KR19990084946A - Sterilization composition containing quaternary ammonium phosphate and glutaraldehyde - Google Patents

Abstract

The bactericidal composition comprising the quaternary ammonium phosphate compound represented by the formula (1) and glutaraldehyde can effectively control a wide range of microorganisms, has a broad instantaneous bactericidal power and a microbial spectrum, has excellent anticorrosive properties, and shows synergistic effects. Even if a small amount is used, it shows a high effect, and even in the presence of a biofilm, the microbial removal efficiency is excellent, and since each compound has a different mechanism of killing microorganisms, it is possible to obtain the expected effect of lowering the frequency of occurrence of resistant strains than when used alone. have.

[Formula 1]

In Formula 1, R ₁ may include a hetero atom as a linear or pulverized alkyl group or aryl group having 1-27 carbon atoms which does not include a hydroxyl group, and R ₂ and R ₃ may be the same as a methyl group, or R ₂ and R ₃ is a heterocyclic structure having 4 to 6 carbon atoms containing oxygen and nitrogen formed by bonding to each other, and R ₄ is a linear or crushed alkyl or aryl group having 1-27 carbon atoms including a hetero atom or a benzyl group.

Description

Bactericidal Compositions Containing Quaternary Ammonium Phosphate and Glutaraldehyde

[Industrial use]

The present invention relates to a disinfectant composition comprising quaternary ammonium phosphate and glutaraldehyde, and more particularly, can be used as a disinfectant for disinfection in various industries and homes, such as pulp and paper mills and cooling towers. A bactericidal composition comprising quaternary ammonium phosphate of formula 1 and glutaraldehyde.

[Formula 1]

In Formula 1, R ₁ may include a hetero atom as a linear or pulverized alkyl group or aryl group having 1-27 carbon atoms which does not include a hydroxyl group, and R ₂ and R ₃ may be the same as a methyl group, or R ₂ and R ₃ is a heterocyclic structure having 4 to 6 carbon atoms containing oxygen and nitrogen formed by bonding to each other, and R ₄ is a linear or crushed alkyl or aryl group having 1-27 carbon atoms including a hetero atom or a benzyl group.

[Prior art]

In general, industrial water has a large amount of organic matter, and thus, a lot of water is collected, such as cooling water equipment, and microbial growth such as algae, bacteria, and mold occurs easily in a recycled place, and thus fouling occurs. Degradation of heat transfer efficiency and corrosion of metals in cooling water facilities is caused, and sometimes the erosion of wood can occur.

Among these microorganisms, algae are eukaryotes, and they consume nutrients by photosynthesis even under light, air, and small amounts of minerals. Therefore, algae multiply in sun-exposed areas such as cooling water facilities or swimming pools, which causes algal fouling. Rises, causing clogging of the water pipe, lowering the heat transfer efficiency, proliferating on the metal surface to generate oxygen, and upon death, promoting local corrosion through local cell action. In addition, carbohydrates produced by algae can be used as a nutrient for other microorganisms such as bacteria and fungi, which can cause fouling.

Bacteria are multicellular prokaryotes that can multiply by breaking down various types of organic matter, and some of them secrete polysaccharides to the outside, which leads to the formation of biofilms, which cause microbiologically induced corrosion. do.

Fungi are eukaryotic organisms that can proliferate and decompose various types of organic matter, similar to bacteria, and the cells that secrete cellulase cause discoloration and decay of wood by decomposing and proliferating wood fiber such as cooling towers. do.

Therefore, various types of fungicides added to industrial water are aimed at killing microorganisms causing fouling or preventing growth and surface adhesion of metals and the like, and are generally classified into oxidizing fungicides and non-oxidizing fungicides.

Halogenous compounds such as chlorine and bromine are mainly used as oxidizing fungicides, which are widely used in terms of oxidizing power and economics, but have a great effect on cooling tower wood erosion and metal corrosion, and are easily released into the atmosphere. In particular, in a state in which biofilms are formed, they react with polysaccharides secreted before they react with microorganisms, thereby reducing the effective bactericidal effect.

Non-oxidizing fungicides include 3-isothiazolone, quaternary ammonium compound, formaldehyde releasing compound, glutaraldehyde and the like. Among them, glutaraldehyde is described in US Pat. Nos. 4,376,094, 5,322,856, 4,539,071, and the like. Patents relating to synergistic effects of glutaraldehyde and benzisothiazolone are disclosed in US Pat. No. 5,004,749 and glutaraldehyde. Patents for synergistic effects with thiocyanomethylthiobenzthiazole (TCMTB) are described in US Pat. No. 5,198,453, respectively.

In addition, U.S. Patent No. 3,282,775 describes the improvement of sporicidal function by combining glutaraldehyde and quaternary ammonium chloride in order to increase sterilization power and give fast-acting effect, and U.S. Patent No. 4,107,312 and Europe Patent No. 0,217,339 describes the combination of glutaraldehyde and quaternary ammonium chlorides for use in the disinfectant for toilet and for the disinfection of algae, respectively.

However, since the quaternary ammonium chloride emits a halogen compound such as chlorine, which is a corrosive substance, it has a disadvantage in that it is difficult to apply to a place containing corrosive metal materials such as carbon steel, cast iron, stain steel, and copper, and in the case of glutaraldehyde Aspergillus niger, Cryptococcus spp. It has the disadvantage of poor sterilization power against mold.

Therefore, in order to overcome the above-mentioned shortcomings of the quaternary ammonium chlorides, researches on disinfectants which can be applied to a place containing a corrosive metal material without releasing a halogen compound have been conducted. Among them, quaternary ammonium phosphate is disclosed in Korean Patent Application No. 97 -46517. Quaternary ammonium phosphate removes chlorides from known quaternary ammonium compounds and replaces phosphate (H ₃ PO ₄ ) to be applied without corrosion problems to corrosive metals including carbon steel, cast iron, stainless steel and copper. It is a substance that has antiseptic power, detergency and anticorrosive property. Since quaternary ammonium phosphate is a novel material with high instantaneous sterilization and excellent anticorrosive property, it can be used in places where microorganism control is needed, especially in corrosive materials, equipment and devices, but in the presence of biofilm, the removal efficiency is reduced. have.

The present invention is to solve the problems of the prior art as described above, the object of the present invention does not emit a corrosive material such as a halogen compound, it is applied to a place containing a corrosive metal material such as carbon steel, cast iron, stainless steel, copper It is possible to provide a bactericidal composition which is effective in controlling a wide range of microorganisms and having excellent microbial removal efficiency even in the presence of a biofilm.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a sterilizing composition comprising a quaternary ammonium phosphate compound represented by the following formula (1) and glutaraldehyde.

[Formula 1]

In Formula 1, R ₁ may include a hetero atom as a linear or pulverized alkyl group or aryl group having 1-27 carbon atoms which does not include a hydroxyl group, and R ₂ and R ₃ may be the same as a methyl group, or R ₂ and R ₃ is a heterocyclic structure having 4 to 6 carbon atoms containing oxygen and nitrogen formed by bonding to each other, and R ₄ is a linear or crushed alkyl or aryl group having 1-27 carbon atoms including a hetero atom or a benzyl group.

Hereinafter, the present invention will be described in detail.

The disinfectant composition comprising the quaternary ammonium phosphate compound and glutaraldehyde compound of the present invention is mainly applied to various industrial fields such as pulp and paper mills, cooling towers and disinfectants, and can be used for effective and extensive control of microorganisms. This is to overcome the disadvantages of using a quaternary ammonium phosphate compound and a glutaraldehyde compound, respectively. Since the fungicide composition of the present invention is mainly used in industrial water, it is preferable to be water-soluble, and both quaternary ammonium phosphate compounds and glutaraldehyde satisfy this condition.

The quaternary ammonium phosphate compound is represented by the following Chemical Formula 1, and does not emit halogen compounds such as chlorine, and thus can be applied to corrosion-resistant metals including carbon steel, cast iron, stainless steel, copper, etc. without corrosion problems. Although the material has both the cleaning power and the anticorrosion at the same time, there is a disadvantage that the removal efficiency is reduced in the presence of a biofilm.

[Formula 1]

In Formula 1, R ₁ may include a hetero atom as a linear or pulverized alkyl group or aryl group having 1-27 carbon atoms which does not include a hydroxyl group, and R ₂ and R ₃ may be the same as a methyl group, or R ₂ and R ₃ is a heterocyclic structure having 4 to 6 carbon atoms containing oxygen and nitrogen formed by bonding to each other, and R ₄ is a linear or crushed alkyl or aryl group having 1-27 carbon atoms including a hetero atom or a benzyl group.

In Formula 1, R ₁ , R ₂ , R ₃ and R ₄ are the same as defined above, but R ₁ is a para- (α, α, γ, γ) -tetramethyl butyl phenoxy ethoxy ethyl group, and R ₂ and Particularly preferred are compounds in which R ₃ is a methyl group and R ₁ is a tetradecyl group, and R ₂ and R ₃ are morpholinium groups, wherein R ₄ is a carbon atom containing a hetero atom or a benzyl group. Linear or pulverized alkyl group or aryl group.

Glutaraldehyde compounds are generally used as a non-oxidizing fungicide, but has a disadvantage in that the bactericidal effect against fungi and some bacteria is inferior.

Thus, quaternary ammonium phosphate compounds generally provide anticorrosive effects, while glutaraldehyde has a poor bactericidal effect against some bacteria and fungi, and in the case of instantaneous bactericidal power and biofilms, glutaraldehyde is used for quaternary ammonium phosphate compounds. Replenish the role.

In addition, the preservative composition of the present invention can not only overcome the disadvantages of using each compound, but also shows a synergistic effect that is greater than the sum of the respective bactericidal action when used in combination. The mixing ratio of the quaternary ammonium phosphate compound and glutaraldehyde is preferably 20: 1 to 1:30 by weight, more preferably 1: 4 to 1:20. If the mixing ratio of the quaternary ammonium phosphate compound and glutaraldehyde is less than 20: 1 or exceeds 1:30, no synergy between the two fungicides is observed.

In addition, the bactericidal composition of the present invention can suppress microorganisms more effectively and broadly by using two kinds of compounds having different sterilization mechanisms, and can obtain an expected effect of lowering the frequency of resistant strains when used alone. .

EXAMPLE

The following presents preferred examples and comparative examples to aid in understanding the invention. However, the following examples are merely provided to more easily understand the present invention, and the present invention is not limited to the following examples.

Example 1

In order to test the synergy of quaternary ammonium phosphate and glutaraldehyde, the microbial inhibitory effect was tested using a microbial mixture and benzyl ammonium phosphate and glutaraldehyde.

The microorganisms were Enterobacter aerogenes ATCC 13048, Escherichia coli ATCC 11229, Micrococcus luteus ATCC 9341, Pseudomonas aeruginosa ATCC 15442, Klebsiella pneumoniae ATCC 1560, Staphylococcus epidermis ATCC 155, Staphylococcus aureus ATCC 6538, Bacillus 6 al subs. Eight types of mixed microorganisms of Rhodotorula rubra ATCC 9449, Cryptococcus neoformans ATCC 34144, Saccharomyces cerevisiae ATCC 9763, Penicillium citrinum ATCC 9849, Trichoderma viridae ATCC 6047, Rhizopus oryzae ATCC 10404, and Aspergillus niger ATCC 9642 were used.

In the formula (1), each of R ₁ is a linear alkyl group having 12-14 carbon atoms, R ₂ and R ₃ are methyl groups, and R ₄ is a benzyl group. Diluted according to the two fold dilution method) to prepare a wide concentration range, these were mixed in various ratios were used as a fungicide mixture. Phosphate buffer containing microbicides and microorganisms was incubated at 30 ° C. for 3 days, and then reinoculated into Tryptic Soy Broth of Difco, and then visually determined by microorganism growth based on turbidity. Minimum Inhibitory Concentration (MIC) of fungicides or mixtures thereof was determined.

Such a method is generally modified in a method of measuring turbidity by culturing in a nutrient medium, when glutaraldehyde is directly tested in a general nutrient medium due to the nature of glutaraldehyde, amine of amino acids in the components of the nutrient medium Since it is difficult to measure the correct sterilization by reacting with the microorganisms, the first experiment was to minimize the experimental error caused by the nutrient medium by measuring the turbidity by reacting the fungicide and the microorganism in the phosphate buffer first and then inoculating it into the nutrient medium.

The synergy of fungicides is Kull. According to the method published in FC et al. (Appl. Microbiol. 9, 538-544 (1961)), it was measured using the ratio measured by Equation 1 below, and the sum of QA / Qa and QB / Qb was If it is less than 1, it was judged that synergism appeared.

[Equation 1]

Synergy index (SI) = (QA / Qa) + (QB / Qb)

Qa: minimum growth inhibition concentration (ppm) of Compound A alone

Qb: minimum growth inhibition concentration (ppm) of Compound B alone

QA: minimum growth inhibition concentration (ppm) of compound A in the mixture

QB: minimum growth inhibition concentration (ppm) of compound B in the mixture

The results for an example of synergy of the fungicide mixture are shown in Table 1.

Synergy Results of Fungicide Mixtures Qa ^* Qb ^* QA ^* QB ^* QA / Qa QB / Qb SI 1250 156 625 39 0.50 0.25 0.75 1250 156 313 78 0.25 0.50 0.75 1250 156 313 15 0.25 0.10 0.35

^* Qa: minimum growth inhibition concentration (ppm) of glutaraldehyde alone at a concentration of 50% by weight of the mixed strain

Qb: Minimum growth inhibition concentration (ppm) of quaternary ammonium phosphate alone at 50% by weight concentration for mixed strains

QA: Minimum growth inhibition concentration (ppm) of glutaraldehyde at a concentration of 50% by weight in a mixture

QB: Minimum growth inhibitory concentration (ppm) of quaternary ammonium phosphate at a concentration of 50% by weight in a mixture

From the results shown in Table 1, when the ratio of 50% by weight quaternary ammonium phosphate and 50% by weight glutaraldehyde is 39: 625, 78: 313, 15: 313, that is, about 1:16, 1: 4, 1 It is found that the synergistic ratio of 50% by weight quaternary ammonium phosphate and 50% by weight glutaraldehyde is most preferable in the range of 1: 4-1: 20 since the index of rise is 0.35-0.75 when: 21. Can be.

Example 2

Using the synergistic ratio obtained in Example 1, a solution containing 50% by weight of glutaraldehyde component and benzyl ammonium phosphate having a linear alkyl structure of 12-14 carbon atoms used in Example 1 were 9: 1 and 5, respectively. The minimum growth inhibitory concentrations of 12 individual strains of the fungicide mixture 1 and the fungicide mixture 2 mixed at 1: 1 were measured.

The minimum growth inhibition concentration was diluted by two-fold serial dilution using a 96 multi-well plate, inoculated with microorganisms at a concentration of 10 ⁴ CFU / mL, and then cultured at 30 ° C. for 48 hours for turbidity. It measured by the method of visual inspection as a reference | standard. The medium was initially reacted in phosphate buffer as in Example 1, and turbidity was observed using Tryptic Soy Broth (Difco), and the strains used were bacteria 7 as shown in Table 2 of the strains used in Example 1. Species and five fungi were used. The experimental results are shown in Table 2.

Comparative Example 1

The experiment was carried out in the same manner as in Example 2, except that a solution containing 50% by weight glutaraldehyde instead of a mixture of glutaraldehyde and benzyl ammonium phosphate was used as a bactericide. The experimental results are shown in Table 2.

Result of minimum growth inhibition concentration experiment of Example 2 and Comparative Example 1 Use strain Fungicide Mixture 1 ^* Fungicide mixture 2 ^* 50% by weight glutaraldehyde Enterobacter aerogenes ATTC 13048 40 40 40 Escherichia coli ATCC 11229 40 40 40 Micrococcus luteus ATCC 9341 20 40 40 Pseudomonas aeruginosa ATCC 15442 40 40 313 Bacillus subtilis ATCC 6984 20 20 20 Staphylococcus epidermis ATCC 155 20 20 20 Staphylococcus aureus ATCC 6538 40 40 40 Candida albicans ATCC 10231 80 20 40 Rhodotorula rubra ATCC 9449 40 40 80 Cryptococcus neoformans ATCC 34144 40 20 156 Penicillium citrinum ATCC 9849 40 20 80 Aspergillus neiger ATCC 9642 80 80 313

^* Sterilizer Mixture 1: A sterilizer mixture of 50 wt% glutaraldehyde and 50 wt% quaternary ammonium phosphate compound in Example 2

Sterilizer Mixture 2: A sterilizer mixture of 50% by weight glutaraldehyde and 50% by weight quaternary ammonium phosphate compound in 5: 2

From the results shown in Table 2, the fungicide of Example 2 in which 50% by weight of quaternary ammonium phosphate and 50% by weight of glutaraldehyde were mixed using an elevated index than in the case of Comparative Example 1 using 50% by weight of glutaraldehyde alone It was found that the mixture was much more effective at controlling a wide range of microorganisms.

Example 3

The killing time for killing the microorganisms of the fungicide mixture used in Example 2 was measured. The microbial concentration of the 12 kinds of microbial mixtures used in Example 2 was adjusted to 10 ⁴ -10 ⁵ CFU / ml, and the solution was turbid in the phosphate buffer solution, and 50, 100 and 200 ppm of the fungicide mixtures 1 and 2 were added thereto. Immediately after (0 hour), 2 hours, 4 hours, and 6 hours, the bacterial solution was collected and the number of bacteria was measured. At this time, the solution without the addition of the fungicide was used as a control, the experimental results are shown in Table 3.

Comparative Example 2

The experiment was carried out in the same manner as in Example 3, except that a solution containing 50% by weight glutaraldehyde component was used instead of the fungicide mixture used in Example 3. The experimental results are shown in Table 3.

Result of measuring microbial reduction rate according to time of Example 3 and Comparative Example 2 (unit: CFU / ml) Hour Control Disinfectant mixtures 1 Disinfectant mixtures 2 50% by weight glutaraldehyde 50 ppm 100 ppm 200 ppm 50 ppm 100 ppm 200 ppm 50 ppm 100 ppm 200 ppm 0 600000 600000 (870) 600000 (840) 600000 (830) 600000 (900) 600000 (880) 600000 (870) 600000 (910) 600000 (860) 600000 (820) 2 600000 6040 (360) 1880 (40) 1060 (0) 7270 (400) 1940 (10) 720 (0) 9230 (690) 7320 (640) 5690 (430) 4 650000 1260 (320) 980 (0) 760 (0) 2370 (0) 990 (0) 720 (0) 5710 (410) 3950 (280) 1850 (190) 6 800000 880 (60) 720 (0) 630 (0) 1170 (0) 960 (0) 400 (0) 4210 (150) 2160 (230) 1180 (240)

^* () Indicates mold count

From the results in Table 3, in the case of a 50% by weight glutaraldehyde alone compound and a 50% by weight glutaraldehyde and a fungicide mixture of quaternary ammonium phosphate, the microorganisms are killed after 2 hours at all concentrations, The mixture is more effective than the glutaraldehyde alone compound, and in the case of 50% by weight glutaraldehyde alone compound, the fungus is not completely killed, but the fungicide mixture of the present invention inhibits the growth of the fungus. You can see that it appears. In addition, it can be seen that the sterilizing power of the fungus increases as the composition ratio of the quaternary ammonium phosphate in the fungicide mixture increases.

The bactericidal composition of the present invention is considerably effective in controlling a wide variety of microorganisms by using a disinfectant mixture of glutaraldehyde and quaternary ammonium phosphate compounds, and in general, glutaraldehyde has a poor bactericidal effect against some bacteria and fungi. The quaternary ammonium phosphate compound supplements the shortcomings and gives anticorrosion. In the case of instantaneous sterilization and biofilm, glutaraldehyde supplements the role of quaternary ammonium phosphate compound, so that microorganisms contaminate industrial water and living environment. In applications for controlling microorganisms, it is possible to provide bactericidal compositions having broad instantaneous sterilizing power and microbial spectrum and excellent corrosion resistance.

In addition, the quaternary ammonium phosphate used in the present invention is a novel material having excellent anticorrosive properties, and thus, relative to the place where microorganism control is required, in particular, facilities, devices, and apparatuses of corrosive materials such as carbon steel, cast iron, stainless steel, and copper, etc. It can reduce the use of aldehydes, add broad spectrum and anticorrosion for microorganisms, and because quaternary ammonium phosphate and glutaraldehyde have different mechanisms for killing microorganisms, they are resistant strains than when used alone. The expected effect of lowering the occurrence frequency of is obtained.

Claims (4)

Quaternary ammonium phosphate compounds represented by Formula 1 below; And Glutaraldehyde; Sterilizing composition comprising. [Formula 1] In Formula 1, R ₁ may include a hetero atom as a linear or pulverized alkyl group or aryl group having 1-27 carbon atoms which does not include a hydroxyl group, and R ₂ and R ₃ may be the same as a methyl group, or R ₂ and R ₃ is a heterocyclic structure having 4 to 6 carbon atoms containing oxygen and nitrogen formed by bonding to each other, and R ₄ is a linear or crushed alkyl or aryl group having 1-27 carbon atoms including a hetero atom or a benzyl group. The method according to claim 1, wherein in Formula 1 R ₁ is a para- (α, α, γ, γ) -tetramethyl butyl phenoxy ethoxy ethyl group, R ₂ and R ₃ are each a methyl group, R ₄ is a hetero atom or A sterilizing composition which is a linear or pulverized alkyl or aryl group having 1-27 carbon atoms including a benzyl group. The preservative composition of claim 1, wherein a mixing ratio of the quaternary ammonium phosphate compound and glutaraldehyde is 20: 1 to 1:30 by weight. The preservative composition of claim 1 or 3, wherein a mixing ratio of the quaternary ammonium phosphate compound and glutaraldehyde is 1: 4 to 1:20 by weight.