JPH08165497A - Solid germicidal fining composition - Google Patents

Abstract

(57) [Summary] [Structure] (A) a halogenated hydantoin, (B) one or more kinds of polyethylene oxides represented by the general formula (1) or (2), and (C) a powdery alkaline agent. A solid sterilizing and clarifying agent composition containing. Embedded image (In the formula, R ¹ is a C11 to C21 alkyl group, and R ² is H.
Or a C12-C22 alkanoyl group, R ³ is H, C 1
To C4 alkyl groups, n and m are values that make the melting point or softening point of the compound 10 ° C. or higher) [Effect] The solid sterilizing and clarifying agent composition of the present invention exhibits an excellent sterilizing and clarifying action for a long period of time. Moreover, generation of chlorine gas is small, and adhesion of slime stains derived from bacteria can be easily prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid sterilizing and clarifying agent composition, and more particularly, to a solid sterilizing and clarifying composition which maintains stable sterilizing action for a long period of time, and produces very little chlorine gas, and is safe for the human body. Agent composition.

[0002]

2. Description of the Related Art Wastewater from the human body, food residues, etc. are used in the drainage outlets of bathrooms and washrooms, toilet bowls, kitchen sinks and waste wire nets that are used around water and have a lot of moisture at all times. It is often the case that bacteria-derived slime is generated or gives off an offensive odor by using as a nutrient source. The above-mentioned place is complicated or narrow, and it takes a lot of trouble to clean it. Such slime may be removed by simply rubbing it with a brush or the like, but various cleaning agents for drainage pipes have been proposed so far in order to remove dirt easily and easily. These cleaning agents were developed with the selling point that the stains can be removed simply by sprinkling them on the spots of dirt and flushing them with water.

The above-mentioned cleaning agent is mainly composed of a concentrated solution of caustic alkali, and is a cleaning agent that dissolves away slime derived from bacteria, hair that causes clogged drainage pipes, denatured oil stains that cannot be washed away with water, and the like. Those with a mechanism are the mainstream. However, although these detergents have excellent cleaning performance, they may have adverse effects on the human body, such as irritation to the skin and effects on the eye mucous membrane, and since they have a strong cleaning effect, gloves must be used during use. In some cases, poor workability has been pointed out.

Therefore, in recent years, solid sterilizing and clarifying agents have been developed and put on the market from the viewpoint of safety and workability. This solid sterilizing and clarifying agent is used by hanging it in a sink trap or by throwing it into a low tank in the toilet.The sterilizing agent contained in the sterilizing agent is gradually dissolved to maintain the sterilizing agent concentration in water at a certain level or more. It has a function to do. With this function, slime derived from bacteria is less likely to adhere to the drain pipe and the like, and the frequency of cleaning can be reduced.

The above solid sterilizing and clarifying agent is mainly formed by molding a halogen-releasing agent which is solid at room temperature into a desired shape by a method such as tableting. Calcium chlorite, dichloroisocyanuric acid salt, trichloroisocyanuric acid salt, high-grade ground bean powder and the like can be mentioned.

[0006] However, the solid sterilizing and clarifying agent having salari powder as a halogen-releasing agent has a problem that it causes scale stain derived from calcium contained therein. on the other hand,
Examples of detergents using halogenated hydantoin as a halogen-releasing agent include toilet cleaning blocks in which halogenated hydantoin and aluminum hydroxide are combined (JP-A-5-171671), and chlorinated hydantoin and magnesium oxide or hydroxide. A mixture of barium (US Pat. No. 4,537,697) has been reported. However, since the pH of the aqueous solution in the former cleaning block is acidic, the risk of chlorine gas generation cannot be avoided.
In addition, the latter mixture had the drawbacks of high dissolution rate and almost no sustainability.

[0007]

Therefore, the object of the present invention is to provide a solid type which is excellent in bactericidal and clarification performance, has low toxicity, and can easily prevent adherence of slime stains derived from bacteria over a long period of time. It is to provide a sterilizing and clarifying agent composition.

[0008]

Under such circumstances, the present inventor has conducted diligent research and, as a result, conducted research on a halogenated hydantoin, which is a halogen-releasing agent having low solubility in water, into powdery alkaline agents and polyethylene oxides. By combining them, the system can be kept alkaline to significantly reduce the emission of chlorine gas, and a fixed amount of halogenated hydantoin can be released slowly and stably over a long period of time. The present invention has been completed by finding that a solid sterilizing and clarifying agent composition having a function capable of safely preventing adhesion of bacteria-derived slime stains generated in a toilet bowl over a long period of time can be obtained.

That is, the present invention provides the following component (A),
(B) and (C): (A) halogenated hydantoin, (B) general formula (1) or (2);

[0010]

Embedded image

(In the formula, R ¹ represents an alkyl group having 11 to 21 carbon atoms, R ² represents a hydrogen atom or an alkanoyl group having 12 to 22 carbon atoms, and R ³ represents a hydrogen atom or 1 to 4 carbon atoms.
And an n and m each represent a value that makes the melting point or softening point of the compound 10 ° C. or higher. The present invention provides a solid sterilizing and clarifying agent composition containing one or more kinds of polyethylene oxides represented by (4) and (C) a powdery alkaline agent.

The halogenated hydantoin of the component (A) used in the present invention is represented by the following formula (3)

[0013]

Embedded image

(Wherein, X ¹ and X ² represent a chlorine atom or a bromine atom, and R ⁴ and R ⁵ represent a hydrocarbon group), N, N'-dihalogeno-5,5-di-substituted hydantoin Is mentioned.

Examples of R ⁴ and R ^{5 in the} formula (3) include an alkyl group having 1 to 5 carbon atoms and a phenyl group.
An alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group,
Particularly preferred are ethyl group, n-propyl group, isopropyl group and the like. A chlorine atom is particularly preferable as X ¹ and X ² .

Preferred specific examples of the halogenated hydantoin include 1,3-dichloro-5,5-dimethyl-hydantoin, 1-bromo-3-chloro-5,5-dimethyl-hydantoin and 1,3-dibromo-5. , 5-dimethyl-hydantoin, 1-bromo-3-chloro-5,5-diphenyl-hydantoin, 1,3-dichloro-5-ethyl-5-methyl-hydantoin and the like, 1,3
-Dichloro-5,5-dimethylhydantoin is particularly preferred.

The component (A) is blended in the solid germicidal fining composition of the present invention in an amount of 30 to 90% by weight (hereinafter simply referred to as%), particularly 50 to 80%. Is not too low, and an effective bactericidal and fining action can be provided with a limited product size, which is preferable.

The polyethylene oxides as component (B) act as a binder during molding and as a sustained release agent.

In the above formula (1), R ¹ has 11 to 11 carbon atoms.
The alkyl group of 21 includes both straight chain and branched chain, and in the present invention, the alkyl group has 1 carbon atoms.
Those having 1 to 17 are preferable. Specifically, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and the like can be mentioned. R ² is preferably an alkanoyl group having an alkyl group exemplified as R ¹ or a hydrogen atom. R ³
Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. R ³
Is preferably a hydrogen atom. Specific examples of the polyethylene oxides (B) include polyethylene glycol,
Polyethylene glycol monostearate, polyethylene glycol distearate, polyoxyalkylene glycol, and the like, particularly polyethylene glycol,
It is preferable to use polyethylene glycol monostearate or polyethylene glycol distearate.

The polyethylene oxides (1) and (2) need to have a melting point or softening point of 10 ° C. or higher in view of tableting moldability, crushing strength, storability and ease of use. For this purpose, in the polyethylene oxides (1) and (2), the addition mole numbers of ethylene oxide, n and m, are preferably from 2 to 200, and in the polyethylene oxides (1), n is particularly preferably from 20 to It is preferably 200, and in the polyethylene oxides (2), m is particularly preferably 20-100. That is, the polyethylene oxides (1) and (2) have a molecular weight of 2000 to 100.
00, especially 4000 to 8000 are preferably used.

The component (B) is incorporated in the solid sterilizing and clarifying composition of the present invention in an amount of 1 to 50%, preferably 1 to 30%.
It is particularly preferable to set it to 2 to 20% from the viewpoint of uniformly dissolving the effective amount of the sterilizing and clarifying component for a long period of time and keeping the product size small. Melting point or softening point is 20
C. or higher is preferable.

As the powdery alkaline agent of the component (C), magnesium hydroxide, calcium hydroxide, potassium carbonate,
Sodium carbonate, sodium hydrogen carbonate, potassium silicate and sodium silicate are preferable, and one kind may be used alone or two or more kinds may be used in combination. It is preferable to use a powdery alkaline agent having a low hygroscopicity, and from this viewpoint, Mg (OH) ₂ and Ca (OH) ₂ are preferable as the hydroxide. Sodium carbonate is particularly preferable other than hydroxide.

The amount of the component (C) blended in the solid sterilizing and clarifying agent composition of the present invention is 1 to 60%, especially 5 to 50% to keep the pH of the system high and inhibit the slow dissolution property. It is preferable because it does not.

The solid sterilizing and clarifying agent composition of the present invention comprises a salt, a polymer and a chelate as an effect enhancer within the range not impairing the effect of the present invention for the purpose of improving the balance component or the sustained release effect of the composition. An optional component such as an agent or a compound having a chelating effect, a coloring agent, a fragrance, a surfactant and a bactericide can be added.

Examples of the salt include sodium sulfate, sodium chloride, sodium paratoluenesulfonate, sodium acetate and magnesium sulfate. Of these, sodium sulfate, sodium chloride and magnesium sulfate are preferable, and sodium sulfate is most preferable. These are added for the purpose of controlling the dissolution of the solid sterilizing and clarifying agent composition.

Examples of the polymer include a homopolymer of acrylic acid having a molecular weight of 100,000 or more, a crosslinked acrylic polymer, a sugar polymer such as guar gum, and the like.
Acrylic acid homopolymers of 0,000 or more are preferred. These are added for the purpose of enhancing the sustained dissolution effect in a small amount.

Examples of the effect enhancer include EDTA, citric acid, acrylic acid type polymers having a molecular weight of less than 100,000, acrylic acid / maleic acid copolymers, etc., and particularly ED
TA and citric acid are preferred. The colorant may be either a pigment or a dye, and a pigment such as a copper phthalocyanine pigment is preferably used because of its high stability. The fragrance is not particularly limited, but alcohol-based fragrances, particularly terpene alcohol-based fragrances are preferably used in consideration of stability and damage to equipment.

The surfactant is not particularly limited, but an anionic surfactant is preferable in consideration of the difficulty of causing a chemical reaction with the halogen-releasing agent and the cleaning performance. Among them, alkylbenzene sulfonate, sulfosuccinate, etc. are particularly preferable. Of these, sulfonate-based, alkyl sulfate and alkyl ether sulfate-based surfactants are preferably used. Examples of the bactericide include 1,2-benzisothiazolin-3-one, trichlorocarbanilide, and benzethonium chloride. In addition, binders such as hydroxypropyl cellulose, carboxymethyl cellulose, sorbitol, corn starch and lactose, lubricants such as benzoate and magnesium stearate and the like can be added.

The preferred formulation examples of the solid sterilizing and clarifying agent composition of the present invention include 50 to 80% of component (A) and component (B).
2 to 20%, component (C) 5 to 50%, salt 5 to 20%, polymer 1 to 10%, and fragrance 1 to 20% (these are available as reagents, for example, from Wako Pure Chemical Industries, Ltd.). Can be mentioned.

The solid sterilizing and clarifying agent composition of the present invention is prepared by mixing the above-mentioned components (A), (B), (C) and optional components and applying a pressure of about ²⁰ to 150 kg / cm ² according to a conventional method. It can be manufactured by tableting and molding.

The amount of one solid sterilizing and clarifying agent composition (tablet molding) is not particularly limited, but the concentration of the active ingredient is lowered, for example, because the total amount of water during use becomes the largest. Assuming an in-tank type toilet bowl cleaner that tends to be easy to do, assuming an average flushing frequency of 500 liters per month for a family of four with a low tank volume of 10 liters, one flush of tap water has an effective chlorine concentration of 1 pp.
Since it is desirable to mix m or more, one dose that can maintain the effect for one month is 5 g of available chlorine, and 10 to 20 g of a molded product by mixing an alkaline agent and a binder. preferable. In this way, the dosage form can be appropriately controlled by blending a dissolution control agent or setting the product size depending on the desired duration and the use situation.

The solid sterilizing and clarifying agent composition of the present invention is used as a sterilizing and clarifying agent for drains of bathrooms and kitchens or as an auto cleaner for flush toilets, but it is preferably used as an auto cleaner for flush toilets. .

[0033]

The solid sterilizing and clarifying agent composition of the present invention exhibits an excellent sterilizing and clarifying action for a long period of time, produces little chlorine gas, and can easily prevent adhesion of slime stains derived from bacteria. .

[0034]

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

Examples 1 to 6 and Comparative Examples 1 to 5 (sterilizing and clarifying agent for bathroom drainage port) 10 g of the mixed raw materials shown in Table 1 were put into a trial tableting mold having a diameter of 3 cm and compressed at 100 kg / cm ^2. I used it as a sample. The slime stain prevention effect was evaluated by the following test method using each sample. The results are shown in Table 1.

[Test Method] The drainage outlet of the bathroom of each household of 11 panelists using a unit bath was cleaned and used as an experiment target. Put one type of sample per household in a polyethylene net, tie the net's mouth with a polyethylene string, and tie the other end to the drain lid so that it does not flow with the drainage, then bathtub as usual After 3 weeks, the state of adhesion of slime-like dirt at the drainage port was visually observed and judged according to the following criteria.

◯: No slime stain is attached. Δ: Slime stain is slightly attached. X: Slime is attached.

The chlorine gas concentration at the drainage port was measured with a gas detector tube one week after the start of the test, and the chlorine gas concentration was 1 ppm.
When less than, it can be said that there is practically no harm. Furthermore, the residual state of the sample after the test start week was also observed and judged according to the following criteria. It can be said that the larger the remaining amount of the sample, the higher the sustaining effect.

[0039]

[Table 1]

Examples 7 to 8 and Comparative Examples 6 to 13 (sterilizing and clarifying agent for toilet bowl) A sterilizing and clarifying agent was produced as follows. First, a mixture of polyethylene glycol distearate (EO = 100, softening point: about 50 ° C.) 40% and sodium sulfate 60% was sufficiently melt-mixed while being heated to 90 ° C. with a kneader. Then, granulate this while running tap water as cooling water,
Of these, those having a particle size range of 16 to 32 mesh were fractionated to obtain a dissolution control agent / binder mixture. 40% of the mixture and the various components shown in Table 2 and 25% of the alkaline agent were placed in a trial tableting mold having a diameter of 5 cm in an amount of 50 g.
Tabletd at 0 kg / cm ² to obtain a sample. Each sample was used to evaluate the effect of preventing ring-shaped stains on the draft part of the toilet bowl by the following test method. Table 2 shows the results.

[Test Method] The toilet bowl of each household of 10 panelists using a flush toilet was cleaned cleanly and used as an experiment target. One type of sample per household was immersed in a low tank, and after 3 weeks, the degree of attachment of ring-shaped stains on the draft part was visually observed and judged according to the following criteria. It can be said that a product that has no ring stains is acceptable as a product.

◯: There is no ring stain. Δ: Some ring stains are attached. X: Ring stains are attached.

The remaining state of the sample was observed 3 weeks after the start of the test and judged according to the following criteria. Even if 3% or more of the initial 5% remains, it can be judged that the available chlorine has been released as set. Further, the sample was placed in a 100 ml beaker and moistened with 5 ml of ion-exchanged water, and after 1 minute, the chlorine gas concentration immediately above 1 cm was measured with a detector tube.

Good: 50% to 25% of the original amount remains. Δ: 25% to 5% of the original amount remains. X: Less than 5% of the original amount remains.

[0045]

[Table 2]

Claims (6)

[Claims] 1. The following components (A), (B) and (C): (A) halogenated hydantoin, (B) general formula (1) or (2); (In the formula, R ¹ represents an alkyl group having 11 to 21 carbon atoms,
R ² represents a hydrogen atom or an alkanoyl group having 12 to 22 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and n and m each have a melting point or a softening point of 10 ° C. or higher. Indicates the value to be set. ) A solid sterilizing and clarifying agent composition containing one or more polyethylene oxides represented by the formula (C) and (C) a powdery alkaline agent. 2. The powdery alkaline agent is magnesium hydroxide,
The solid sterilizing and clarifying agent composition according to claim 1, which is selected from calcium hydroxide, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium silicate and sodium silicate. 3. The component (A) is 30 to 90% by weight, the component (B) is 1 to 50% by weight, and the component (C) is 1 to 60% by weight.
The solid sterilizing and clarifying agent composition according to claim 1, which is contained. 4. The solid germicidal fining composition according to claim 1, wherein n and m in the general formulas (1) and (2) are 10 to 200. 5. The solid germicidal fining composition according to claim 1, which is an autocleaner composition for flush toilets. 6. The solid germicidal fining composition according to any one of claims 1 to 4, wherein the solid germicidal fining agent composition is a germicidal fining agent composition for bathroom and kitchen drainage ports.