JPH1135994A - Solid detergent composition for hard surface use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a detergent excellent in the long-term storage stability in the form of powder and capable of preventing the concentration of its aqueous solution from being reduced after preparation of the solution and of preventing the cationic germicide from being degraded by blending solium percarbonate or sodium perborate, a cationic germicide and a glycine-N, Ndiacetate salt in specific proportions. SOLUTION: In 100 pts.wt. of sodium percarbonate or sodium perborate (A), are incorporated 0.5-100 pts.wt. of a cationic germicide (B) and 0.05-100 pts.wt. of a glycine-N,N-diacetate salt (C) represented by the formula wherein M is H, Na, K or NH4 and R is a 1-18C alkyl). The component B may include cationic surfactant-base germicides, biguanide-base germicides and amino acid- base surfactants. In addition, the composition may preferably contain an alkaline inorganic metal salt (D) and further a surfactant, particularly a nonionic surfactant (E). Usually, 10-800 pts.wt. of component D and 0.5-100 pts.wt. of component E are blended based on 100 pts.wt. of component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a bactericide suitable for hard surfaces such as plastics, metals, glass and tiles using glycine-N, N-diacetate which is a metal chelating agent having good biodegradability. An object of the present invention is to provide a solid detergent composition having performance. 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. Cleaning agents and pre-cleaning agents for medical instruments (before sterilization) such as endoscopes, catheters, syringes, etc., which can be expected to prevent hospital-acquired infections by sterilizing detergents and sterilizing with one agent at the time of washing. Suitable as. In addition, since it has a deodorant property by sterilization, it can be used as a deodorant for cleaning pits, pipes, and the like. In addition, the kitchen,
It is suitable as a floor sanitizer for places where it is necessary to control the number of bacteria in the environment, such as toilets and hospital facilities. Also,
As a method of using the composition of the present invention, the composition may be used by dissolving it 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 bactericides are excellent in bactericidal properties and bactericidal quick-acting properties, but have little washing performance and bleaching ability, and cannot be used alone as a bactericidal detergent.

[0004] In view of 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 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 imparting the cleaning action. 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 in that the performance of each of the agents that can simultaneously perform sterilization and washing is deteriorated if they are combined into one agent.

[0005]

The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, mixed solid sodium percarbonate or sodium perborate with a solid cationic fungicide. In addition, the combined use of solid glycine-N, N-diacetate enables long-term storage stability in powder form, furthermore, prevention of a decrease in concentration after preparation of an aqueous solution and prevention of decomposition of a cationic fungicide. It turns out.

That is, the present invention relates to sodium percarbonate or sodium perborate (a) and 100 parts by weight of the component (a),
~ 100 parts by weight of cationic fungicide (b) and 0.05-100
The present invention provides a solid detergent composition for hard surfaces having a bactericidal performance, characterized by containing parts by weight of glycine-N, N-diacetate (c) represented by the following general formula (I). is there.

[0007]

Embedded image

[Wherein M represents H or Na, K, NH ₄ ,
R is an alkyl group having 1 to 18 carbon atoms. As the cationic bactericide of the component (b), benzethonium chloride and benzalkonium chloride (alkyl group having 8 to 1 carbon atoms)
8), dialkyl (C ₈ -C ₁₈₎ dimethyl ammonium halide, monoalkyl (C ₈ -C ₁₈₎ sterilization of trimethylammonium halide or cationic surfactant system wherein the counterion is converted into another anion of these fungicides And biguanide bactericides such as chlorhexidine and chlorohexidine gluconate; amino acid surfactants such as alkyl (C ₈ -C ₁₈ ) diaminoethyl glycine and dialkyl (C ₈ -C ₁₈ ) aminoethyl glycine.

The metal chelating agent is not particularly limited as long as it has the ability to chelate metal ions, but in recent years, from the viewpoint of impact on the environment,
The need for a metal chelating agent that does not contain phosphorus, has good biodegradability, and has excellent sequestering ability is increasing every day, and it is inevitable to cope with it.

For example, phosphate-type chelating agents such as phosphonates and tripolyphosphoric acids are effective but contain phosphorus, and also include ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, Aminoacetate chelating agents such as ethylenetetraminehexaacetic acid are also highly effective, but have poor biodegradability. On the other hand, gluconic acid, citric acid,
Oxycarboxylic acid-based compounds such as succinic acid and polyacrylic acid-based compounds do not contain phosphorus and have little problem of biodegradability, but are inferior in effect and need to be added in a large amount.

As described above, a metal chelating agent which does not contain phosphorus, has good biodegradability, and has excellent sequestering ability has been demanded. From this viewpoint, in the present invention, the following formula (I) is used. Glycine-N, N-diacetate is used.

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 (c) the glycine-N, N-diacetate metal chelating agent is added in an amount of 0.5 mol or more with respect to the cationic fungicide (b). In particular, 0.5 to 5 times mol,
Further, the amount is preferably 0.5 to 2 times, particularly preferably 1 to 2 times.

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, instead of the solid cationic fungicide and the solid glycine-N, N-diacetate (c),
Each can be used in the form of an aqueous solution. In other words, an alkali inorganic metal salt is first supported with an aqueous solution of a cationic bactericide, glycine-N, N-diacetate type metal chelating agent, and then or after heating and drying, mixed with sodium percarbonate or sodium perborate to form a formulation. By doing so, the solid detergent composition of the present invention 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 cleaning composition for hard surfaces of the present invention having a bactericidal performance can be prepared by mixing and stirring water-containing solids (including aqueous solutions) when each component 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.

[0018]

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

Examples 1-5 and Comparative Examples 1-2 Cleaning compositions were prepared from the components shown in Tables 1-2. 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, the retention rate of the cationic bactericide and the effective oxygen concentration after 10 hours was calculated, taking the value immediately after the dilution as 100. The results are shown in Tables 1 and 2. The concentration of the cationic bactericide was determined by HPLC (manufactured by Hitachi, Ltd.).
Using L-7100), the effective oxygen concentration is JIS-K 3362 (5.9
Section).

[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 Tables 1 and 2.

<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 Tables 1 and 2.

<1-4; Starch Dirt Washing Test> A model glass dirt piece 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 Tables 1 and 2.

[2] Evaluation of bactericidal activity The bactericidal activity was evaluated by 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. The obtained results are shown in Tables 1 and 2.

[0024]

[Table 1]

[0025]

[Table 2]

(Note) * 1: When the alkyl composition is 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 a bactericidal performance shown in Table 3 was prepared, and a storage stability test in solid state (40 ° C. × 85%, 3 months) was performed. Table 3 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.

[0027]

[Table 3]

(Note) * 1: When the alkyl composition is lauryl / myristyl = 2/1
(Molar ratio). * 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 7:32)

Claims (6)

[Claims] 1. Sodium percarbonate or sodium perborate (a)
And 0.5 to 100 parts by weight of the cationic fungicide (b) and 0.05 to 100 parts by weight of glycine-N, N- represented by the following general formula (I) based on 100 parts by weight of the component (a). A solid detergent composition for hard surfaces having a bactericidal performance, comprising a diacetate (c). Embedded image [Wherein, M represents H or Na, K, NH ₄ , and R represents 1 carbon atom.
~ 18 alkyl groups. ] 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. Sodium percarbonate or sodium perborate (a)
And 0.5 to 100 parts by weight of the cationic fungicide (b), and 0.05 to 100 parts by weight of glycine-N, N- represented by the following general formula (I) based on 100 parts by weight of the component (a). Diacetate (c) and 10
A solid detergent composition for hard surfaces having a bactericidal performance, comprising -800 parts by weight of an alkali inorganic metal salt (d). Embedded image [Wherein, M represents H or Na, K, NH ₄ , and R represents 1 carbon atom.
~ 18 alkyl groups. ] 4. The solid detergent composition for hard surfaces according to claim 3, wherein the alkali inorganic metal salt (d) is selected from carbonates, silicates and sulfates. 5. Sodium percarbonate or sodium perborate (a)
And 0.5 to 100 parts by weight of the cationic fungicide (b), and 0.05 to 100 parts by weight of glycine-N, N- represented by the following general formula (I) based on 100 parts by weight of the component (a). Diacetate (c), 10-
A solid cleaning composition for hard surfaces having a bactericidal performance, comprising 800 parts by weight of an alkali inorganic metal salt (d) and 0.5 to 100 parts by weight of a nonionic surfactant (e). Embedded image [Wherein, M represents H or Na, K, NH ₄ , and R represents 1 carbon atom.
~ 18 alkyl groups. ] 6. The nonionic surfactant (e) is selected from the group consisting of polyoxyethylene alkyl ether ether, polyoxyethylene alkylene ether, polyoxyethylene sorbitan fatty acid ester, alkyl polyglycoside, sucrose fatty acid ester and alkyl polyglycerin ether. The solid detergent composition for hard surfaces according to claim 5, which is selected.