JPH1129796A - Solid detergent composition for hard surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a solid detergent capable of preventing the decrease in the long term storage stability in its powder form and further preventing the decrease in the concentration after preparing the aqueous solution and the decomposition of a cationic antibacterial agent by mixing sodium percarbonate or sodium perborate with the cationic antibacterial agent and a metal chelating agent in a specific amount. SOLUTION: A solid detergent comprises, based on 100 pts.wt. sodium percarbonate or sodium perborate, 0.5-100 pts.wt. cationic antibacterial agent and 0.05-100 pts.wt. metal chelating agent. As the cationic antibacterial agent, a cationic surfactant-based antibacterial agent, a biguanide-based anti-bacterial agent, an amino acid-based surfactant, etc., can be exemplified. As the metal chelating agent, ethylenediamine-tetraacetic acid, hydroxyethylethylenediaminetriacetic acid, gluconic acid, citric acid, tripolyphosphoric acid and salts thereof are particularly preferred. It is also preferred to jointly use an alkali inorganic metal salt.

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 cleaning composition of the present invention may be indirectly in contact with food, such as plastic containers for food, containers for storing beverage bottles, etc. As a germicidal cleaning agent, one agent has a bactericidal effect, so prevention of hospital-acquired infections can be expected, and endoscopes, catheters,
It is suitable as a cleaning agent for medical devices such as syringes (before sterilization) and as a preliminary cleaning agent. In addition, since it has a deodorant property by sterilization, it can be used as a deodorant for cleaning pits, pipes, and the like. Furthermore, it is suitable as a disinfectant for floors in places where it is necessary to control the number of bacteria in the environment, such as kitchens, toilets, and hospital facilities. Further, as the method of using the composition of the present invention,
The composition may be used after being dissolved in water, or the composition may be directly sprayed on a floor or the like.

[0002]

BACKGROUND OF THE INVENTION Compounds which generate active oxygen in aqueous solution, such as hydrogen peroxide, sodium percarbonate or sodium perborate, have a cleaning, disinfecting and bleaching action. However, the bactericidal action is weak, and the effect cannot be sufficiently exhibited in a time of about several minutes.

[0003] Cationic germicides are excellent in bactericidal properties and bactericidal immediate effect, but have almost no washing performance and bleaching ability, and cannot be used alone as a germicidal detergent.

[0004] Considering the characteristics of these agents, it can be easily inferred that a detergent having a bactericidal performance can be obtained by mixing these two agents. However, these are known as contraindicated compounds, and can not be stored for a long time simply by using them together, and their functions are offset each other,
Each cleaning performance and sterilization performance cannot be exhibited. In other words, when both are mixed, the cationic bactericide is inactivated by oxidative decomposition, the bactericidal performance is reduced, and the storage stability is very poor because the oxygen concentration is reduced due to the active oxygen releasing compound that imparts the cleaning effect. In the case of an aqueous solution, the performance of each further decreases rapidly, and the cleaning properties and sterilization properties disappear in a short time. In an acidic atmosphere, the two agents can be present in a relatively stable manner, but the detergency of stains, especially protein components, is extremely reduced. Therefore, in the conventional techniques, there is a problem that the performance of each of the agents that can simultaneously perform sterilization and washing is deteriorated when they are combined into one agent.

[0005]

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the solid sodium carbonate or sodium perborate was mixed with the solid cationic fungicide at a specific ratio. By mixing and further using a solid metal chelating agent at a specific ratio, it is possible to prevent long-term storage stability in powder form, further prevent the decrease in concentration after adjusting the aqueous solution, and prevent the decomposition of the cationic fungicide. I understood.

That is, the present invention relates to sodium percarbonate or sodium perborate (a) and 0.5 parts by weight based on 100 parts by weight of the component (a).
The present invention provides a solid detergent composition for hard surfaces having a bactericidal performance, characterized in that the composition comprises -100 to 100 parts by weight of a cationic bactericide (b) and 0.05 to 100 parts by weight of a metal chelating agent (c). is there.

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 metal chelating agent of component (c) includes
There is no particular limitation as long as it has the ability to chelate metal ions, for example, ethylenediaminetetraacetic acid,
Hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, triethylenetetraminehexaacetic acid, phosphonate, tripolyphosphoric acid, ethylene glycol bis (2-aminoethyl ether) tetraacetic acid, citric acid, maleic acid, polyacrylic acid, isoamylene -Maleic acid copolymers, silicic acid, gluconic acid, hydroxybenzylimidinoacetic acid, imidinoacetic acid, and salts thereof. Among them, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, gluconic acid, citric acid, tripolyphosphoric acid and salts thereof are particularly preferred.

The weight ratio of the components (a) to (c) in the composition of the present invention is such that the component (b) is 0.5 to 100 parts by weight, preferably 5 to 50 parts by weight per 100 parts by weight of the component (a). The amount of the component (c) is 0.05 to 100 parts by weight, preferably 5 to 50 parts by weight. Within this range, excellent sterilizing power and detergency can be obtained.

It is preferable that the metal chelating agent of the component (c) is blended in an amount of at least 0.5 times the mol of the cationic bactericide (b). In particular, 0.5 to 5 times mol, and further 0.5 to 2 times
1-fold, especially 1- to 2-fold mole is preferred.

In the solid detergent composition for hard surfaces of the present invention, it is preferable to use an alkali inorganic metal salt (d) in combination. The alkali inorganic metal salt (d) is used in an amount of 10 to 800 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the component (a). Examples of such alkali inorganic metal salts include sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium sulfate, potassium sulfate and the like. In particular, when an alkali inorganic metal salt is used, each of them can be used in the form of an aqueous solution instead of a solid cationic bactericide and a solid metal chelating agent. In other words, the alkali inorganic metal salt is first supported with an aqueous solution of a cationic bactericide and a solid metal chelating agent, and then or after heating and drying, and then mixed with sodium percarbonate or sodium perborate to form a solid. A cleaning composition is obtained.

In the solid detergent composition for hard surfaces of the present invention, surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants can be used in combination. Among them, the effect of the nonionic surfactant is particularly high. That is, the detergency of the active oxygen component generated from sodium carbonate or sodium perborate, particularly the oil detergency, can be further enhanced by the addition of a nonionic surfactant. As the nonionic surfactant, those selected from polyoxyethylene alkyl ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester, and alkyl polyglycerin ether are preferable. Nonionic surfactant (e) is (a) component 10
0.5 to 100 parts by weight, preferably 1 to 100 parts by weight,
10 parts by weight are blended.

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, granulating agents, thickeners, proteases, catalase, etc. The enzymes, fragrances, coloring agents, extenders, abrasives and the like can be appropriately compounded within a range that does not impair the effects of the present invention.

The solid detergent composition for hard surfaces having a bactericidal performance according to the present invention can be prepared by mixing and stirring each component when it is a solid containing no water such as powder or granules. )), An alkali metal salt, a cationic bactericide and other components are first mixed and dried at 60 to 120 ° C., and finally mixed and mixed with sodium percarbonate or sodium perborate. The final dosage form is not particularly limited as long as it is a solid such as a powder, a granule, and a tablet.

[0015]

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 and 2 Detergent compositions were prepared from the components shown in Table 1. An aqueous solution obtained by diluting this composition 100 times with 3.5 ° DH hard water was prepared as a practical system. The diluent was used to evaluate the detergency and bactericidal activity against oil stains, protein stains and starch stains in the following manner. At the same time, 10 immediately after dilution is taken as 10
The retention rate of the cationic bactericide and the effective oxygen concentration after time was calculated. Table 1 shows the results. In addition, the concentration of the cationic bactericide was determined by HPLC (L-7100 manufactured by Hitachi, Ltd.), and the effective oxygen concentration was determined by JIS-K 3362 (Section 5.9).

[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. A cleaning test is also performed on a solution left for 10 hours after preparation of the cleaning solution (diluent). 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.
Excluding the two that showed the maximum and minimum values of each value,
Determined from the average of the four cleaning rate values. A cleaning test is also performed on a solution left for 10 hours after preparation of the cleaning solution (diluent). The results are shown in Table 1.

<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. Immediately after preparing the washing liquid (diluent) of the above-mentioned model stained glass piece, washing, and the area of the blue portion generated by the iodine color reaction
(P ₁ ) is measured by photographic judgment, and the washing rate (%) is calculated from the initial protein stain area (P ₀ ). That is, cleaning rate (%) = (P ₀ −P ₁ ) / P ₀ × 100 The cleaning test was performed on six pieces of model stained glass pieces.
Excluding the two that showed the maximum and minimum values of each value,
Determined from the average of the four cleaning rate values. A cleaning test is also performed on a solution left for 10 hours after preparation of the cleaning solution (diluent). The results are shown in Table 1.

[2] Evaluation of bactericidal activity The bactericidal activity was evaluated using Escherichia coli IFO39 as a test bacterium.
72. Using Staphylococcus aureus IFO12732, the contact time was fixed at 60 seconds, and the maximum dilution ratio that could be 100% sterilized when the washing solution (diluent) was further diluted was determined. The maximum dilution ratio 10 hours after the dilution was also determined. That, SCD medium (Nippon Pharmaceutical Co., Ltd.) before cultured bacteria (about ^{10 9} ~10 10 cell / ml) with 0.1ml up, in 3.5 ° DH hard water was further sterilized prepared washing solution (diluted solution),
10 ml of a 1, 2, 3, 5, 7, 10, 20, 30, 50, 70, or 100-fold diluted solution (that is, a maximum of 100 × 100 = 10000-fold dilution)
And allowed to act for 60 seconds at room temperature. After 60 seconds, one loopful of the bacterial contact solution was collected and a micro-chalet containing 0.3 ml of SCD medium for post-culture (CORNING, 96-Cell Wells)
). The cells were cultured at 30 ° C. for 3 days, and the growth of the bacteria was visually observed to determine the strength of the effect. In other words, find the maximum dilution factor at which no bacterial growth is observed on the micro planter,
The higher the magnification, the higher the bactericidal effect. Table 1 shows the obtained results.

[0021]

[Table 1]

* 1: Those having an alkyl composition of lauryl / myristyl = 2/1 (molar ratio). * 2: Polyoxyethylene lauryl ether (trade name:
Kao Corporation Emulgen 108) Examples 6 to 8 A powder detergent composition having the bactericidal performance shown in Table 2 was prepared and subjected to a storage stability test in solid state (40 ° C x 85%, 3 months). Table 2 shows the results of calculating the retention rates of the cationic bactericide and the effective oxygen concentration after storage by the same method as in Examples 1 to 5 and Comparative Examples 1 and 2.

[0023]

[Table 2]

* 1: The alkyl composition is lauryl (C ₁₂ ) /
Myristyl (C ₁₄₎ = 50/50 (weight ratio) one. * 2: Polyoxyethylene lauryl ether (trade name:
Kao Corporation Emulgen 108)

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 7:18 7:22 7:08) (72) Inventor Takashi Itoi 1334 Minato, Wakayama-shi, Wakayama Pref.

Claims (8)

[Claims] 1. Sodium percarbonate or sodium perborate (a)
And a bactericidal performance comprising 0.5 to 100 parts by weight of a cationic bactericide (b) and 0.05 to 100 parts by weight of a metal chelating agent (c) per 100 parts by weight of the component (a). A solid detergent composition for hard surfaces having the formula: 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 method according to claim 1, wherein the metal chelating agent (c) 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. The solid cleaning composition for hard surfaces according to 1 or 2. 4. Sodium percarbonate or sodium perborate (a)
And 0.5 to 100 parts by weight of a cationic fungicide (b), 0.05 to 100 parts by weight of a metal chelating agent (c), and 10 to 800 parts by weight of an alkali inorganic metal with respect to 100 parts by weight of the component (a). salt
A solid detergent composition for hard surfaces having a bactericidal performance, characterized by containing (d). 5. The solid detergent composition for hard surfaces according to claim 4, wherein the alkali inorganic metal salt is selected from carbonates, silicates and sulfates. 6. Sodium percarbonate or sodium perborate (a)
And 0.5 to 100 parts by weight of a cationic fungicide (b), 0.05 to 100 parts by weight of a metal chelating agent (c), and 10 to 800 parts by weight of an alkali inorganic metal, based on 100 parts by weight of the component (a). Salt (d)
And a solid detergent composition for hard surfaces having a bactericidal performance, comprising 0.5 to 100 parts by weight of a nonionic surfactant (e). 7. The nonionic surfactant is selected from polyoxyethylene alkyl ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester and alkyl polyglycerin ether. The solid cleaning composition for a hard surface according to claim 6. 8. The solid cleaning composition for hard surfaces according to claim 1, wherein the amount of the metal chelating agent (c) is at least 0.5 times the molar amount of the cationic bactericide (b).