JPH1135974A - Bactericide/detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a bactericide/detergent compsn. which has excellent safety to the human body and environmental safety and possesses excellent bactericidal activity against a wide spectrum of pathogenic bacteria by comprising specified quaternary ammonium salt and hinokitiol as bactericidal components. SOLUTION: This bactericide/detergent compsn. comprises, as bactericidal components, 0.1 to 50 wt.% at least one quaternary ammonium salt selected from among dialkyl dimethyl ammonium halides represented by formula I (wherein R<1> and R<2> represent a 6-12C alkyl group or alkenyl group; and X is a halogen), alkyl dimethyl benzyl ammonium halides represented by formula II (wherein R<3> represents an 8-20C alkyl group or alkenyl group; and X is a halogen), and benzyl dimethyl 2-[2-(p-1,1,3,3-tetramethylbutylphenoxy) ethoxy]ethyl} ammonium halides, pref. compds. represented by formula III with the halide component being chlorine, and 0.01 to 5 wt.% hinokitiol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a disinfectant for cleaning used in sanitization in food factories and kitchens, and more particularly, to a neutral system which is safe for the human body and environmentally safe. The present invention relates to a liquid germicidal detergent composition having excellent properties.

[0002]

2. Description of the Related Art Dialkyl quaternary ammonium salts have recently been used as a disinfectant in detergents used in food factories and kitchens. Dialkyl-type quaternary ammonium salts are more widely used than conventional cationic surfactant-type germicides in that they are less susceptible to anionic surfactants, proteins, hard water, etc., and have excellent bactericidal performance. I have. However, such a dialkyl-type quaternary ammonium salt is not versatile, and its antibacterial spectrum is limited. That is, for example, S. For gram-negative bacilli such as marsesens (Serratia marcescens ), satisfactory bactericidal effects cannot be obtained with conventional quaternary ammonium salts alone. In order to solve such problems, a combination of a quaternary ammonium salt, a biguanide compound and a phenol compound (Japanese Patent Application Laid-Open No. 62-132806), and a combination of a dialkyldimethylammonium salt and a biguanide compound (Japanese Patent Application Laid-Open No. 2-184609) ), A combination of a dialkyldimethylammonium salt and a cetyltrimethylammonium salt (Japanese Patent Application Laid-Open No. 2-18 / 1990)
No. 4609), and a disinfectant comprising a combination of a di-linear alkyl di-short-chain alkyl ammonium salt and a zwitterionic surfactant (JP-A-5-65203) has been proposed.

[0003]

However, the above-mentioned biguanide compounds have a bactericidal effect by adsorbing to the cell membrane of bacteria, causing cell membrane damage and cell membrane leakage, etc., and have the same bactericidal effect as quaternary ammonium salts. It depends on the mechanism. Therefore, a bacterium that is resistant to a quaternary ammonium salt will also be a bacterium that is resistant (cross-resistant) to a biguanide compound, and the same problem will occur. Also, the use of a zwitterionic surfactant such as a betaine type may reduce the bactericidal activity of the quaternary ammonium salt due to the ionic interaction of the surfactant in combination with the quaternary ammonium salt. Furthermore, phenolic compounds are erosive to skin and mucous membranes,
Furthermore, there is a problem in safety such as carcinogenicity. In addition, there is a problem that these drugs have a weak effect on fungi.

[0004] That is, the present inventors have solved the above-mentioned problems found in conventional disinfectants, and have excellent safety.
It is an object of the present invention to provide a germicidal detergent composition having an excellent bactericidal effect against a wide range of pathogenic bacteria.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a germicidal detergent comprising a specific quaternary ammonium salt and hinokitiol as bactericidal components. It has been found that the above problems can be effectively achieved by using the composition. The present invention has been completed based on such findings. That is,
The present invention provides a dialkyldimethylammonium halide,
One or more quaternary alkyl halides selected from alkyldimethylbenzylammonium halide and benzyldimethyl [2- (2- (p-1,1,3,3-tetramethylbutylphenoxy) ethoxy) ethyl] ammonium halide
Disclosed is a germicidal detergent composition comprising a quaternary ammonium salt and hinokitiol.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. In the present invention, specific quaternary ammonium salts, that is, dialkyldimethylammonium halide, alkyldimethylbenzylammonium halide and benzyldimethyl [2- (2- (p-1,1,1,2)] are used as bactericidal components.
One or two or more quaternary ammonium salts selected from 3,3-tetramethylbutylphenoxy) ethoxy) ethyl] ammonium halide are used. Examples of the dialkyldimethylammonium halide include those represented by the following formula 1.

[0007]

Embedded image

Wherein R ¹ and R ² each have 6 carbon atoms
Represents a straight-chain or branched-chain alkyl group or alkenyl group, and X represents a halogen atom. In the formula 1, R ¹ and R ² are a linear or branched alkyl group or alkenyl group, respectively, and have 6 to 12, preferably 8 to 10 carbon atoms. Any one having a carbon number outside the above range may be unfavorable due to poor sterilization ability. The sum of the carbon numbers of R ¹ and R ² is 1
It is preferably from 6 to 24, and more preferably from 16 to 20. If the sum is outside the above range, the sterilization ability may be poor. In the present invention, each of R ¹ and R ² is preferably a linear or branched alkyl group.
It is preferably a linear alkyl group such as an octyl group and a decyl group.

The halogen atom represented by X includes a bromine atom, an iodine atom, a chlorine atom and the like, and among them, a bromine atom or a chlorine atom is preferable. Examples of the quaternary ammonium salt represented by the above formula 1 include didecyldimethylammonium chloride, octyldecyldimethylammonium chloride, dioctyldimethylammonium chloride, and in the present invention, didecyldimethylammonium chloride is particularly used. Is preferred. Examples of the alkyldimethylbenzylammonium halide include those represented by the following formula 2.

[0010]

Embedded image

(Wherein R ³ represents a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms;
Represents a halogen atom. In the formula 2, R ³ is a linear or branched alkyl or alkenyl group, and has 8 to 20, preferably 12 to 18 carbon atoms. Any one having a carbon number outside the above range may be unfavorable due to poor sterilization ability.
In the present invention, R ³ is preferably a linear or branched alkyl group, particularly a linear alkyl group,
For example, octyl, decyl and dodecyl groups are preferred. Examples of the halogen atom represented by X include a bromine atom, an iodine atom, and a chlorine atom, and among them, a bromine atom or a chlorine atom is particularly preferable. As the alkyldimethylbenzylammonium halide, benzalkonium chloride represented by the following formula 3 is preferably mentioned.

[0012]

Embedded image

(Wherein, n represents an integer of 8 to 16) In the formula 3, n is an integer of 8 to 16, preferably 10 to 14. Also, benzyl dimethyl [2- (2- (p
Examples of -1,1,3,3-tetramethylbutylphenoxy) ethoxy) ethyl] ammonium halide include those whose halide component is bromine, iodine, chlorine or the like, and particularly those represented by the following formula (4). No.

[0014]

Embedded image

The above quaternary ammonium salt is preferably incorporated in the germicidal detergent composition of the present invention in an amount of 0.1 to 50% by weight, more preferably 2 to 20% by weight. If the compounding amount is less than the above range, a sufficient effect may not be obtained, and even if an amount exceeding the above range is added, no remarkable improvement in the effect is observed for the added amount.

The bactericidal detergent composition of the present invention contains hinokitiol in addition to the above-mentioned quaternary ammonium salt as a bactericidal component. In the present invention, hinokitiol is added as a bactericidal component. Such products include, for example, Taiwan cypress oil, Aomori hiba oil,
Natural crystalline acidic substances separated from Western Red cedar oil or the like, or synthetic substances are used. As the above-mentioned synthetic product, any of those obtained by using various conventionally known methods can be used. The amount of the hinokitiol in the germicidal detergent composition is 0.0
It is preferably from 1 to 5% by weight, more preferably from 0.1 to 3.0% by weight. When the amount is less than the above range, a synergistic effect in the bactericidal effect may not be obtained, and when the amount exceeds the above range, the stability of the composition may be deteriorated and cost is not desirable.

In the germicidal detergent composition of the present invention, a nonionic surfactant is preferably used together with the germicidal components. Nonionic surfactants function as penetrants to enhance cleaning performance and further add wetting performance to the composition;
This facilitates dissolution and solubilization of the germicide. Furthermore, this nonionic surfactant facilitates the solubilization of greasy soils. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, sucrose fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, alkylamine oxide, polyoxyethylene polyoxypropylene polymer, Fatty acid alkanolamides and the like can be mentioned. Among them, in the present invention, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene polymer or fatty acid alkanolamide is preferably used. The above nonionic surfactant is preferably incorporated in the germicidal detergent composition of the present invention in an amount of 0.5 to 50% by weight, more preferably 15 to 35% by weight. If the amount is less than 0.5% by weight, the washing performance or the wetting performance may not be recognized. If the amount exceeds 50% by weight, a remarkable effect is not recognized in proportion to the amount and the cost is reduced. Disadvantageous.

The polyoxyethylene alkyl ether is preferably an ethylene oxide (hereinafter referred to as EO) adduct of an aliphatic alcohol, for example, lauryl alcohol EO (7) or lauryl alcohol EO (9) (provided that the parenthesized parenthesis is used). The numbers represent the number of moles of EO added). Here, examples of the aliphatic alcohol include linear or branched alcohols having 6 to 20, preferably 12 to 18 carbon atoms. The number of moles of EO added is usually 2
To 20 to obtain particularly excellent permeability, 5 to 10 is preferred. When the number of added moles is out of the above range, a sufficient penetration effect may not be obtained. It is preferable that the polyoxyethylene alkyl ether is incorporated in the germicidal detergent composition of the present invention in an amount of 15 to 35% by weight, particularly 20 to 30% by weight. If the amount is less than 15% by weight, a sufficient penetrating effect may not be obtained. Even if an amount exceeding 30% by weight is added, no remarkable effect is observed for the added amount.

Examples of the fatty acid alkanolamides include, for example, coconut oil fatty acid diethanolamide (1: 1).
Lauric acid diethanolamide, lauric acid myristic acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, oleic acid diethanolamide, coconut oil fatty acid diethanolamide (1: 2 type)
And particularly, coconut fatty acid diethanolamide,
Lauric diethanolamide is preferred. The above fatty acid alkanolamide is present in the germicidal detergent composition of the present invention in an amount of 0.
It is preferable that 5 to 10% by weight, especially 2.5 to 7.5% by weight be blended. If the amount is less than 0.5% by weight, a sufficient cleaning effect may not be obtained, and if it exceeds 10% by weight, the stability of the sterilizing detergent composition may be deteriorated. In the present invention, the above nonionic surfactants can be used alone or in combination of two or more.

It is preferable that the germicidal detergent composition of the present invention further contains a chelating agent. The chelating agent has the effect of sequestering metal ions in the cleaning solution, thereby enhancing the detergency of the surfactant and at the same time preventing the removal and reattachment of dirt. Such chelating agents include ethylenediaminetetraacetic acid, citric acid,
Organic acids selected from gluconic acid, succinic acid, malic acid, fumaric acid and tartaric acid, acrylic acid polymers, copolymers of acrylic acid and maleic acid, and salts selected from these salts. Examples of the above salts include alkali metal salts such as sodium salts and potassium salts, amine salts, ammonium salts and the like. In the present invention, ethylenediaminetetraacetate or citrate is preferably used as the chelating agent, particularly from the viewpoint of antibacterial properties.
In particular, disodium ethylenediaminetetraacetate is preferably used. Further, as a polymer or copolymer of acrylic acid and maleic acid, for example, a molecular weight of 1,000
A polyacrylic acid polymer having a molecular weight of 0 to 100,000, preferably 6,000 to 30,000 is used, and a copolymer has a molecular weight of 10,000 to 150,000, preferably 30,000 to
A copolymer of 100,000 acrylic acid and maleic acid is used.

The compounding amount of the above chelating agent in the germicidal detergent composition of the present invention is preferably in the range of 0.1 to 5% by weight, more preferably 1 to 3% by weight. The above amount is 0.1
When the amount is less than 5% by weight, a synergistic effect in the cleaning effect may not be recognized. On the other hand, when the amount is more than 5% by weight, the stability of the sterilizing cleaning solution is deteriorated, and the sufficient cleaning effect may not be exhibited. In the present invention, the above chelating agents can be used alone or in combination of two or more.

The germicidal detergent composition of the present invention may further contain a solubilizing agent in addition to the germicidal components and, if necessary, a nonionic surfactant and a chelating agent. Solubilizers are used not only to solubilize the bactericide and maintain the stability of the composition, but also as a cleaning component, especially for oily soils. As such a solubilizing agent, those usually used in detergent compositions can be used, and preferably, alcohols such as ethanol and glycols such as propylene glycol are used. It is preferable that the solubilizer is incorporated in the germicidal detergent composition of the present invention in an amount of 2 to 35% by weight, more preferably 4 to 30% by weight. When the amount is less than 2% by weight, the above effects may not be sufficiently obtained, and when the amount exceeds 35% by weight, it is not desirable in terms of cost. In the present invention, the solubilizing agent can be used alone,
Two or more kinds can be used in combination.

The germicidal detergent composition of the present invention may further contain a thickener, a fragrance, a coloring agent, and the like, if necessary, in addition to the above components, as long as the object of the present invention is not impaired. . Thickener is intended to be compounded for the purpose of imparting a certain viscosity according to the application to the sterilizing detergent composition,
For example, when cleaning cooking utensils, dishes, and the like, the cleaning composition is usually used directly for a sponge or the like,
In order to adapt to such a case, a certain degree of viscosity is imparted to the germicidal detergent composition. As such a thickener, for example, carboxymethylcellulose (CM
C), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), xanthan gum, guar gum and the like can be used. Sulfates, amphoteric surfactants, sodium chloride and the like can be used as viscosity modifiers. The viscosity characteristics of the thickener may be affected by the coexistence of metal ions in tap water at the time of use, and in view of this, when a thickener is used, it is preferable to use the above-mentioned chelating agent together.

In consideration of the above points, the amounts of the thickener and the viscosity modifier are appropriately determined depending on the use conditions.
Suitably, it is in the range of 1-0.5% by weight. As the fragrance and the coloring agent, any of those generally used in a germicidal detergent composition or the like can be used according to the purpose. The mixing amount is not particularly limited,
From the viewpoints of smell transfer and color transfer to a cutting board and the like, it is appropriate that each of them is usually added in an amount of 0.2% by weight or less in the germicidal detergent composition. The germicidal detergent composition of the present invention,
In order to suppress the adverse effects on cooking utensils and cutting boards, pH
Is preferably in a neutral region, for example, a pH region of 6.0 to 8.0. The amount of the germicidal detergent composition of the present invention can be appropriately determined according to the purpose of use, or can be appropriately diluted before use. When diluted and used, for example, it is appropriate to dilute with tap water 10- to 500-fold and use as a quaternary ammonium salt concentration in the range of 50 to 1000 mg / L.

[0025]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 56 and Comparative Examples 1 to 10 Disinfectant detergent compositions as shown in Table 1 were prepared, and each was subjected to an antibacterial activity test, a detergency test, and a permeability test by the following methods to evaluate its properties. did. The results are shown in Table 1.

<Antibacterial activity test> The antibacterial activity was evaluated by measuring the minimum inhibitory concentration (MIC) determined by the Japanese Society of Chemotherapy. That is, a bacterial solution diluted so that the number of bacteria becomes 10 ⁶ CFU / milliliter was inoculated on a drug-mixed agar plate, and cultured at 37 ° C. for 18 to 24 hours for bacteria and at 27 ° C. for fungi for 5 days for fungi. Thereafter, the maximum dilution ratio (antibacterial activity) of the sterilizing detergent in which the growth of the test bacteria was inhibited was measured. That is, it is determined that the higher the dilution ratio, the better the antibacterial performance. The strains were Escherichia coli IFO-12734 Pseudomonas aeruginosa IFO-13275 Aspergillus niger IFO-9455 Candida albicans IFO-1594 from the Fermentation Research Institute, and Serratia marcescens isolated and identified at a food factory.
Was used.

<Detergency Test> The detergency of an artificially soiled plate contaminated with oils was evaluated using a detergency tester according to the following procedure and method. The washing efficiency (removal rate) was calculated from the measured value and the weight of the artificial soil plate before washing according to the following equation. Washing efficiency (%) = [(weight of artificial stain plate before washing (g)
-Weight (g) of artificial soil plate after washing) / (weight of glass plate after soil coating (g)-weight of glass plate before soil coating (g))] x 100 Preparation 10 g of tallow, 10 g of soybean oil, 0.25 g of monoolein and 0.1 g of oil red were dissolved in 60 ml of chloroform, and a glass plate was immersed in this solution to form a film having a uniform thickness on the glass plate. , Take out the glass plate 25
Chloroform was volatilized at a temperature of 1 ° C. for 1 hour to 2 hours to prepare an artificially soiled plate. Evaluation of Detergency The detergency was evaluated by a stirring method using a detergency test apparatus according to JIS K3370, a method for evaluating the detergency of a synthetic detergent for kitchen, according to the method for improving the leanuts. That is, after washing the artificial stain plate in each sterilizing detergent sample solution adjusted to 30 ° C. and 0.1% for 3 minutes, the artificial stain plate is taken out, washed with tap water for 1 minute, rinsed, and ventilated. After drying to sufficiently evaporate water, the weight was measured with an analytical balance. The washing efficiency (removal rate) was calculated from the measured value and the weight of the artificial soil plate before washing. In addition, each sample solution was prepared using tap water.

<Permeability Test> The felt cut into 2 cm × 2 cm is dried in a dryer adjusted to 100 ° C. for 2 hours or more, and further cooled in a desiccator for 1 hour or more. Prepare 100% of the test sterilizing detergent at 100% and keep at 25 ° C. A piece of felt is placed at the center of the liquid surface of the test sterilizing detergent with tweezers, and the time (sec) until the sterilizing cleaning solution permeates the entire felt piece is measured, which is defined as the permeation time. The smaller the number, the better the permeability.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

[0037]

[Table 9]

[0038]

[Table 10]

[0039]

[Table 11]

* Acrylic acid polymer; Sokaran PA-40P (BAS
F: molecular weight 14,000) * Acrylic acid / maleic acid copolymer; Sokalan CP-5P (BAS
F: molecular weight 70,000) * Ethanol / propylene glycol ratio 1: 1 * Polyoxyethylene alkyl ether A; C12, C14-E
O Number of moles added 7 (Nonipol Soft SS-70: manufactured by Sanyo Chemical Industries) * Polyoxyethylene alkyl ether B; C12, C14-E
O Number of added moles 9 (Nonipol Soft SS-90: manufactured by Sanyo Chemical Industries) * Polyoxyethylene alkyl phenyl ether; C12
Phenyl-EO addition mole number 10 (Nonipol 100: manufactured by Sanyo Chemical Industries) * Polyoxyethylene polyoxypropylene polymer; Pluronic L-31 (manufactured by Asahi Denka Kogyo: molecular weight 2,200)

[0041]

As described above, the germicidal detergent composition of the present invention uses a specific quaternary ammonium salt and hinokitiol as essential bactericidal components, and is capable of reducing the quaternary ammonium salt against both gram-negative bacteria and fungi. A remarkably excellent bactericidal effect can be obtained that cannot be predicted from the case where hinokitiol is used alone. Further, the composition of the present invention can be sterilized and washed at the same time, so that it is very effective for sanitation in food factories and kitchens. Furthermore, since the sterilizing detergent composition of the present invention is neutral, it does not damage materials such as cooking utensils, and the components of this composition have high toxicity because they have almost no toxicity. is there. It is therefore particularly useful in situations where the use of chemical germicides has been ruled out due to the danger of food factories, kitchens or other toxic residues.

Claims (14)

[Claims] 1. A dialkyldimethylammonium halide, an alkyldimethylbenzylammonium halide and benzyldimethyl [2- (2- (p-1,1,3,3
-Tetramethylbutylphenoxy) ethoxy) ethyl
A germicidal detergent composition comprising one or more quaternary ammonium salts selected from ammonium halides and hinokitiol. 2. The germicidal detergent composition according to claim 1, wherein the quaternary ammonium salt is a dialkyldimethylammonium halide represented by the following formula 1. Embedded image (In the formula, R ¹ and R ² each represent a linear or branched alkyl or alkenyl group having 6 to 12 carbon atoms, and X represents a halogen atom.) 3. The germicidal detergent composition according to claim 2, wherein the total number of carbon atoms of R ¹ and R ² in Formula 1 is 16 to 24. 4. The germicidal cleaning composition according to claim 2, wherein in the formula 1, X is chlorine, bromine or iodine. 5. The germicidal detergent composition according to claim 1, wherein the quaternary ammonium salt is an alkyldimethylbenzylammonium halide represented by the following formula 2. Embedded image (In the formula, R ³ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and X represents a halogen atom.) 6. The germicidal cleaning composition according to claim 5, wherein in the formula 2, X is chlorine, bromine or iodine. 7. The germicidal detergent composition according to claim 1, wherein the quaternary ammonium salt is benzalkonium chloride represented by the following formula 3: Embedded image (Where n represents an integer of 8 to 16) 8. A quaternary ammonium salt comprising a benzyl dimethyl [2- (2- (p-1,1,1,
3. The germicidal detergent composition according to claim 1, which is 3,3-tetramethylbutylphenoxy) ethoxy) ethyl] ammonium chloride. Embedded image 9. The composition according to claim 1, further comprising a chelating agent.
8. The germicidal detergent composition according to any one of 8. 10. The chelating agent is ethylenediaminetetraacetic acid, citric acid, gluconic acid, succinic acid, malic acid,
The germicidal detergent composition according to claim 9, which is selected from an organic acid selected from fumaric acid and tartaric acid, an acrylic acid polymer, a copolymer of acrylic acid and maleic acid, and salts thereof. 11. The germicidal detergent composition according to claim 1, further comprising a nonionic surfactant. 12. The nonionic surfactant is one or more selected from polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polyoxypropylene polymer and fatty acid alkanolamide. A germicidal detergent composition according to the above. 13. The method according to claim 1, further comprising a solubilizing agent.
A germicidal detergent composition according to any one of 12 above. 14. The germicidal detergent composition according to claim 13, wherein the solubilizing agent is selected from alcohols and glycols.