JP2002521313A - Synergistic antimicrobial compositions of peroxyacetic acid and phosphorus compounds - Google Patents

Abstract

  (57) [Summary] An effective amount of peracetic acid (PAA) and an effective amount selected from the group consisting of tetrakis (hydroxymethyl) phosphonium sulfate (THPS), tetrakis (hydroxymethyl) phosphonium phosphate (THPP), and tetrakis (hydroxymethyl) phosphonium chloride (THPC) A synergistic antimicrobial combination comprising an amount of a phosphorus compound is disclosed. Also disclosed are methods of growing microorganisms using these synergistic antimicrobial combinations.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to synergistically useful compounds for inhibiting the growth of microorganisms wherever they are found, for example, in aqueous systems associated with a wide variety of industrial applications. It relates to an antimicrobial composition. More specifically, the present invention relates to a synergistic mixture of peroxyacetic acid and a phosphorus compound. Its use is also disclosed.

[0002] Each in the background herein invention is referred to as PAA and THPS, known both peroxyacetic acid (also sometimes referred to as peracetic acid) and tetrakis (hydroxymethyl) phosphonium sulphate phosphorus compounds of the like is, as individual antibacterial agents Have been. A surprising finding of the present invention is that it is synergistic when used in combination. As used herein, the terms "synergism" and "synergistic" refer to the efficacy of a composition comprising two or more biocides, such as PAA and THPS, as the sum of the efficacy of the individual components obtained alone. Means greater than Thus, a synergistic biocide combination may allow the use of lower total concentrations of biocide or the realization of enhanced antimicrobial effects at equivalent dosages.

[0003] Peroxyacetic acid is known for its antibacterial properties, and its use as an antibacterial agent is described in US Pat. Nos. 5,368,749, 5,494,588, 5,624,575.
No. 5,658,467 and 5,670,055.
Also disclosed are synergistic mixtures of peroxyacetic acid and certain biocides and methods of use.

Similarly, tetrakis (hydroxymethyl) phosphonium sulfate (THP
The use of certain phosphorus compounds as antimicrobial agents, including S) and related compounds, is known;
It is disclosed in U.S. Patent Nos. 4,673,509 and 5,670,055. However, a synergistic combination of PAA and a THPS-related compound has not been disclosed or suggested in the art.

As used herein, the terms “antimicrobial,” “biocidal,” and “inhibiting microbial growth” refer to killing, inhibiting, or controlling the growth of bacteria, yeast, mold, and / or algae. means. Many important industries use their process water on the raw materials they use,
On the various components of the manufacturing process, and in the final product manufactured, there are severe deleterious effects resulting from the effects of the growth of the microorganism. Such industries include paint, wood, textiles, cosmetics, leather, tobacco, fur, rope, paper, pulp, plastic,
Includes the fuel, petroleum, rubber, and machinery industries.

[0006] Systems utilizing circulating water or an aqueous medium are contaminated with microorganisms, and their effectiveness is greatly impaired if microbial deposition is established in the system. Deposits cover the walls of tanks and other vessels used and any machinery or process equipment, causing obstructions to pipes and valves. Deposits also cause discoloration and other imperfections in the manufactured product, necessitating costly shutdowns. Microbial control is particularly important for aqueous media in which the particles or microparticles are dispersed in an aqueous medium, such as dispersed cellulose fibers and dispersing excipients and pigments in papermaking, and dispersed pigments in paint manufacturing.

[0007] Slime control in the papermaking process is particularly important. The control of bacteria and fungi in pulp and paper mill aqueous systems, including aqueous dispersions of paper fibers of various consistency, is particularly critical. The establishment of uncontrolled slime caused by bacterial and fungal accumulation can cause off-grade production, reduced production due to increased downtime and cleaning frequency, increased raw material usage, and increased maintenance costs. The problem of slime deposition is particularly important in view of the widespread use of closed cloudy water systems in the paper industry.

[0008] Another important area that requires the use of good antimicrobial compositions to control bacterial and fungal growth is clay and pigment slurries. These slurries contain various clays (e.g., kaolin) and pigments (e.g., calcium carbonate and titanium dioxide) and are usually manufactured at a location separate from the end use application. This means that they are generally transported and stored at the application site for later use. Due to the high quality standards of the paper and paint products in which such slurries are used, it is essential that these clay or pigment slurries have a very low microbial count per gram of sample.

Accordingly, the growth of microorganisms on industrial aqueous systems and manufactured articles is effectively controlled and / or
Or there is still a very real and substantial need for an antimicrobial composition that can be inhibited. Due to increasing environmental regulations, there is still a further need to provide biocidal compositions with enhanced antimicrobial activity that are effective at lower doses than previously used. The use of lower doses of biocide has a positive impact on the environment and allows the user to realize significant cost savings.

In addition, there is still a substantial need for environmentally safe antimicrobial compositions at relatively high levels.

[0011] Synergistic antimicrobial combination according to Summary of the Invention The present invention is an effective amount of peroxyacetic acid (PAA) and tetrakis (hydroxymethyl) phosphonium sulfate (THPS),
An effective amount of a phosphorus compound selected from the group consisting of tetrakis (hydroxymethyl) phosphonium phosphate (THPP) and tetrakis (hydroxymethyl) phosphonium chloride (THPC). The amount of the PAA and the phosphorus compound can be any amount that provides an antimicrobial effect. Preferably, this amount is such that even when added in much higher amounts to the system, a synergistic coefficient (K value) of less than 1 is obtained after the decomposition of some biocides.

The synergistic antimicrobial combination according to the invention also comprises a) PAA and b) THPS,
THPP, and a phosphorus compound selected from the group consisting of THPC, wherein the weight ratio of a) to b) ranges from about 1000: 1 to 1: 1000 on an active basis.

[0013] The synergistic antimicrobial combination according to the present invention may also comprise a) about 0.0001 to about 0.1% by weight of PAA; b) about 0,1 selected from the group consisting of THPS, THPP, and THPC. 0001 to about 0.1% by weight of the phosphorus compound; and c) may be in an aqueous concentrate containing the remaining water (and other ingredients of the system to be treated); wherein the weight ratio of a) to b) is: On an activity basis, it ranges from about 1000: 1 to 1: 1000.

The present invention also provides a method for inhibiting microbial growth on aqueous systems and articles of manufacture that are prone to such growth, wherein an effective amount of a synergistic antimicrobial combination as described above is added to the system or the article as described above. Including applying to.

[0015] Combinations detailed description PAA and the phosphorus compound of the invention (THPS, THPP, and / or THPC) is, this combination generally in that meet the antimicrobial requirement described for many applications, synergistic antimicrobial It was surprisingly found to be a combination. This synergistic combination is even more valuable for some industrial desires to refrain from the use of halogens to reduce the risk of harmful effects on the environment.

As used herein, the term “effective amount” refers to a composition comprising a PAA and a phosphorus compound necessary to achieve the desired level of inhibition or control of microbial growth on an aqueous system or article to be treated. Means the amount of

The phosphorus compounds used in the synergistic blends of the present invention are described in US Pat. No. 4,673,5
No. 09, the disclosure of which is incorporated herein by reference in its entirety. The phosphorus compound is preferably selected from the group consisting of THPS, THPP, and THPC, with THPS being most preferred. THPS is most preferred because of its proven efficacy and utility, along with the fact that it is not a halogenated biocide.

[0018] The synergistic mixtures of PAA and phosphorus compounds disclosed herein, and methods of use thereof, may be used in virtually any aqueous system or article of manufacture where inhibition of microbial growth is desired and without compatibility issues. Or it is considered useful for the product. Suggested uses of the synergistic antimicrobial combinations of the present invention include, for example, inhibiting bacterial and fungal growth in aqueous paints, adhesives, latex emulsions, inks, binders, and caulking compounds; preservation of wood; cutting oils and metals Preservation of processing fluids; control of slime-producing bacteria and fungi, including yeasts and molds, in pulp and paper mills and cooling towers; as spraying or dipping textiles and leather to prevent mold growth; As components of antifouling paints; protection of paint films, especially exterior paints, from fungal attack during weathering of paint films; slime deposition during production of cane sugar and beet sugar, food, nutrients and food additives Protection of process equipment from waste; air fresheners or washer systems and fresh water in industrial fresh water supply systems Establishment and prevention of deposits; control of microbial contamination in closed loop and recirculating water cooling systems; control of microbial contamination and deposits in oilfield drilling and mud and secondary oil recovery processes; detrimental to paper processing quality Prevention of bacterial and fungal growth in paper processing processes that can have significant impact; control of bacterial and fungal growth and deposits during the manufacture of various feature boards, such as cardboard, particle board and food board; various types of new Prevent discoloration of sap stains on cut wood; bacteria and various types of clay and pigment slurries manufactured for later use in paper processing and paint production and susceptible to microbial degradation during storage and transport Control of fungal growth; as a hard surface disinfectant to prevent the growth of bacteria and fungi on walls, floors, etc .; To prevent algae growth comprising fine cyanobacteria (blue-green algae);
And controlling bacterial and fungal growth in various cosmetics. In addition, the synergistic mixtures of the present invention are believed to be equally useful for various types of non-aqueous systems.

The synergistic antimicrobial compositions disclosed in the present invention are particularly applicable for controlling microbial slime in papermaking processes. The need to control bacteria and fungi in pulp and paper mill aqueous systems, including aqueous dispersions of paper fibers of varying consistency, is disclosed above.

Another important area where the antimicrobial compositions of the present invention are particularly useful is in the control of bacterial and fungal growth on clay and pigment slurries as disclosed above. It is essential that these clay or pigment slurries have a very low microbial count per gram of sample.

Furthermore, the synergistic combination of the present invention and its use have been found to be particularly useful for controlling the detrimental effects of microorganisms on water or aqueous media. Specific examples of aqueous systems that require use of the present invention to control microorganisms include cooling water used in the chemical industry and power generation, treatment of wastewater from public and industrial plants, and food and beverage industries. Including a sterile system.

As disclosed above, any system that utilizes circulating water or an aqueous medium is contaminated by microorganisms, resulting in a substantial reduction in efficacy when microbial deposition is established in the system, and according to the present invention. Can be processed. The control of microorganisms in an aqueous medium according to the present invention can be achieved by dispersing particles or microparticles in an aqueous medium, such as dispersed cellulose fibers and dispersed excipients and pigments in papermaking, and dispersed pigments in paint manufacturing. Especially important if present.

The present invention relates to a synergistic antimicrobial composition comprising a) PAA and b) a phosphorus compound selected from the group consisting of THPS, THPP, and THPC, wherein a) versus b)
Is preferably in the range of about 1000: 1 to 1: 1000 on an active basis. The invention further relates to a method for inhibiting microbial growth on aqueous systems and articles of manufacture that are prone to such growth, the method comprising: a) PAA and b) THPS;
The weight ratio of an effective amount of the antimicrobial composition (where a) to b) comprising a phosphorus compound selected from the group consisting of THPP and THPC is in the range of about 1000: 1 to 1: 1000 on an active basis. Treating the above system or the above article.

According to the invention, the weight ratio of the two components of the synergistic combination is determined in relation to each end use application, based on the 100% active ingredient, by the dose level of each synergistic component. Typically, the weight ratio of the PAA of component a) and the phosphorus compound of component b) is from about 1000: 1 to 1: 1000, preferably from about 100: 1 to 1: 100, more preferably on an active basis. It ranges from about 10: 1 to 1:10. However, as will be appreciated by those skilled in the art, the synergistic weight ratio of the two components will generally vary to some extent depending on the application and the microorganism being controlled. For example, increasing the ratio of PAA to phosphorus compound may be more effective in one application, while increasing the ratio of phosphorus compound to PAA may be more effective in another application. The PAA / phosphorus compound composition has been found to be particularly effective against bacteria when used in a weight ratio of about 5: 1 to 1: 5.

In aqueous systems treated with a synergistic composition of PAA and a phosphorus compound, the amount of each biocide present can range from about 0.05 parts per million (ppm) to about 200 ppm. Preferably, from about 1 ppm to about 100 pp based on the weight of the water of the system to be treated.
m, more preferably about 2 ppm to 60 ppm of each biocide. However, an effective amount of the synergistic combination of the present invention must be added to the aqueous system to be treated, even if very small amounts of one biocide and large amounts of others are present.
This amount of the synergistic composition of the present invention is at least about 0.1 ppm, preferably at least 1 ppm, more preferably at least 10 ppm, based on the weight of the water of the system to be treated.
ppm.

The upper limit of each component and the upper limit of the total synergistic combination of the present invention depends on economic and environmental concerns. The total amount of the synergistic biocide combination of the present invention present in the aqueous system is less than about 300 ppm, preferably less than about 200 ppm, more preferably less than about 150 ppm.
pm or more, and most preferably about 100 ppm or less. However, determining an effective amount of a biocide for a system based on various system parameters, including but not limited to the size of the system, the pH of the system, the type of organisms present, and the desired amount of control, is a challenge. It is within the skill of ordinary artisans in the field.

Further, in certain applications, a higher proportion of the biocide is required for controlling or killing microorganisms. In these applications, higher amounts of each biocide can be added while maintaining a measurable synergistic effect. Therefore, the upper limit of the synergistic effect of the combination varies depending on the application. For storage applications, for example, each biocide in the blend may have about 0.05
It may be present at concentrations ranging from as high as ppm to 1000 ppm.

[0028] Much higher amounts of one or both biocides can be added to the system to provide protection from microbial growth. This is because the concentration throughout the system is not always the same and the local ratio can vary very widely. Also, initially higher amounts can be added with the expectation that one or both biocides will degrade or degrade over time and fall within the above ranges. An amount higher than the above is added to the system to be treated, but it is important that the local amount or time-resolved amount falls within the stated range at a certain point in time, so that the microorganisms of the system are controlled and a synergistic combination Benefits.

Further, if one of the two biocides of the present biocide blend is added at relatively high concentrations (eg, 200 ppm or more), the addition of the second biocide still has a synergistic effect. However, the effect is masked by the overall high concentration of all biocides present in the system. For example, the phosphorus compound THPS was added to the E.A. When added to a system containing E. coli in amounts of 200 ppm or more, the kill rate will be faster than THPS alone. However, the final killing or deterrent effect is
All E. It will be significantly different since E. coli bacteria will eventually be killed by only 200 ppm THPS.

[0030] An effective amount of a synergistic combination of PAA and a phosphorus compound is also applicable to the article of manufacture to be treated. Generally, the above synergistic antimicrobial combination solution having a concentration of at least 0.1 ppm is incorporated, sprayed or poured onto the substrate to be treated in order to prevent the growth of bacteria, mold, yeast or algae. Used for immersion or otherwise applied, for example by immersion or submersion. Again, determination of the effective amount of biocide to apply to the particular article of manufacture being processed and determination of the appropriate form of application are within the skill of the ordinary artisan in the art.

The active ingredients of the synergistic antimicrobial compositions of the present invention may also include a wide variety of formulations; solids, including finely divided powders and granular materials; and solutions, emulsions, suspensions, concentrates, emulsifiable concentrates. Liquids such as liquids, slurries and the like can be used depending on the intended use and the desired formulation medium. In addition, when the synergistic antimicrobial combination is liquid, it can be used neat, in various formulations (both solid and liquid), in talc, clay, diatomaceous earth, etc., or in water or lower alkanols, kerosene, benzene, It can be incorporated as an adsorbent on a suitable inert carrier, such as various organic liquids such as toluene and other petroleum distillation fractions or mixtures thereof.

The amount of the synergistic combination of PAA and the phosphorus compound can be added to the aqueous system to be processed as a solid single component or as a dry blend. However, the synergistic combination is preferably added as a solution, which is an aqueous suspension diluted in situ to the above-mentioned amounts. The synergistic combination is preferably added as two separate single component solutions that are blended and diluted in situ. This separate addition is preferred due to the instability of the blend solution over time due to decomposition. PAA is an oxidizing biocide and phosphorus compounds are non-oxidizing biocides. Therefore, over time PA
A degrades in the solution blend as it degrades and oxidizes the phosphorus compounds (THPS, THPP, and / or THPC).

[0033] The aqueous concentrate of each single component solution used in the synergistic antimicrobial combination contains a much higher amount of each biocide than is present in the final treated aqueous system and is a matter of ordinary skill in the art. Within the technology. The concentrate can vary widely depending on the desired weight savings with decreasing water volume, while maintaining ease of application with minimal in situ mixing.
What is important is the ratio and final concentration of each biocide in the aqueous system to be treated. These should be within the above limits. Each concentrate can include other standard ingredients and can be added in combination with other standard additives used in a particular aqueous system.

PAA is available in liquid form from English China Clays Inc. /
It is commercially available from Calgon Corporation (ECC / Calgon), Pittsburgh, Pa., As Metasol® PAA, a 12% active PAA, CH3COOOH. This product also contains about 18% hydrogen peroxide, about 20% acetic acid and about 50% water. THPS also uses ECC /
It is commercially available from Calgon, Pittsburgh, Pa., And is in liquid form as Methasol® LT, a 35% active THPS in aqueous solution.

To prepare two synergistic composition solutions under the present invention, an effective amount of each active ingredient is combined in a suitable carrier such as water, an organic solvent, and the like. Preparation of such compositions is within the skill of the ordinary artisan in the field.

[0036] It will also be appreciated by those skilled in the art that the synergistic antimicrobial combinations disclosed herein may be used in combination with other antimicrobial agents. For example, the combination can be combined with other fungicides and fungicides at appropriate concentrations and, where appropriate, combining the respective effects to achieve particularly useful results. Such combinations may find particular use in the preparation of germicidal soaps, in the preparation of cosmetic and aqueous coatings, and in the control of paper mill microbial slime accumulation. Also, the synergistic antimicrobial combination of the present invention can be combined with other algicides as well.

The invention further provides a method of inhibiting the growth of at least one of the following: bacteria, yeast, mold and algae. By the method of the present invention, this growth is prevented on aqueous systems or articles of manufacture or products that are prone to such growth. These methods include adding to an aqueous system or treating an article or product comprising the bacterium, yeast, mold and / or algae with an effective amount of a synergistic combination of PAA and a phosphorus compound (eg, THPS). Including. This addition can be accomplished by simply adding the components together as a single mixture, or by preferably adding the two components separately. Such separate administrations can be simultaneous or at different times. The net effect is the same: the system, article or product to be treated is ultimately incorporated therein or applies the desired dose concentration of each component thereto.

Furthermore, the compositions of the present invention are believed to be effective regardless of the application (unless the blend has been stored for a long time before addition). For example, the antimicrobial compositions described herein may be added to the system to be treated as two separate streams or one stream, via a low level continuous feed, a semi-continuous feed, or through a bulk feed. it can. Those skilled in the art are familiar with all of these supplies. Feeding in chunks is particularly effective and is therefore the preferred method of practicing the method of the present invention. This type of supply allows the user to monitor the microbial concentration in the system and can only supply the product when the microbial concentration increases. The user realizes cost savings by providing effective amounts of PAA and the phosphorus compound only when needed.

As noted above, the present invention provides a synergistic result from the use of PAA in combination with certain types of phosphorus compounds, which can be used in various industrial and other applications for bacteria, yeast, mold and Based on the finding that it is effective in controlling algae growth. The utility of the synergistic antimicrobial combinations disclosed herein derives from their pluripotency in both a number of applicable industries as well as a number of effective microorganisms. In particular, the large economic losses in papermaking operations caused by the accumulation of bacterial and fungal slime in various parts of the system can be significantly eliminated by the use of the synergistic combinations described herein.

The superior antimicrobial activity of the synergistic antimicrobial combination of PAA and the phosphorus compound was confirmed using standard laboratory techniques. The antimicrobial combination has been found to be effective in inhibiting bacterial growth, including but not limited to Klebsiella pneumoniae and Escherichia coli, and has been found to be particularly effective against Pseudomonas aeruginosa. . The combination may also include other aerobic bacteria such as Bacillus, Staphylococcus, Flavobacterium, Enterobacter, Xanthomonas, freshwater organisms such as anaerobic bacteria, filamentous fungi, various species of Candida and yeast. It is believed to be effective against fungi, including but not limited to fungi, white and pink yeasts, molds, and various species of green and blue algae.

The following examples are given to illustrate the present invention, not regarded as limiting the invention in any way.

Example 1 The biological efficacy of the antimicrobial composition of the present invention in a microtiter test is demonstrated below. 3
A mixture of three different bacterial strains, Klebsiella pneumoniae, Escherichia coli, Pseudomonas aeruginosa, and all three strains was used.

Each of the three bacteria was grown separately on a standard Method's Agar (STM) plate and incubated at 37 ° C. for about 24-48 hours. Various bacteria,
A small tissue flask containing about 25 ml of Allen's medium was inoculated using a sterile cotton swab.
The culture was then diluted by adding 10 ml of the bacterial suspension to 90 ml of fresh Allen medium. To prepare a mixed culture of all three organisms, an equal volume of about 20 ml of each diluted culture was mixed together into a large tissue culture flask. Samples of the mixture and individual bacterial suspensions were then used for microtiter testing.

An 8 × stock solution of PAA for use in combination with THPS was prepared by dissolving 6.6 g of 12% active PAA in about 100 ml of deionized water. A 4 × stock solution of THPS used in combination with PAA was prepared in the same manner with 0.106 g of THP
Prepared using S (35% active THPS). 4x of THPS used alone
Stock solutions were prepared in the same manner, using 0.53 g of THPS. THPS
PAA 8 × stock solution used in combination with about 6.6 g of 12% active PAA,
Prepared by dissolving in 100 ml of deionized water. A 4 × stock solution of THPS for use in combination with PAA was prepared in the same manner, using only 0.05 g of THPS. A 4 × stock solution of PAA used alone was prepared in the same way using 3.3 g of PAA. Subsequently, two other plates were loaded with 6.6 g PAA.
And 0.16 g and 0.26 g of THPS, respectively. 8
One microtiter plate was used in the examples (PAA and THPS alone plates were not counted), and each microtiter plate contained eight rows AH
And 12 columns 1-12. The amount of each biocide in each well of the eight plates is shown below.

[0045]

[Table 1]

As shown in the table above, the amount of PAA in the wells of plates 1-9 was 100
The concentrations of the other components (THPS) were kept constant at 200, 100, 300, 500, and 0 ppm activity, although varied in serial dilution series ranging from 0 ppm activity to 2 ppm activity. Plate 10 showed the use of THPS alone in a serial dilution series. Plates 9 and 10 show the use of each biocide alone and were used to determine the minimum amount of each biocide that, when used alone, would inhibit microbial growth. No biocide was added to column 12 of the wells of any plate, indicating a biological or positive control. This positive control was performed to confirm that the organism could grow in a given environment. No bacteria was added to column 11 of the wells of any plate, which represented an Allen medium control or negative control. This was performed to ensure that the plates were free of contamination. To each of the ten microtiter plates, Pseudomonas aeruginosa was added to rows A and B, Klebsiella pneumoniae was added to rows C and D, Escherichia coli was added to rows E and F, and the mixture of all three bacteria was added to row G. And H.

Plates 1-4 contain the minimum inhibitory concentration (MI) of each biocide combination for each bacterial strain.
Used to determine C). The MIC is the minimum amount of biocide required to prevent growth in a well, and growth is measured as turbidity in the medium or as a "pellet" of cells emerging from the medium and settling to the bottom of the well. Define.

[0048] Plates 5-8 were then subcultured from plates 1-4, respectively, 24 hours after biocide addition. Subculture was performed to determine the minimum biocide concentration (MBC). MBC is the minimum concentration of biocide that does not cause growth after subculture and subsequent incubation.

[0049] All microtiter plates, including MIC and MBC plates, were incubated for 24 hours at 37 ° C. After a 24-hour incubation period,
The presence or absence of growth in each well of the plate was determined. Growth in microtiter plates was determined by picking from each macrotiter well and subculturing the plates on solid agar plates. The plate was then incubated at 37 ° C. for 24 hours. The presence or absence of growth in each well was then used with the concentration of biocide in each well to determine the synergistic properties of the biocidal combination. The synergistic property is Kul
Evaluated by determination of 1 value / K value; K value was determined for each bacterium tested. K
Methods for calculating the values are known to those skilled in the art. In this example, the K value is given by the following equation:

[0050]

(Equation 2)

Wherein “combination [PAA]” means the concentration of PAA that, when used in combination with THPS, results in microbial growth inhibition; “combination [THPS]”
When used in combination with AA, refers to the concentration of THPS that results in microbial growth inhibition; "[PAA] alone" means the concentration of PAA that results in microbial growth inhibition when used alone. "[THPS] alone" means the concentration of THPS that, when used alone, results in microbial growth inhibition.

A K value less than 1 indicates synergy between the two biocides, a K value greater than 1 indicates antagonism between the two biocides, and a K value equal to 1 indicates that 9 shows the additive effect of a biocide.

The K values determined for each organism used in the examples are recorded in Tables 2-9.

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

[0057]

[Table 5]

[0058]

[Table 6]

[0059]

[Table 7]

[0060]

[Table 8]

[0061]

[Table 9]

[Procedure amendment]

[Submission date] January 23, 2001 (2001.1.23)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

(Equation 1) Wherein THPS indicates a phosphorus compound and “combination (PAA)” means the concentration of PAA that, when used in combination with THPS, results in microbial growth inhibition;
“Combination (THPS)” means the concentration of THPS that, when used in combination with PAA, results in the inhibition of microbial growth; “(PAA) alone”, when used alone, inhibits microbial growth. Means the concentration of PAA that results in
2. "Alone" means the concentration of THPS that, when used alone, results in the inhibition of microbial growth, as defined by: an amount that results in a synergistic coefficient (K-value) of less than one. Antimicrobial combination composition.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZA, ZW (71) Applicant One Nelco Center, Naperville, Illinois 60563 -1198, United States of America (72) Inventor Miller, Patrick, C .; Royal Oak Drive, Wexford, Pennsylvania, United States, 15020 1375 F-term (reference) 4H011 AA02 BA01 BA06 BB06 BB17 BC18 DA16 DD01 DF06

Claims (20)

[Claims] 1. An effective amount of peracetic acid (PAA) and tetrakis (hydroxymethyl) phosphonium sulfate (THPS), tetrakis (hydroxymethyl) phosphonium phosphate (THPP), and tetrakis (hydroxymethyl) phosphonium chloride (THPC). An antimicrobial combination comprising an effective amount of a phosphorus compound selected from the group. 2. The amount of peracetic acid and phosphorus compound in the above amount is determined by the following formula in which THPS represents the phosphorus compound: Wherein "combination (PAA)" means the concentration of PAA that, when used in combination with THPS, results in microbial growth inhibition; "combination (THPS)"
When used in combination with A, refers to the concentration of THPS that results in microbial growth inhibition; "(PAA) alone" means the concentration of PAA that results in microbial growth inhibition when used alone. "(THPS) alone" means the concentration of THPS that, when used alone, results in the inhibition of microbial growth, and is an amount that results in a synergistic coefficient (K value) of less than 1 as determined by: Item 7. An antibacterial combination composition according to Item 1. 3. a) PAA and b) the phosphorous compound THPS, THPP or THPC can be used in aqueous systems in an amount of from about 1000: 1 to 1: 1000 a) on an active basis.
The antimicrobial combination composition according to claim 1, which is present in a weight ratio of to b). 4. The combination comprises: a) about 0.0001 to about 0.1% by weight of PAA.
B) about 0.0001 to about 0.1% by weight of a phosphorus compound; and c) in an aqueous concentrate containing the balance of water, wherein the weight ratio of a) to b) is about 1000
The antimicrobial combination composition of claim 1, wherein the composition ranges from 1: 1 to 1: 1000. 5. The combination of the two, comprising firstly: a) about 0.0001 to about 0.1% by weight of PAA; and b) about 0.0001 to about 0.1% by weight of the phosphorus compound. Wherein the balance of each concentrate is water; wherein the weight ratio of a) to b) ranges from about 1000: 1 to 1: 1000 on a once combined activity basis. An antimicrobial combination composition according to claim 1. 6. A) peracetic acid and b) THPS, THPP and THPC
A synergistic antimicrobial combination comprising a phosphorus compound selected from the group consisting of: wherein the weight ratio of a) to b) ranges from about 1000: 1 to 1: 1000 on an active basis. Antibacterial combination. 7. The phosphorus compound is THPS and the weight ratio of a) to b) is about 10
7. The composition of claim 6, wherein the composition ranges from 0: 1 to 1: 100. 8. A method for inhibiting microbial growth in an aqueous system, comprising adding an effective amount of the synergistic antimicrobial combination of claim 1 to the system. 9. A method for inhibiting microbial growth in an aqueous system, comprising adding an effective amount of the synergistic antimicrobial combination of claim 6 to the system. 10. The method of claim 9, wherein the weight ratio of a) to b) ranges from about 10: 1 to 1:10. 11. The method of claim 9, wherein the peracetic acid and the phosphorus compound are added together as a single composition to the system to be treated. 12. The method according to claim 9, wherein the peracetic acid and the phosphorus compound are separately added to the system to be treated. 13. The method of claim 9, wherein at least 0.1 ppm of the synergistic antimicrobial composition is added to a system selected from the group consisting of a paper mill water system, a clay and dye slurry system, a cooling water system, and a wastewater treatment system. the method of. 14. The method of claim 1, wherein the amount of peracetic acid is from about 1 ppm to about 100 ppm.
10. The method of claim 9, wherein about 100 ppm of the phosphorus compound THPS is added to the system to be treated. 15. A method of inhibiting the growth of microorganisms on an article of manufacture, comprising applying an effective amount of the synergistic antimicrobial combination of claim 1 to said article. 16. A method of inhibiting the growth of microorganisms on an article of manufacture, comprising applying to the article an effective amount of the synergistic antimicrobial combination of claim 6. 17. The method of claim 16, wherein the weight ratio of a) to b) ranges from about 100: 1 to 1: 100. 18. The method of claim 16, wherein the peracetic acid and the phosphorus compound are added together as a single composition to the article to be treated. 19. The method according to claim 16, wherein the peracetic acid and the phosphorus compound are separately added to the article to be treated. 20. The method of claim 16, wherein said synergistic antimicrobial composition is at a concentration of at least 0.1 ppm.