JPH1135987A - Solid detergent composition for hard surface use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent which ensures cleaning and sterilization simultaneously by blending an inorg. peroxide, a cationic sterilizer and a foaming agent comprising a carbonate or a bicarbonate and a solid acid. SOLUTION: (A) An inorg. peroxide is selected from the group consisting of sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate and a sodium sulfate-sodium chloride-hydrogen peroxide adduct. (B) As a cationic sterilizer enumerated are a cationic surfactant type steritizer, a biguanide type sterilizer and an amino acid type surfactant and the like. (C) As a carbonate or a bicarbonate, an ammonium salt of an alkali metal or an alkaline earth metal is pref. and as a solid acid, an org. acid is pref. With 100 pts.wt. of component A are generally blended 0.5-300 pts.wt. of component B and 5-800 pts.wt. of component C. It is also possible to blend a metal chelating agent, a surfactant and, in particular, a nonionic surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid detergent composition having a bactericidal performance, which is suitable for hard surfaces such as plastic, metal, glass, and tile. In particular, the detergent composition of the present invention is suitable as a disinfectant detergent for floors and utensils of food factories, kitchens, hospitals, nursing homes, public toilets and the like where it is necessary to reduce the number of bacteria in the environment.

[0002] Further, since the detergent composition of the present invention is solid and contains a foaming agent, when sprayed directly on a wet floor or the like, bubbles due to carbon dioxide gas are generated, and the location of the spray is easily recognized and generated. If it is a light oil stain due to the force of the foam, washing and sterilization can be performed only by flushing with water after standing without performing brushing or the like. Naturally, more effective cleaning and sterilization can be performed by brushing. Further, it can be dissolved in water and used as a immersion detergent having a sterilizing performance.

[0003]

2. Description of the Related Art Many food manufacturing factories, pharmaceutical manufacturing factories, hospitals, nursing homes, kitchens, toilets, and the like require a sanitary environment. In these cases, in order to maintain a sanitary environment, frequent washing and disinfection treatment of floors, walls, etc., used equipment, and the like are indispensable.

[0004] Generally, the number of bacteria present on the floor surface is overwhelmingly higher than at other locations. Therefore, the number of bacteria existing on the floor determines the number of bacteria in the environment, and the sterilization of the floor is important in improving environmental hygiene.

Conventionally, plastics such as floors and walls, metals,
For cleaning and disinfecting hard surfaces such as glass and tiles, (1) liquid detergent, (2) liquid disinfectant detergent, and (3) powder detergent are mainly used.

However, most of the liquid cleaning agents (1) are used by diluting the undiluted solution in actual use. It takes time and effort to dilute the liquid, and it is difficult to spray it because it is a liquid. It ’s clear,
Effective cleaning is difficult. In addition, since it is a liquid, it may be washed away after application and a sufficient cleaning effect may not be exhibited. In addition, since it contains only the cleaning component, a bactericidal effect cannot be expected, and a separate bactericidal treatment must be performed. In addition, the liquid sterilizing detergent of (2) can be expected to have a cleaning effect and a sterilizing effect,
There is the same problem as the liquid cleaning agent of (1). Further, at present, there is no powder-based cleaning agent of (3) that can sterilize and wash at the same time, and since it is a solid, the amount of spraying tends to be large and undissolved residue may occur. That is, there has been no known agent capable of more easily and surely sterilizing and cleaning hard surfaces such as floors.

[0007]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the present inventors mixed solid sodium percarbonate or sodium perborate with a solid cationic fungicide. Further, by adding a foaming agent comprising a carbonate or a bicarbonate and a solid acid, a washing agent and a germicidal agent can be obtained, and further, a solid agent that can surely perform them can be obtained. This led to the completion of the present invention.

That is, the present invention relates to (a) sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate and sodium sulfate / sodium chloride / hydrogen peroxide adducts (B) a cationic disinfectant, (c) a disinfectant characterized by containing a foaming agent comprising a carbonate or bicarbonate (c ₁ ) and a solid acid (c ₂ ). An object of the present invention is to provide a solid cleaning composition for hard surfaces having performance.

The component (a) is one selected from sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate, and adducts of sodium sulfate, sodium chloride, and hydrogen peroxide. Of the above inorganic peroxides, of these, sodium percarbonate and sodium perborate are preferred.

The cationic bactericide of the component (b) includes benzethonium chloride, benzalkonium chloride (alkyl group having 8 to 18 carbon atoms), dialkyl (C _{8 to} C ₁₈ ) dimethyl ammonium halide, and monoalkyl (C ₈ to C ₁₈ ) trimethylammonium halide or a bactericide of a cationic surfactant system in which a counter ion of these bactericides is converted to another anion; chlorhexidine, chlorohexidine gluconate,
And other amino acid-based surfactants such as alkyl (C ₈ -C ₁₈ ) diaminoethyl glycine and dialkyl (C ₈ -C ₁₈ ) aminoethyl glycine.

The component (c) is a carbonate or bicarbonate (c ₁ )
And a solid acid (c ₂ ), which generates carbon dioxide in the presence of water.

Here, the carbonate or bicarbonate (c ₁ ) is
Alkali metal salts, alkaline earth metal salts, ammonium salts are preferred, specifically, sodium carbonate, sodium bicarbonate,
It is preferable to use one or more selected from potassium carbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, ammonium carbonate and ammonium bicarbonate.

The solid acid (c ₂ ) may be in any form such as powder, granules and granules, and those which react with the above-mentioned carbonate or bicarbonate in the presence of water to generate carbon dioxide gas are used. And organic acids are preferably used. In particular, fumaric acid,
Succinic, glutaric, adipic, maleic, citric, gluconic, lactic, malic, tartaric, malonic, aspartic, glutamic, ascorbic,
It is preferable to use one or more selected from oxyacids, benzoic acids and pyrrolidonecarboxylic acids.

Here, the carbonate or bicarbonate (c ₁ ) and the solid acid (c ₂ ) are used in a ratio such that (c ₁ ) / (c ₂ ) = 0.1 / _{1 to 1} / 0.1. It is desirable to use 2/1 to 1 /
A ratio of 2 is preferred.

The weight ratio of the above components (a) to (c) in the composition of the present invention is such that component (b) is 0.5 to 300 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of component (a). Component (c) is 5 to 800 parts by weight, preferably 50 to 500 parts by weight. Within this range, excellent sterilizing power and detergency can be obtained. The component (a) alone does not maintain the bactericidal effect due to the influence of organic substances and the like, and has no immediate effect, but the use of the component (b) solves these problems. Further, since the foam is generated from the component (c), the spraying position can be surely recognized even in a small amount. Also,
There is also an improvement in the washing and stirring effect due to the foaming force, and higher oil washability, bleachability, and sterilization can be obtained.

In the solid detergent composition for hard surfaces of the present invention, it is also preferable to use a metal chelating agent (d) in combination. When a chelating agent is used in combination, a bactericidal effect and immediate effect in the presence of an organic substance are improved, and storage stability is also improved.
Examples of the metal chelating agent (d) include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonate, tripolyphosphoric acid, ethylene glycol bis (2-aminoethyl ether) tetra Using one or more selected from acetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid and salts thereof preferable. The metal chelating agent (d) is used in an amount of 0.5 to 600 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the component (a).

The solid detergent composition for hard surfaces of the present invention contains one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. An activator (e) can also be included. Surfactant (e) is effective in improving the cleaning performance, particularly the oil cleaning performance. Among the surfactants (e), a nonionic surfactant and an amphoteric surfactant are preferred, and a nonionic surfactant is particularly preferred because it does not reduce the bactericidal performance of the cationic bactericide.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester, and alkyl polyglycerin ether. Polyoxyethylene (average addition number of ethylene oxide 3 to 20) alkyl (12 to 18 carbon atoms) ether is preferred.

Examples of the amphoteric surfactant include amine oxides such as alkyldimethylamine oxide, and betaines such as alkyldimethylamino fatty acid betaine and alkylcarboxymethylhydroxyethyl imidazolium betaine.

Examples of the anionic surfactant include higher fatty acid salts, higher alcohol sulfates, higher alcohol sulfonates, sulfated fatty acid salts, sulfonated fatty acid salts, and the like.
Phosphate esters, sulfate esters of fatty acid esters,
Sulfonate of fatty acid ester, sulfate of higher alcohol ether, sulfonate of higher alcohol ether, acetate of higher alcohol ether substitution, condensate of fatty acid and amino acid, alkylolated sulfate of fatty acid amide, Fatty acid amide alkylated sulfonate, sulfosuccinate, alkylbenzene sulfonate, alkylphenol sulfonate, alkylnaphthalene sulfonate, alkylbenzimidazole sulfonate, amide ether carboxylic acid or salt thereof, ether carboxylic acid or the same Salt, N-acyl-N-methyltaurine or a salt thereof, amide ether sulfate or a salt thereof, N-acylglutamic acid or a salt thereof,
N-amidoethyl-N-hydroxyethylacetic acid or a salt thereof, acyloxyethanesulfonic acid or a salt thereof, N-acyl-β-alanine or a salt thereof, N-acyl-N-carboxyethyltaurine or a salt thereof, N-acyl-N -Carboxyethylglycine or a salt thereof, and alkyl or alkenylaminocarbonylmethyl sulfate or a salt thereof.

The cationic surfactants include primary amine salts excluding the agents shown as cationic fungicides;
A secondary amine salt, a tertiary amine salt, and a quaternary ammonium salt are exemplified. Of these, a quaternary ammonium salt is particularly preferred. Examples of the quaternary ammonium salt include compounds represented by the following general formula (1).

[0022]

Embedded image

[Wherein at least one of R ¹ , R ² , R ³ and R ⁴ has 8 to 28 carbon atoms in total, alkoxyl group, alkenyloxy group, alkanoylamino group, alkenoylamino group, alkanoyloxy A benzyl group, an alkyl group having 1 to 5 carbon atoms, a hydroxyalkyl group having 1 to 5 carbon atoms or a group-(R ⁵ O _m H (where R ⁵ represents an alkylene group having 2 to 3 carbon atoms, and m represents 2 to 2)
20 is shown). The surfactant (e) is used in an amount of 0.5 to 100 parts by weight of the component (a).
200 parts by weight, preferably 5 to 50 parts by weight are blended.

Furthermore, it is preferable that the solid detergent composition for hard surfaces of the present invention contains a silicate and / or a sulfate (f). By blending these silicates and sulfates, components such as the cationic disinfectant (b), the metal chelating agent (d), and the surfactant (e) can be used in an aqueous solution instead of being solid. In this case, the silicate and / or sulfate (f)
An aqueous solution of a cationic bactericide (b), a metal chelating agent (d), a surfactant (e), etc. is supported, and then or after heating and drying, is mixed with the components (a) and (c) to form a formulation. Thus, the solid detergent composition of the present invention is obtained.

As the silicate and / or sulfate (f), alkali metal salts, alkaline earth metal salts of silicic acid or sulfuric acid,
Ammonium salts are preferred, and specifically, one or more selected from sodium silicate, potassium silicate, calcium silicate, magnesium silicate, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate and ammonium sulfate are preferably used. Silicate and / or sulfate (f)
Is used in an amount of 5 to 500 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the component (a).

Further, in the solid detergent composition for hard surfaces having a bactericidal performance of the present invention, if necessary, other additives such as other bactericidal agents, extenders, thickeners, enzymes, fragrances, colorings, etc. An agent, an abrasive, a binder, an acid or an alkali as a pH adjuster, and the like can be appropriately compounded as long as the effects of the present invention are not impaired.

The solid detergent composition for hard surfaces of the present invention having a bactericidal performance can be obtained by mixing and stirring when each component is a solid containing no water such as powder or granules. When containing a hydrate (including an aqueous solution), the solid acid, the component (b) and the optional component are first mixed and stirred, and then dried at 60 to 120 ° C.
Finally, a method of mixing and stirring the components (a) and (c) to produce them is desirable. The final dosage form is not particularly limited as long as it is a solid such as powder, granules, tablets and the like. In the case of the tablet type, it is possible to wash and sterilize the periphery only by placing it in an appropriate place.

[0028]

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

Examples 1 to 5 and Comparative Examples 1 to 4 Cleaning compositions having the sterilizing performance shown in Table 1 were prepared.
An aqueous solution obtained by diluting this composition 30 times with 3.5 ° DH hard water was prepared as a practical use system. The diluent was used to evaluate the detergency and bactericidal activity against oil stains, protein stains and starch stains in the following manner. Table 1 shows the results.

[1] Detergency evaluation <1-1; Cleaning conditions> Washing machine used: Renauts improved washing test machine Washing temperature: 25 ± 2 ° C Washing and rinsing water: 3.5 ° DH hard water Washing time: 5 minutes <1- 2: Oil stain cleaning test> Tallow and soybean oil in a volume ratio of 1:
20 g of the fat and oil, 0.25 g of monoolein and 0.1 g of oil red mixed in 1 are dissolved in 60 ml of chloroform to prepare an oil stain liquid. In addition, a model glass dirt piece is prepared using a clean slide glass. The glass pieces are set as a set of six pieces, and the mass is measured up to 1 mg. Approximately 2 pieces of glass slides in oil stain liquid of 25 ℃ ± 1 ℃ to about 55mm each.
Soak for 2 seconds and remove after attaching oil stains. The pool of oil stains adhering to the lower part of the slide glass is sucked off using a cloth such as clean gauze or filter paper, and the oil stains are uniformly deposited, air-dried at 25 ± 1 ° C., and the mass is measured. The model stained glass piece is used for the test within 1 hour or more and 2 hours or less. At this time, the amount of oil stain adhered per six pieces of model stain glass pieces is adjusted to be 0.140 ± 0.010 g. Immediately after the cleaning liquid (diluent) is prepared, the model stained glass piece is cleaned, the mass is measured, and the cleaning rate (%) is calculated. That is, washing ratio (%) = (weight before washing−weight after washing) / the amount of oil stain adhesion × 100. The results are shown in Table 1.

<1-3: Protein stain cleaning test> Skim milk powder
20 g is diluted and dissolved in ion-exchanged water heated to 60 ° C. to make a total of 100 g, which is used as a protein stain liquid. In addition, a model glass dirt piece is prepared using a clean slide glass. twenty five
Approximately 55 glass slides at a temperature of ± 1 ° C.
mm for about 2 seconds to remove protein stains. A pool of protein stains adhering to the lower part of the slide glass is sucked off using a cloth such as clean gauze or a filter paper, and the protein stains are uniformly attached, and air-dried at 25 ± 1 ° C. This operation is repeated once more, and after one side of the stain is completely removed, the sample is air-dried and denatured at 110 ° C. for 1 hour to obtain a test sample. Use this model stained glass piece for the test within 12 to 24 hours. Immediately after preparing the washing liquid (diluent), the model stained glass piece is washed, rinsed, dried in a 70 ° C. drier for 30 minutes, colored with a 1% erythrosine solution, and then colored.
₁ ) was measured by photographic evaluation, and the initial protein stain area
The washing rate (%) is calculated from (S ₀ ). That is, the cleaning rate (%) = (S ₀ −S ₁ ) / S ₀ × 100. The cleaning test was performed on six pieces of model stained glass pieces, and the values were obtained from the average of the cleaning rate values of four pieces excluding the two pieces showing the maximum and minimum values. Table 1 shows the results
Shown in

<1-4; Starch Stain Cleaning Test> A piece of model glass stain is prepared using a clean slide glass. 30
0.2 g of soft cooked cooked rice left at room temperature for 5 minutes is spread on one side of a slide glass, applied, and dried 6 days at room temperature for 6 days to prepare a test sample. Use this model stained glass piece for testing within 12 hours. The model stained glass piece was washed immediately after the washing solution (diluent) was prepared, and the area of the blue portion generated by the iodine color reaction was measured.
(P ₁ ) is measured by photographic judgment, and the washing rate (%) is calculated from the initial protein stain area (P ₀ ). That detergency ratio _{(%) = (P 0 -P} 1) / P is ₀ × 100. The cleaning test was performed on six pieces of model stained glass pieces, and the values were obtained from the average of the cleaning rate values of four pieces excluding the two pieces showing the maximum and minimum values. Table 1 shows the results
Shown in

[2] Evaluation of bactericidal activity The bactericidal activity was evaluated using Escherichia coli IFO39 as a test bacterium.
72, using Staphylococcus aureus IFO12732, fixed the contact time to 60 seconds, 100% when the composition was diluted
The maximum dilution that can be sterilized was determined. That is, bacteria (about 10 ⁹ to 10 ¹⁰ c) pre-cultured on an SCD medium (manufactured by Nippon Pharmaceutical Co., Ltd.)
ell / ml), the composition was diluted with sterile 3.5 ° DH hard water, inoculated into 10 ml of the solution, and allowed to act at room temperature for 60 seconds. After 60 seconds, collect one platinum loop of the bacterial contact solution and use it for post-culture.
The cells were inoculated into micro-chalets (96-Cell Wells, CORNING) containing 0.3 ml of CD medium. Incubate at 30 ℃ for 3 days,
The growth of the bacterium was visually observed to determine the strength of the effect. That is, the maximum dilution ratio at which no growth of bacteria was observed on the microplanter was determined, and the higher the ratio, the higher the bactericidal effect. Table 1 shows the obtained results.

[0034]

[Table 1]

* 1: Those whose alkyl composition is lauryl / myristyl = 2/1 (molar ratio). * 2: Polyoxyethylene lauryl ether (trade name:
* 3: Lauryl dimethylamine oxide (trade name: Amphitol 20N, manufactured by Kao Corporation) * 4: In Comparative Example 2, CMC (carboxymethyl cellulose) was used instead of sodium carbonate.

Examples 6 to 10 Cleaning compositions having the bactericidal performance shown in Table 2 were prepared.
Examples 1 to 5 and Comparative Examples 1 to 4 using these compositions
Evaluation of detergency and bactericidal power was performed in the same manner as described above. Table 2 shows the results.

[0037]

[Table 2]

* 1: Those having an alkyl composition of lauryl / myristyl = 2/1 (molar ratio). * 2: Polyoxyethylene nonylphenyl ether (trade name: Emulgen 910, manufactured by Kao Corporation) * 3: Lauryl trimethyl ammonium chloride (trade name: Cotamine 24P, manufactured by Kao Corporation)

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI A01N 47/44 A01N 47/44 C11D 3/04 C11D 3/04 (72) Inventor Noboru Matsuo 1334 Minato 1334 Minato, Wakayama-shi, Wakayama Kao Corporation Inside the laboratory (72) Inventor Tadashi Moriyama 1334 Minato, Wakayama-shi, Wakayama Prefecture Kao Corporation

Claims (11)

[Claims] (A) one selected from the group consisting of sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate, and an adduct of sodium sulfate, sodium chloride, and hydrogen peroxide; The above-mentioned inorganic peroxide (b) cationic disinfectant (c) has a disinfection performance characterized by containing a foaming agent comprising a carbonate or bicarbonate (c ₁ ) and a solid acid (c ₂ ) A solid detergent composition for hard surfaces. 2. The solid detergent composition for hard surfaces according to claim 1, wherein the cationic fungicide (b) is selected from a cationic surfactant fungicide, a biguanide fungicide and an amino acid surfactant. Stuff. 3. The hard surface according to claim 1, wherein the carbonate or bicarbonate is selected from sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, calcium carbonate, magnesium carbonate, ammonium carbonate and ammonium bicarbonate. Solid detergent composition for use. 4. The method of claim 1, wherein the solid acid is fumaric acid, succinic acid, glutaric acid, adipic acid, maleic acid, citric acid, gluconic acid,
Lactic acid, malic acid, tartaric acid, malonic acid, aspartic acid,
The solid detergent composition for hard surfaces according to any one of claims 1 to 3, wherein the composition is selected from glutamic acid, ascorbic acid, oxyacid, benzoic acid, and pyrrolidonecarboxylic acid. 5. A compound selected from the group consisting of sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate and an adduct of sodium sulfate, sodium chloride and hydrogen peroxide. (B) a cationic disinfectant, (c) a foaming agent comprising a carbonate or bicarbonate (c ₁ ) and a solid acid (c ₂ ), and (d) a metal chelating agent. A solid detergent composition for hard surfaces having a bactericidal performance. 6. The metal chelating agent (d) is ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonate, tripolyphosphoric acid, ethylene glycol bis (2-amino (Ethyl ether) tetraacetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene-maleic acid copolymer, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid and salts thereof. 6. The solid cleaning composition for hard surfaces according to 5. 7. A compound selected from the group consisting of sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate and adducts of sodium sulfate, sodium chloride and hydrogen peroxide. (B) a cationic fungicide (c) a foaming agent composed of a carbonate or bicarbonate (c ₁ ) and a solid acid (c ₂ ) (d) a metal chelating agent (e) nonionic 1 selected from surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants
A solid detergent composition for hard surfaces having a bactericidal performance, comprising at least one kind of surfactant. 8. The solid cleaning composition for hard surfaces according to claim 7, wherein the surfactant (e) is a nonionic surfactant and / or an amphoteric surfactant. 9. The solid cleaning composition for hard surfaces according to claim 8, wherein the nonionic surfactant is a polyoxyethylene alkyl ether and the amphoteric surfactant is an amine oxide. (A) sodium percarbonate, potassium percarbonate, sodium perborate, potassium perborate, potassium monopersulfate, sodium monopersulfate and sodium sulfate / sodium chloride /
At least one inorganic peroxide selected from hydrogen peroxide adducts; (b) a cationic disinfectant; (c) a blowing agent comprising carbonate or bicarbonate (c ₁ ) and a solid acid (c ₂ ) (d ) Metal chelators (e) 1 selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants
A solid detergent composition for hard surfaces having a bactericidal performance, characterized by containing at least one kind of surfactant (f) silicate and / or sulfate. 11. The silicate and / or sulfate (f) is selected from sodium silicate, potassium silicate, calcium silicate, magnesium silicate, sodium sulfate, potassium sulfate, calcium sulfate, magnesium sulfate and ammonium sulfate. 10. The solid detergent composition for hard surfaces according to 9.