be used. For example, liquid additives are mixed in advance with porous inorganic powder such as zeolite, and the liquid component is supported on the inorganic material before being blended. Also good.

Examples of the bleach include chlorine bleach, which becomes a source of hypochlorous acid when dissolved in water, and oxygen bleach, which becomes a source of hydrogen peroxide when dissolved in water.
Chlorine bleaches and oxygen bleaches are also used as foaming agents that generate oxygen gas, but the portion blended in excess of the reaction equivalent as a foaming agent acts as a bleaching agent. For example, when sodium dichloroisocyanurate and sodium percarbonate are used as foaming agents that generate oxygen gas, hypochlorous acid and hydrogen peroxide are generated when dissolved in water, and these react. to generate oxygen gas. At this time, if sodium dichloroisocyanurate is added in an amount exceeding the reaction equivalent, free hypochlorous acid remains in the aqueous solution after foaming, and the remaining hypochlorous acid acts as a bleaching agent. do. Furthermore, when sodium percarbonate is added in an amount exceeding the reaction equivalent, free hydrogen peroxide remains in the aqueous solution after foaming, and the remaining hydrogen peroxide acts as a bleaching agent.
In this way, when blending bleach, either a hypochlorous acid generating source or a hydrogen peroxide generating source is blended as a foaming agent that generates oxygen gas in an amount exceeding the reaction equivalent for oxygen gas generation. By doing so, the ingredients blended in excess can be used as a bleaching agent.
When blending only a foaming agent that generates carbon dioxide, a bleaching agent may be blended as appropriate.

Suitable chlorine bleaches include, for example, trichloroisocyanuric acid, sodium dichloroisocyanurate, sodium dichloroisocyanurate hydrate, potassium dichloroisocyanurate, dichlorohydantoin, chlorobromohydantoin, dibromohydantoin, calcium hypochlorite, and the like. can be mentioned. From the viewpoint of availability and handleability, trichloroisocyanuric acid, sodium dichloroisocyanurate, and hydrates of sodium dichloroisocyanurate are preferred. These chlorine bleaches may be used alone or in combination of two or more.
Examples of oxygen bleaches include organic peroxides such as sodium percarbonate, sodium perborate, and benzoic acid peroxide, and potassium monopersulfate double salt. Sodium percarbonate and sodium perborate are preferred from the viewpoint of availability and ease of handling. These oxygen bleaches may be used alone or in combination of two or more.

The effective chlorine content (in terms of Cl ₂ ) of a compound (chlorine bleach, etc.) that is a source of hypochlorous acid as a bleaching agent can be calculated using an iodine titration method. That is, iodine liberated by the reaction between active chlorine and potassium iodide is titrated with an aqueous sodium thiosulfate solution, and the effective chlorine content is calculated using the following equation 3.

(Formula 3)
Available chlorine content (%) = a x f x 0.35452/b
a: 0.1N sodium thiosulfate aqueous solution (ml) required for titration
b: Sample (g)
f: Factor of 0.1N sodium thiosulfate aqueous solution

Note that the theoretical available chlorine content of trichloroisocyanuric acid is 91.5%, that of sodium dichloroisocyanurate is 64.5%, and that of sodium dichloroisocyanurate dihydrate is 55.4%.

As a source of hydrogen peroxide, for example, the effective oxygen content ( _O2 equivalent value) of oxygen-based bleaches such as hydrogen peroxide adducts represented by sodium percarbonate can be determined using the following iodine titration method: It can be calculated using Formula 4.
That is, iodine liberated by the reaction between active oxygen and potassium iodide is titrated with an aqueous sodium thiosulfate solution, and the effective oxygen content is calculated using the following equation 4. In order to accelerate the reaction between active oxygen and potassium iodide, a small amount of ammonium molybdate aqueous solution adjusted to 1% by mass may be added.

(Formula 4)
Effective oxygen content (%) = a x f x 0.08000/b
a: 0.1N sodium thiosulfate aqueous solution (ml) required for titration
b: Sample (g)
f: Factor of 0.1N sodium thiosulfate aqueous solution The theoretical effective oxygen content of sodium percarbonate, in which 1.5 mol of hydrogen peroxide is added to 1 mol of sodium carbonate, is 15.3%. be.

The blending ratio of the bleaching agent is preferably 1 to 50% by weight, more preferably 2 to 40% by weight, and even more preferably 5 to 35% by weight, based on the total weight of the tablet and powder (in the foaming detergent).

A surfactant can be added to tablets and powders of foaming detergents. By incorporating a surfactant, the foam generated by foaming of the foaming detergent will last, making it easier for the cleaning agent components to come into contact with the object to be cleaned, and the surfactant itself will cause the foaming of the object to be cleaned. Contributes to removing dirt. The surfactant may be blended only in the powder, may be blended only in the tablet, or may be blended in both the powder and the tablet. From the viewpoint of rapid dissolution and foaming, it is preferable to incorporate a surfactant only into the powder.

The blending ratio of the surfactant is expressed in mass % based on the total mass of the tablet and powder. For example, when a surfactant is blended into either the powder or the tablet, the mass of the surfactant blended only into the powder or the tablet is divided by the total mass of the powder and the tablet, and the result is 100. The multiplied value is the blending ratio (mass%) of the surfactant.
The blending ratio of the surfactant is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, based on the total mass of the tablet and powder. If it is 0.1% by mass or more, sufficient surfactant action is obtained and the amount of foaming increases, so it is preferable, if it is 1% by mass or more, the amount of foaming increases even more, so it is preferable, and if it is 2% by mass or more, it is preferable. This is preferable since the foaming amount further increases.

If the amount of the surfactant is too large, not only will it not contribute to foaming, but the amount of other detergent components such as a foaming agent will be limited. Therefore, the blending ratio of the surfactant is preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, based on the total mass of the tablet and powder. . If it is 20% by mass or less, the surfactant is not wasted, so it is preferable, and if it is 10% by mass or less, the surfactant is not wasted and more other detergent components can be added. Preferably, the amount is 8% by mass or less, which is even more preferable because more other detergent components can be blended.

Further, the surfactant may not be added to the tablet or powder, but may be added separately to the water reservoir to be cleaned. For example, a surfactant may be added in advance to a water puddle in contact with the object to be cleaned, and then a foaming cleaning agent may be added. In this case, the amount of the separately added surfactant used can be in the same range as when the surfactant is blended into the tablet and/or powder. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and one or more selected from these groups can be used.
In this way, a container containing tablets and powder and a container containing other ingredients can be combined into a form (e.g. , forms in which these are packaged together) are also included in the foaming detergent of the present invention.

Examples of the anionic surfactant that can be used in the present invention include fatty acid salts such as potassium oleate soap, potassium castor oil soap, semi-hardened beef tallow fatty acid sodium soap, and semi-hardened beef tallow fatty acid potassium soap; Alkyl sulfate ester salts such as sodium sulfate, higher alcohol sodium sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; Alkylbenzene sulfonates such as C12 to C14 branched or linear alkylbenzenesulfonate sodium; C14 to C18 α-olefin sulfones sulfonates such as sodium alkylnaphthalenesulfonate; dialkyl sulfosuccinates such as sodium dialkyl sulfosuccinate; alkyl diaryl ether sulfonates such as sodium alkyl diphenyl ether disulfonate; potassium alkyl phosphates Alkyl phosphates such as; naphthalene sulfonic acid formalin condensates such as the sodium salt of β-naphthalene sulfonic acid formalin condensates; aromatic sulfonic acid formalin condensates such as the sodium salt of aromatic sulfonic acid formalin condensates; polyoxyethylene Examples include one or more selected from the group consisting of polyoxyethylene alkyl ether sulfate salts such as sodium lauryl ether sulfate; alkyl sulfosuccinates such as sodium alkyl sulfosuccinate; and mixtures thereof.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene higher alcohol ether; sorbitan laurate, sorbitan palmitate; Sorbitan fatty acid esters such as , sorbitan stearate, and sorbitan oleate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, and polyoxyethylene sorbitan oleate; Polyethylene glycol fatty acid esters such as polyethylene glycol laurate, polyethylene glycol stearate, and polyethylene glycol oleate; polyoxyethylene alkyls such as polyoxyethylene laurylamine, polyoxyethylene stearylamine, and ethylene diamine-polyoxyethylene-polyoxypropylene block polymers Amines; alkyls such as lauric acid monoethanolamide, lauric acid diethanolamide, myristic acid monoethanolamide, myristic acid diethanolamide, stearic acid monoethanolamide, stearic acid diethanolamide, coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, etc. Alkanolamide; one or more selected from the group consisting of glycerin fatty acid esters such as stearic acid monoglyceride, stearic acid diglyceride, palmitic acid monoglyceride, palmitic acid diglyceride, oleic acid monoglyceride, and oleic acid diglyceride; sucrose fatty acid ester; and mixtures thereof can be mentioned.

Examples of cationic surfactants include alkyl amine salts such as coconut amine acetate and stearyl amine acetate; lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, distearyl dimethyl ammonium salt, alkylbenzyl dimethyl ammonium salt, and cetyl trimethyl ammonium salt. Quaternary ammonium salts such as stearyltrimethylammonium salt, behenyltrimethylammonium salt, distearyldimethylammonium salt, diisotetradecyldimethylammonium salt, cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride, didecyldimethylammonium chloride, etc. and mixtures thereof.

Examples of amphoteric surfactants include alkyl betaines such as lauryl betaine, stearyl betaine, and 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine; amine oxides such as lauryl dimethylamine oxide; and groups thereof. One or more selected from:

As the surfactant used in the present invention, anionic surfactants are preferred from the viewpoint of excellent blending stability with chlorine bleaches such as sodium dichloroisocyanurate. From the viewpoint of particularly excellent blending stability with chlorine bleach, good foam retention during foaming, and fine foam, for example, sodium linear alkylbenzene sulfonate, sodium α-olefin sulfonate, sodium alkyl sulfate, and More preferably, it is one or more selected from the group consisting of a mixture of these.

Examples of organic polymers include carrageenan, guar gum, locust bean gum, alginic acid, and alkali metal salts of alginic acid; polysaccharides such as dextrin, xanthan gum, pectin, starch, and derivatives thereof; and alkali metals such as methylcellulose, carboxymethylcellulose, and carboxymethylcellulose. One or more salts selected from the group consisting of ethyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, other cellulose derivatives, and mixtures thereof may be mentioned. Alternatively, polyvinyl alcohol, polyacrylamide, polyethylene glycol, polyacrylic acid, polymaleic acid, olefin-maleic anhydride sodium salt copolymer, acrylic acid-maleic acid sodium salt copolymer, diallyldimethylammonium-acrylic acid sodium salt copolymer Examples include one or more selected from the group consisting of polyester, diallylmethylamine-sodium maleate copolymer, other synthetic polymer compounds, and mixtures thereof. Furthermore, a combination of a plurality of organic polymers may be used.

Among organic polymers, polysaccharides are more preferably blended because they have an excellent effect of maintaining foam generated by foaming for a long time. Among the polysaccharides, carrageenan, guar gum, locust bean gum, and xanthan gum are preferred, and guar gum is more preferred, from the viewpoint of stability in combination with chlorine bleach. The polysaccharide may be blended into either the tablet or the powder, or may be blended into both. From the viewpoint of rapid dissolution, it is preferable to incorporate it only into powder.
The blending ratio of polysaccharide is preferably 0.01 to 2.5% by mass, more preferably 0.01 to 1.25% by mass, and 0.01 to 0.25% by mass based on the total mass of the tablet and powder. % is more preferable. When the foaming detergent is dissolved in water, in order to prevent the viscosity of the water from becoming too high and to suppress a decrease in the amount of foaming, the blending ratio of polysaccharides is 2% to the total mass of the tablet and powder. The content is preferably .5% by mass or less. If it is 2.5% by mass or less, it is possible to maintain foam for a long time and the amount of foaming is difficult to decrease, so it is preferable. It is more preferable because it is difficult to reduce the amount of foaming, and even more preferable if it is 0.25% by mass or less because the amount of foaming is difficult to decrease while maintaining the foam for a long time.

Examples of chelating agents include aminocarboxylate salts such as nitrilotriacetate, ethylenediaminetetraacetate, β-alanine diacetate, aspartate diacetate, methylglycine diacetate, and iminodisuccinate, and hydrates thereof. ;Hydroxyaminocarboxylate salts such as serine diacetate, hydroxyiminodisuccinate, hydroxyethylethylenediaminetriacetate, dihydroxyethylglycine salt, and their hydrates;tripolyphosphate, 1-diphosphonic acid, α-methylphosphonate Phosphonocarboxylic acids such as nosuccinic acid and 2-phosphonobutane-1,2-dicarboxylic acid, alkali metal salts thereof and hydrates thereof; polyacrylic acid and alkali metal salts thereof; glutamic acid diacetate and these One or more selected from the group consisting of hydrates; and mixtures thereof can be used. From the viewpoints of availability, ease of handling, and metal ion trapping effect, aminocarboxylate salts, hydrates of aminocarboxylate salts, hydroxyaminocarboxylate salts, hydrates of hydroxyaminocarboxylate salts, and mixtures thereof. One or more chelating agents selected from the group consisting of are preferred.

Examples of pigments include Scarlet G Conch, Permanent Red GY, Seika First (registered trademark) Carmine 3870, Seika First Yellow 2200, Seika First Yellow 2700 (B) (trade names, manufactured by Dainichiseika Kagyo Co., Ltd.), and Acid. Blue 9, Direct Yellow 12 (all trade names, manufactured by Tokyo Chemical Industry Co., Ltd.), Phthalocyanine Blue, Riboflavin (all trade names, manufactured by Wako Pure Chemical Industries, Ltd.), Ultramarine Blue (all trade names, manufactured by Hayashi Pure Chemical Industries, Ltd.) (manufactured by a company). These dyes may be used alone or in combination of two or more.

As the fragrance, conventionally known fragrances can be used.

As the enzyme, various enzymes useful for cleaning can be used.

Examples of inorganic substances (excluding carbonates) include silicates, sulfates, phosphates, acetates, alkali metal hydroxides, alkali metal chlorides, aluminum sulfates, siloxanes, clay minerals, Examples include boron compounds.

Examples of silicates include alkali metal silicates such as sodium silicate, sodium metasilicate, sodium orthosilicate, and hydrates thereof; examples of sulfates include alkali metal sulfates such as sodium sulfate and potassium sulfate; Alkaline earth metal sulfates such as magnesium sulfate; Phosphates include alkali metal phosphates such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, sodium tripolyphosphate, ammonium dihydrogen phosphate; alkali metal water Oxides include sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkali metal chlorides include sodium chloride and potassium chloride; clay minerals include hectorite; boron compounds include boric acid and metaboric acid. , boron oxide, a mixture thereof, and the like. Examples of siloxanes include dimethylpolysiloxane and the like. These silicates, sulfates, phosphates, alkali metal hydroxides, siloxanes, clay minerals, and boron compounds may be used alone or in combination of two or more.

A lubricant may be added to the tablets of the present invention for the purpose of improving production efficiency during tabletting. The lubricant that can be used is not particularly limited, but includes, for example, one or more selected from the group consisting of stearate metal salts such as magnesium stearate and calcium stearate, talc, and mixtures thereof.

(Preferred embodiment of foaming cleaning agent)
The foaming detergent of the present invention is formed by combining a tablet containing a foaming agent and a powder containing a foaming agent. The mass ratio of tablet to powder (tablet/powder) is preferably 0.14 to 5, more preferably 0.3 to 2.5.
The shape of the tablet is preferably cylindrical. The diameter of the bottom surface of the cylinder is preferably 5 to 40 mm, more preferably 20 to 30 mm. The height of the cylinder is preferably 5 to 40 mm, more preferably 10 to 30 mm. The total length of the diameter of the tablet bottom and the height of the tablet is preferably 10 to 50 mm, more preferably 20 to 45 mm. The value obtained by dividing the diameter of the bottom surface of the tablet by the height of the tablet is preferably 1 to 10, more preferably 1.5 to 3.5.

The blending ratio of the foaming agent contained in the tablet and powder is preferably 20% to 90% by mass, more preferably 40% to 90% by mass, based on the total mass of the tablet and powder (in the foaming detergent). Preferably, 50% by mass to 85% by mass is more preferred.
The foaming agent contained in the tablets and powders may include one or both of a foaming agent consisting of a hypochlorous acid generating source and a hydrogen peroxide generating source, and a foaming agent consisting of an organic acid and a carbonate. preferable. Among these, it is more preferable to include a foaming agent consisting of a hypochlorous acid generating source and a hydrogen peroxide generating source. As the hypochlorous acid generating source, halogenated isocyanuric acid or a salt thereof (especially sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.) is preferable, and sodium dichloroisocyanurate is more preferable. As the hydrogen peroxide generating source, sodium percarbonate, sodium perborate, etc. are preferable, and sodium percarbonate is more preferable. As the organic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, citric acid, benzoic acid, etc. are preferable, and succinic acid and fumaric acid are more preferable. As the carbonate, sodium carbonate, sodium hydrogen carbonate, etc. are preferred, and sodium hydrogen carbonate is more preferred.

It is preferable that the foaming detergent tablet and/or powder of the present invention further contains a bleaching agent and/or a surfactant. In particular, it is more preferable that the powder contains a surfactant.
The blending ratio of the bleaching agent is preferably 1 to 50% by mass, more preferably 5 to 20% by mass, based on the total mass of the tablet and powder (in the foaming detergent).
As the bleaching agent, chlorine bleaching agents are preferred, and among these, halogenated isocyanuric acids or salts thereof (particularly sodium dichloroisocyanurate, potassium dichloroisocyanurate, etc.) are more preferred, and sodium dichloroisocyanurate is even more preferred.
The blending ratio of the surfactant is preferably 0.1 to 10% by mass, more preferably 0.3 to 8% by mass, based on the total mass of the tablet and powder (in the foaming detergent).
As the surfactant, anionic surfactants are preferred, and among these, alkyl sulfate salts (sodium lauryl sulfate, etc.), alkylbenzene sulfonates, sulfonate salts (sodium α-olefin sulfonate), and the like are more preferred.
The foaming detergent of the present invention further includes organic polymers (especially polysaccharides, etc.), inorganic substances (especially boron compounds, silicates, phosphates, etc.), lubricants (magnesium stearate, etc.), and other substances. It is preferable that the additives include:

(How to use foaming detergent)
The foaming detergent of the present invention can efficiently clean or bleach stains on an object to be cleaned by adding it to an object to be cleaned that has a puddle of water. Objects to be cleaned include hard surfaces around water that are constantly in contact with water and tend to accumulate dirt. Specifically, examples include water pools in kitchens, washrooms, baths, toilets, etc., drains, and inside drain pipes.

The foaming cleaning agent of the present invention generates a large amount of foam when added to water, and the foam containing the cleaning agent components generated by the foaming is transferred to the draft surface of the water pool, around the drain outlet, and inside the drain pipe. It can reach a wide range of areas where dirt has adhered, and can be efficiently cleaned.
For example, when the cleaning agent composition of the present invention is poured into a water puddle in a toilet, bubbles swell up and reach around the draft surface (inner wall of the toilet bowl), while at the same time cleaning the bottom of the water puddle and inside the pipes deep inside the water puddle. Furthermore, when the cleaning agent composition of the present invention is poured into water in a puddle at the bottom of a kitchen drain, the foam rises up and spreads around the drain lid, inner wall, strainer, etc. The cleaning agent components can be distributed evenly. Furthermore, the foaming detergent of the present invention can be used in places where water is not normally collected, as long as water can be added in combination. Examples include bathroom drains, bathtubs, kitchen sinks, etc.

In order to effectively exhibit the effect of the foaming detergent of the present invention, the concentration of the foaming detergent in the aqueous solution after injection is preferably 1 to 500 g/L, and preferably 5 to 300 g/L. More preferably, it is 10 to 100 g/L. If the concentration of the foaming detergent is 1 g/L or more, a sufficient amount of foam can be obtained, so it is easier to obtain the effect of increasing the foam amount compared to the case where only powder is used, and 5 g/L or more. If the amount is 10 g/L or more, it is easier to obtain an effect of increasing the amount of foaming.

From the viewpoint of safety in use, the foaming detergent of the present invention preferably has a pH around neutral when dissolved in water. The pH of the aqueous solution is around neutrality means that when both tablets and powder of the foaming detergent are dissolved in water, the pH of the 5% by mass aqueous solution (20-25°C) is 6-8. means. In the foaming detergent of the present invention, the pH of the 5% by mass aqueous solution is preferably 6 to 8, more preferably 6.5 to 7.5. When the pH of the 5% by mass aqueous solution is 6 or more, the risk of generating harmful gases such as chlorine gas is reduced, and when the pH is 6.5 or more, the risk is further reduced. On the other hand, when the pH is 8 or less, the risk of corrosive effects on the skin and eyes due to alkalinity is reduced, and when the pH is 7.5 or less, this risk is further reduced, making it possible to use the foaming detergent more safely. Further, the foaming detergent can be used to act on the object to be cleaned at a high concentration. Therefore, it is preferable to measure the pH of the aqueous solution of the foaming detergent using a 5% by mass aqueous solution, which has a relatively high concentration.

EXAMPLES Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto.
The raw materials and experimental equipment used in the Examples and Comparative Examples are as follows.

[raw materials]
・Sodium dichloroisocyanurate: Manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name “Neochlor 60MG” (available chlorine content 64.0%)
・Sodium percarbonate: Manufactured by Hodogaya Chemical Co., Ltd., trade name "PC-A" (available oxygen content 11.8%)
・Sodium hydrogen carbonate (sometimes called baking soda): Manufactured by Tokuyama Corporation ・Succinic acid: Manufactured by Nippon Shokubai Corporation ・Boron oxide: Manufactured by Nippon Denko Corporation ・Boric acid: Manufactured by Nippon Denko Corporation ・Sodium lauryl sulfate: Manufactured by Kao Corporation, Product name: “Emaar 10PT”
・Sodium α-olefin sulfonate: Manufactured by Lion Specialty Chemicals, product name “Liporan PB800”
・Guar gum: Manufactured by Sanshosha, product name “Neobisco G”
・Magnesium stearate: Manufactured by Taihei Kagaku Sangyo Co., Ltd. ・Sodium alkylbenzenesulfonate: Manufactured by Lion Specialty Chemicals Co., Ltd. ・Synthetic layered silicate: Manufactured by BIC Chemi-Japan Co., Ltd., product name "Laponite"
[device]
[Sieve shaker]
・“AS200CONTROL” manufactured by Lecce
[Pot mixer]
・“PM-01” manufactured by As One
[pH meter]
・Horiba Manufacturing “F-51”
[pH electrode]
・“9615S-10D” manufactured by Horiba, Ltd.

[Method for producing foaming detergent]
A composition mixed according to the tablet composition listed in each table was compressed at a pressure of 20 MPa using a small hydraulic compressor (lab bender) using a hard chrome-plated steel mortar. A cylindrical tablet was obtained. As described in each table, the tablets were prepared to have a diameter of 20.0 to 30.0 mm, a height of 9.50 to 18.5 mm, and a mass of 5.00 to 20.0 g.
Similarly, each component is placed in a polyethylene bag so as to have the powder composition listed in each table, the mouth of the bag is tightly sealed, and the entire bag is manually shaken vigorously for at least 5 minutes to mix. A powder composition was obtained.

The average particle diameter of the powder was measured by the method described in the (Powder) section of this specification. The raw material powders used in the present invention all had an average particle size within the range of 200 μm to 1000 μm.

The obtained tablets and powders were mixed at a predetermined mass ratio and packaged in an aluminum laminated film container to obtain a foaming detergent (example) consisting of tablets and powders. The obtained tablets were packaged in an aluminum laminated film container to obtain a foaming detergent (comparative example) consisting only of tablets. The obtained powder was packaged in an aluminum laminated film container to obtain a foaming detergent (comparative example) consisting only of powder.

[How to use foaming detergent]
The aluminum laminate film containing the foaming detergent (Example) consisting of the tablets and powder obtained above was opened, and the tablets and powder were simultaneously put into the water reservoir. That is, the tablets and powder packaged in the same manner were placed in the water reservoir at the same time, compared to the case where only the foaming detergent powder was placed.

For comparison, similar tests were conducted on foaming detergents made of only the tablets or powder obtained above. In general, foaming detergents made only of tablets usually produce less foam than foaming detergents made only of powder. The cleaning agent was evaluated.

[Foaming amount measurement test]
To determine the amount of foam of the foaming detergent, put 2000ml of tap water adjusted to 25℃ into a 5000ml resin graduated cylinder, add 40.0g of the foaming detergent, and add 2, 5, 10, 20. The scale of the measuring cylinder was read at the point where the foam reached after 30 and 60 minutes, and the amount of water (2000 ml) was subtracted from it to determine the amount of foam (ml) after each time. The amount of foam 0 minutes after the addition was 0 ml. The amount of foam after 60 minutes was defined as the amount of foam after a predetermined time (60 minutes).

The amount of foam when the amount of foam became the largest after 2, 5, 10, 20, 30, and 60 minutes was defined as the maximum amount of foam (ml).
When the amount of foam after 0, 2, 5, 10, 20, 30, and 60 minutes is respectively A, B, C, D, E, F, and G (ml),
(a)=[(B+A)/2]×(2-0)
(b)=[(C+B)/2]×(5-2)
(c)=[(D+C)/2]×(10-5)
(d)=[(E+D)/2]×(20-10)
(e)=[(F+E)/2]×(30-20)
(f)=[(G+F)/2]×(60-30)
was calculated, and [total value of (a) to (f)]/60 was calculated, which was defined as the average foam volume (ml).

Retention rate after 30 minutes (%) and retention rate after 60 minutes (%) are determined by measuring the amount of foam 30 minutes and 60 minutes after reaching the maximum amount of foam, and determining whether the amount of foam reaches the maximum amount of foam. It means the percentage held against.
Retention rate after 30 minutes (%) = [(foam volume after 30 minutes)/(maximum foam volume)] x 100
Retention rate after 60 minutes (%) = [(foam volume after 60 minutes)/(maximum foam volume)] x 100

The maximum foaming amount increase rate (%) is the ratio of the maximum foaming amount of the foaming detergent according to the present invention (example) to the maximum foaming amount of the foaming detergent made only of powder (comparative example). means. If the maximum foam volume increase rate exceeds 100%, it is evaluated that the maximum foam volume has increased.
Maximum foam volume increase rate (%) = [(Maximum foam volume in Example)/(Maximum foam volume in Comparative Example)] x 100

The rate of increase (%) in the amount of foam after 60 minutes is the increase rate (%) of the amount of foam after 60 minutes in the foaming detergent of the present invention (Example) compared to the foam amount after 60 minutes in the foaming detergent made only of powder (Comparative Example). Means the percentage of foam volume. If the rate of increase in the amount of foam after 60 minutes exceeds 100%, it is evaluated that the amount of foam after 60 minutes has increased.
Increase rate of foam volume after 60 minutes (%) = [(foam volume after 60 minutes in Example)/(maximum foam volume after 60 minutes in Comparative Example)] x 100

If the foaming detergent according to the present invention (example) has an increase in at least one of the maximum foam volume and the foam volume after 60 minutes compared to the foaming detergent made only of powder, the foaming volume is increased. It is evaluated that it is increasing.
The larger the maximum amount of bubbles, the more the bubbles will spread over a wider area, making it possible to spread the cleaning agent components over a wider range of objects to be cleaned. Further, the larger the amount of foam after 60 minutes, the more the foam is maintained even after a long period of time. When a foaming detergent is added to water, the foam spreads over a wide range of objects to be cleaned, and the foam is maintained for a long time, so that the foam containing the cleaning component can act on the object to be cleaned for a long time. can. It is preferable that the foaming detergent according to the present invention (Example) has both an increased maximum foam volume and a foam volume after 60 minutes compared to a powder-only foaming detergent (Comparative Example). .
Therefore, as a result of the foaming amount measurement test, the foaming is determined when either the maximum foaming amount or the foaming amount after 60 minutes has increased compared to when using a powder-only foaming detergent. The case where the amount of foaming is increasing is evaluated as "○", and the case where both the maximum foaming amount and the foaming amount after 60 minutes are increasing is evaluated as "◎" because the foaming amount is increasing.

[Measurement of pH]
A foaming detergent of 5% by mass based on the mass of water was dissolved in distilled water (ion-exchanged water may also be used) and stirred for 30 minutes. Approximately 50 ml of the aqueous solution after stirring was transferred to a glass beaker, and the pH was measured with a pH meter. Immediately before measurement, three-point calibration was performed using a pH4 standard solution, a pH7 standard solution, and a pH9 standard solution. Note that the temperature of the 5% by mass aqueous foaming detergent solution at the time of measurement was 20°C to 25°C.

(Examples 1 to 9, Comparative Examples 1 to 9)
Tablets and powder containing a foaming agent that generates oxygen gas but not a foaming agent that generates carbon dioxide gas are prepared with the formulations listed in Tables 1 to 3, and the tablets and powder are mixed to form aluminum A foaming detergent was prepared by packaging it in a laminated film container. Using the foaming detergents prepared in Tables 1 to 3, the tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 1 to 9) ).
As a comparison, a foaming detergent consisting only of powder having the same composition as the powder and tablets contained in Examples 1 to 9 was prepared and evaluated in the same manner (Comparative Examples 1 to 9).
The results were as shown in Table 4. In all of Examples 1 to 9, the rate of increase in foam volume after 60 minutes was higher than in Comparative Examples 1 to 9. In Examples 3 to 8, the maximum foam volume increase rate also increased.

(Examples 10 to 16, Comparative Examples 10 to 16)
A powder containing a foaming agent that generates carbon dioxide gas but not a foaming agent that generates oxygen gas is prepared with the formulation shown in Tables 5 to 7, and powder containing a foaming agent that generates oxygen gas is prepared. Tablets containing no foaming agent that generates carbon dioxide gas were prepared, and the tablets and powder were mixed and packaged in an aluminum laminated film container to prepare a foaming cleaning agent. Using the foaming detergents prepared in Tables 5 to 7, the tablets and powder were simultaneously introduced into a graduated cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 10 to 16) ).
For comparison, a foaming detergent consisting only of powder having the same composition as the powder and tablets contained in Examples 10 to 16 was prepared and evaluated in the same manner (Comparative Examples 10 to 16).
The results were as shown in Table 8. In Examples 10 to 16, the foam volume increase rate after 60 minutes increased compared to Comparative Examples 10 to 16, which were made only of powders of the same composition, and in Examples 11 to 16, the maximum foam volume increase rate was further increased. It also increased.

(Examples 17-25, Comparative Examples 17-25)
A powder containing a foaming agent that generates oxygen gas but not a foaming agent that generates carbon dioxide gas is prepared with the formulation shown in Tables 9 to 11, and the powder does not contain a foaming agent that generates oxygen gas. Tablets containing a foaming agent that generates carbon dioxide gas were prepared, and the tablets and powder were mixed and packaged in an aluminum laminated film container to prepare a foaming cleaning agent. Using the foaming detergents prepared in Tables 9 to 11, tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 17 to 25) ).
For comparison, a foaming detergent consisting only of powder having the same composition as the powder and tablets contained in Examples 17 to 25 was prepared and evaluated in the same manner (Comparative Examples 17 to 25).
The results were as shown in Table 12. In Examples 17 to 25, the rate of increase in foam volume after 60 minutes was increased, and the maximum rate of increase in foam volume was also increased, compared to Comparative Examples 17 to 25, which were made only of powders of the same composition.

(Examples 26-34, Comparative Examples 26-34)
Tablets and powder containing a foaming agent that generates carbon dioxide gas but not containing a foaming agent that generates oxygen gas are prepared with the formulation compositions listed in Tables 13 to 15, and the tablets and powder are mixed to form aluminum powder. A foaming detergent was prepared by packaging it in a laminated film container. Using the foaming detergents prepared in Tables 13 to 15, the tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 26 to 34) ).
As a comparison, a foaming detergent consisting only of powder having the same composition as the powder and tablets contained in Examples 26 to 34 was prepared and evaluated in the same manner (Comparative Examples 26 to 34).
The results were as shown in Table 16. In Examples 26 to 34, the maximum rate of increase in foam volume increased, and in Examples 26 to 30 and 32 to 34, the rate of increase in foam volume after 60 minutes also increased.

(Examples 35-41, Comparative Examples 35-38)
Tablets and powder containing a foaming agent that generates carbon dioxide gas but not containing a foaming agent that generates oxygen gas are prepared with the formulation shown in Table 17, and the tablets and powder are mixed to form an aluminum laminate film. Foaming detergents (Examples 35 and 36) were prepared by packaging them in containers. Also, Table 1
Tablets and powder containing both a foaming agent that generates oxygen gas and a foaming agent that generates carbon dioxide are prepared according to the formulation composition described in 8 to 19, and the tablets and powder are mixed to form an aluminum laminate film. Foaming detergents (Examples 37 to 41) were prepared by packaging them in containers. Using the foaming detergents prepared in Tables 17 to 19, tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 35 to 41) ).
For comparison, a foaming detergent (Comparative Example 35) consisting only of powder with the same composition as the powder and tablets contained in Examples 35-36, and a foaming detergent (Comparative Example 35) with the composition of the powder and tablets contained in Examples 35-36. A foaming detergent (Comparative Example 36) consisting only of tablets of the same composition was prepared and evaluated in the same manner. As the tablets of Comparative Example 36, eight tablets (φ20.0 mm, 5.00 g) were used, which were the same as those used in Examples 35 to 36.
Similarly, a foaming detergent (Comparative Example 37) consisting only of powder having the same composition as the powder and tablets contained in Examples 37 to 41, and A foaming detergent (Comparative Example 38) consisting only of tablets of the same composition was prepared and evaluated in the same manner. As the tablets of Comparative Example 38, eight tablets (φ20.0 mm, 5.00 g) were used, which were the same as those used in Examples 37 to 41.
The results of Examples 35 to 36 and Comparative Examples 35 to 36, as well as the results of Examples 37 to 41 and Comparative Examples 37 to 38, were as shown in Table 20. In all of Examples 35 and 36, the rate of increase in foam volume increased after 60 minutes, and the rate of increase in maximum foam volume also increased. In Examples 37 to 41, the foam volume increase rate after 60 minutes increased, and in addition, Examples 37 to 39 and 41 also increased the maximum foam volume increase rate.

(Examples 42 to 47, Comparative Examples 39 to 41)
Tablets and powder containing a foaming agent that generates oxygen gas but not a foaming agent that generates carbon dioxide gas are prepared with the formulation shown in Table 21, and the tablets and powder are mixed to form an aluminum laminate film. Foaming detergents (Examples 42 to 44) were prepared by packaging them in containers. In addition, tablets and powder containing both a foaming agent that generates carbon dioxide and a foaming agent that generates oxygen gas are prepared with the formulation shown in Table 22, and the tablets and powder are mixed to form an aluminum laminate. Foaming detergents (Examples 45 to 47) were prepared by packaging them in film containers. Using the foaming detergents prepared in Tables 21 and 22, tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 42 to 47) ).
For comparison, a foaming detergent (Comparative Example 39) consisting only of powder with the same composition as the powder and tablets contained in Examples 42 to 44, and A foaming detergent (Comparative Example 40) consisting only of tablets of the same composition was prepared and evaluated in the same manner. As the tablets of Comparative Example 40, eight tablets (φ20.0 mm, 5.00 g) were used, which were the same as those used in Examples 42 to 44.
Similarly, a foaming detergent (Comparative Example 41) consisting only of powder having the same composition as the powder and tablets contained in Examples 45 to 47 was prepared and evaluated in the same manner.
The results of Examples 42 to 44 and Comparative Examples 39 to 40, and the results of Examples 45 to 47 and Comparative Example 41 were as shown in Table 23. In Examples 42 to 44, both the maximum foam volume increase rate and the foam volume increase rate after 60 minutes increased. In Examples 45 to 47, both the maximum foam volume increase rate and the foam volume increase rate after 60 minutes increased.

(Examples 48 to 54, Comparative Example 42)
Tablets and powder containing both a foaming agent that generates carbon dioxide gas and a foaming agent that generates oxygen gas are prepared with the formulation compositions listed in Tables 24 to 26, and the tablets and powder are mixed to form aluminum Foaming detergents (Examples 48 to 54) were prepared by packaging in laminated film containers. In Examples 48 to 50 listed in Table 24, 1 to 3 tablets each having a diameter of 20.0 mm were used. In Examples 51 to 54 listed in Tables 25 to 26, one tablet with a diameter of φ30.0 mm was used. Using the foaming detergents prepared in Tables 24 to 26, the tablets and powder were simultaneously introduced into a measuring cylinder filled with tap water to simulate the object to be cleaned, and the amount of foaming etc. was measured (Examples 48 to 54) ).
Similarly, foaming detergents (Comparative Examples 42 to 48) consisting only of powders having the same composition as the powders and tablets contained in Examples 48 to 54 were prepared and evaluated in the same manner.
The results of Examples 48 to 54 and Comparative Examples 42 to 48 were as shown in Table 27. In Examples 48 to 54, both the maximum foam volume increase rate and the foam volume increase rate after 60 minutes increased.

From the above results, the foaming detergent that combines tablets and powder of the present invention has a higher maximum foam volume increase rate and foam volume after 60 minutes compared to foaming detergents that have the same composition but only powder or tablets. It became clear that either or both of the rates of increase increased. It was found that due to this effect of increasing the foaming amount, the foaming detergent of the present invention can more efficiently clean dirt near the draft surface.

Generally, when foaming detergents have the same composition, tablets have a lower maximum foaming amount than powder, so the foaming amount of foaming detergents that combine powder and tablets is It was expected that the amount of foaming would be between the foaming detergent made only by tablets and the foaming detergent made only by tablets. However, it has been revealed that the combination of tablets and powder as in the present invention has a higher foaming amount than either the powder alone or the tablet alone. Such an effect is a remarkable effect that cannot be predicted from the conventional technology. Furthermore, the combination improved the sustainability of the foam and increased the rate of increase in the amount of foam after 60 minutes, which is a remarkable effect that could not have been expected from the prior art.

According to the present invention, it is possible to provide a foaming detergent that has a high foaming amount and can spread the detergent components over a wide range, and a method for using the same, and has great industrial applicability. It is.

Claims (1)

A foaming cleaning agent comprising a combination of a tablet containing a foaming agent and a powder containing a foaming agent.