JPH0550481B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an agent for inhibiting the growth of aquatic microorganisms, a method for inhibiting the growth of the microorganisms, and a concentrated liquid mixture or solid mixture for inhibiting the growth of the microorganisms. [Prior Art] Aquatic microorganisms, especially bacteria such as Pseudomonas aeruginosa, fungi such as Oscillatoria, and yeasts such as Sacharomyces cerevisiae, are commonly used in industrial plants. , chemical plants, or steel plants, brewing plants, power plants or paper plants,
It is grown in various aqueous systems such as marine engines, central heating equipment, and in various aqueous systems such as oil field injection water or water-based products. These microorganisms cause corrosion and/or fouling.
wake up The growth of these microorganisms is inhibited by oxidizing biocides such as chlorine or inorganic biocides such as copper salts or organic biocides including quaternary ammonium or phosphonium compounds containing one or more long-chain alkyl groups. It can be controlled by treatment with biological agents. A problem with using such quaternary compounds is that water foaming occurs. [Problems to be Solved by the Invention] It is desired to suppress the growth of each of the above-mentioned aqueous systems or aqueous microorganisms that grow in water. SUMMARY OF THE INVENTION We have found that phosphine or phosphonium compounds having one or more hydroxyalkyl groups attached to each phosphorus atom are highly effective in controlling aqueous microorganisms. I found it. In particular, such phosphoin or phosphonium compounds are highly cost effective and effective in the absence of long chain alkyl groups that have caused foaming problems with prior art biocides. We have further found that the hydroxyalkyl phosphorus compounds exhibit valuable oxygen scavenging activity, at least under acidic PH conditions. The present invention provides an aqueous microbial system comprising adding at least one phosphorus compound containing at least one hydroxyalkyl group directly bonded to a phosphorus atom to an aqueous microorganism-containing aqueous system or to an aqueous system easily contaminated with aqueous microorganisms. The present invention relates to a method for treating a water system containing or easily contaminated with aqueous microorganisms. The above phosphorus compound contains one phosphorus atom and has the general formula [HORPR′ _o O _n ] _y X _x (where n is 2 or 3,
m is 0 or 1 and n+m is 2 or 3, x is 0 or 1 and n+x is 2 or 4, y is equal to the valence of X, R has 1 to 4 carbon atoms, preferably is an alkylene group of one carbon atom with a hydroxy group bonded to the 1, 2, 3 or 4 carbon atom, each R' may be the same or different, preferably 1 to an alkyl or alkenyl group of 4 carbon atoms or more commonly a group of the formula HOR-, where R has the same meaning as above, and X is an anion which renders the phosphorus compound water-soluble. It is an ion. The (-ROH) group is thus a 1-hydroxyalkyl group or a 2-hydroxyalkyl group such as a hydroxymethyl group or a 1- or 2-hydroxyethyl group or a 1- or 2-hydroxypropyl group or a 1- or 2-hydroxybutyl group. and preferably at least one R' is ROH, but may also be, for example, a methyl, ethyl, propyl, isopropyl or n-, sec-iso- or tertiary-butyl group. . X is a monovalent anion, such as a chloride ion or a bromide ion, or an organic carboxylic acid residue, such as an alkanecarboxylic acid residue, preferably an alkanecarboxylic acid residue of 2 to 5 carbon atoms, such as an acetate residue, a bisulfite residue (bisulfite), bisulfate residues or organic sulfonic acid residues such as methosulfate or benzene, toluene, xylene sulfonate, or dihydrogen phosphate (salt) residues or divalent anions such as sulfate or sulfite. root or monohydrogen phosphate residue or 3
a valent group such as a phosphate ester (salt) residue or
An organic carboxylic acid residue having one or more carboxyl groups, such as a citric acid residue. The phosphorus compound may be phosphine oxide. Alternatively, the phosphorus compound has a concentration of at least 0.5 at 25°C.
It may contain 2 or 3 or more phosphorus atoms as long as it has water solubility at a concentration of 1 g/g.
Such phosphorus compounds usually contain at least one, preferably at least two, hydroxyalkyl groups per phosphorus atom. Such hydroxyalkyl groups are preferably represented by the formula ROH, where R has the same meaning as above. One or more bonding groups that bond phosphorus atoms to each other have the formula -R-,-
R-O-, -R-O-R- or -R-NH-
R- or -R-R''-R (in these formulas R has the same meaning as above, R'' is formed by removing two hydrogen atoms bonded to nitrogen from a diamide or polyamide or a diamine or polyamine) residues formed by removing two hydrogens from urea, dicyandiamide, thiourea or guanidine.Two or more, for example three, hydroxyalkyl groups per phosphorus atom. This kind of compound is 1
Compounds with 3 or 4 hydroxyalkyl groups bonded to 3 or 4 phosphorus atoms, such as those with the formula [HORPR′ _{o
O n ] y} Condensation is 40~
This can be done by heating at 120°C. Preferably the phosphorus compound has only one phosphorus atom and 3
It contains 1 or 4 hydroxyalkyl groups, especially hydroxymethyl groups. Such compounds can be made by reacting an aldehyde, usually formaldehyde or a ketone, with phosphine in the presence of a mineral acid, usually hydrochloric, sulfuric or phosphoric acid. Depending on the proportions of the reactants, the product can be a trishydroxyalkylphosphine or a tetrakis(hydroxyalkyl)phosphonium salt. However, under aqueous alkaline conditions, the former is accompanied by the formation of a dimeric compound with two phosphorus atoms and an ROR bridging group or a phosphine oxide with n=2, m=1, x=0, or a small amount of both. There is a tendency to turn to The product may contain up to 10% by weight of free aldehyde or ketone such as formaldehyde and up to 10% by weight of acid. Phosphorus compounds usually have a pH of 1 to 6 in a 75% by weight aqueous solution. one or more
Compounds in which R' is an alkyl group can be prepared by reaction of the corresponding alkyl-substituted phosphine with an aldehyde or ketone. To avoid foaming, it is preferred that the alkyl or alkenyl groups present have fewer than 5 carbon atoms. However, compounds in which one or two alkyl or alkenyl groups per molecule have up to 24 carbon atoms are effective biocides and can be used according to the invention in applications where foaming is not a problem. . Examples of biocides according to the invention are tetrakis(hydroxymethyl)phosphonium sulfate, tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate and tris(hydroxymethyl)
Phosphine oxide is a preferred example, dodecyltris(hydroxymethyl)phosphonium chloride or oleyltris(hydroxymethyl)phosphonium sulfate are less preferred examples. The phosphorus compound of the present invention is added to the water to be treated in an amount effective to suppress the growth of microorganisms in the water to be treated. The amount added is usually 1 to 500 parts by weight, for example 1 to 1000 parts by weight, preferably 5 to 150 parts by weight, particularly 20 to 50 parts by weight, per 1 million parts by weight of water.
For example, 0.6 to 700 parts by weight of tetrakis(hydroxymethyl)phosphonium groups are added per 1 million parts by weight of water, preferably 3 to 100 parts by weight, especially 10 to 30 parts by weight, or bonded to phosphorus per 1 million parts by weight of water. 0.4 to 400 parts by weight, preferably 2 to 60 parts by weight, especially 8 to 20 parts by weight of hydroxyalkyl groups (especially hydroxymethyl groups) are added. The phosphorus compound is preferably added to water as an aqueous solution. The pH of the water after treatment is usually 5-10, for example 6-10.
9, typically 6-7 or 7.5-9. The water contains scale or corrosion inhibitors, such as phosphonates (including aminomethylene phosphonates), polymerates, polyacrylates, polymethacrylates, polyphosphates, or phosphates, in amounts traditionally used as scale inhibitors, and inorganic corrosion inhibitors. Inhibitors such as water-soluble zinc salts,
Nitrite or sulfite salts or organic corrosion inhibitors such as benzoates (esters), phosphonates (esters), tannins, lignins, benzotriazoles or mercaptobenzotriazoles may also be used in any amounts conventionally used. It is preferred that the phosphorus compounds according to the invention are not used together with chromates. Scale inhibitors or corrosion inhibitors or scale inhibitors and corrosion inhibitors can be added separately or together with the phosphorus compounds according to the invention. Oxygen scavenger for treated water,
It is also possible to add flocculants such as polyacrylamides, dispersants, antifoams such as silicone or polyethylene oxygenated antifoams or other biocides such as tin compounds or isothiazolones. The present invention also provides a treatment agent for inhibiting the growth of aqueous microorganisms, and the treatment agent for inhibiting the growth of aqueous microorganisms according to the present invention comprises a phosphorus compound containing at least one hydroxyalkyl group directly bonded to a phosphorus atom;
That is, the general formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, (n+m) is 2 or 3, x is 0 or 1, and ( n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(wherein R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] The main component is a phosphorus compound represented by the following, or a condensate thereof. In addition to the phosphorus compound, the aqueous aqueous microorganism growth inhibitor of the present invention may contain one or more other biocides, and/or the scale inhibitor or corrosion inhibitor listed above, and the oxygen scavenger. agent,
It may also contain a flocculant, a dispersant and/or an antifoaming agent. The microorganisms to be treated are bacteria, molds, yeasts, and algae that typically grow in aqueous environments. Included within this class are sulfate root-reducing bacteria such as Desulphovibrio, iron-parasitic bacteria such as Gallionella, and slime-producing bacteria such as Pseudomonas, the last of which can be found in aquatic systems. is particularly troublesome. The water to be treated may be industrial cooling water, for example cooling water for power plants or chemical plants, or cooling water for steel, paper or brewing, and may be used in closed or open systems, including evaporation in cooling towers. You can also. Alternatively, the water to be treated may be treated water, particularly treated water containing a large number of nutrients for microorganisms, such as paper manufacturing process treated water or brewing water.
Oilfield injection water or water used in reverse osmosis plants, for example for obtaining boiler feed water or industrial process water, can also be treated. The method according to the invention is applicable to geothermal water, water for domestic, institutional and industrial central heating, water for air conditioning systems and water used for static pressure testing of pipelines and vessels, water for swimming pools and water for marine engines. It can also be applied to cooling water. The present invention is also applicable to controlling microbial contamination of a wide variety of water-based products. For example, hydroxyalkyl phosphorus compounds can be used to add water in the production of various solutions and emulsions such as paints, cutting oils, bituminous emulsions, tar emulsions, adhesives, weedicides and insecticides, and the products mentioned above. can be added to solids and concentrated liquids. Accordingly, the present invention provides for the preparation of water-based products susceptible to microbial damage, to which are added a bacteriostatically or bactericidal effective amount of a phosphorus compound containing at least one hydroxyalkyl group attached to a phosphorus atom. It is on offer.
Representative examples of such compositions consist of an aqueous liquid, suspension or emulsion containing at least one functional ingredient and a minor amount of a phosphorus compound of the invention in an amount sufficient to inhibit the growth of microorganisms. . A particularly suitable system for applying the invention is to store water under conditions that favor the growth of bacteria, especially cold-tolerant bacteria such as P. aeruginosa, e.g. at an ambient temperature that favors the growth of bacteria. A system that circulates or stores large quantities of water under conditions that consist of cyclically increasing the temperature or maintaining bacterial nutrients in the water system. [Example] The present invention will be described below with reference to Examples. These Examples compare the activity of phosphorus compounds to formaldehyde and controls. Unless otherwise specified, the phosphorus compound is a 75% by weight aqueous solution of tetrakis(hydroxymethyl)phosphonium sulfate, which is hereinafter referred to as THPS.
Contains 0.4% free formaldehyde and has a pH of 4
It is. Formaldehyde for comparison was used as a 40% aqueous solution. Unless otherwise specified, all doses are expressed in parts by weight of the aqueous biocide solution based on 1 million parts by weight of the water to be treated. Example 1 Activity against Pseudomonas aeruginosa A lyophilized monoculture of Pseudomonas aeruginosa (NC/B 8295) supplied by Torrey Laboratories was incubated in nutrient broth at approximately 30°C. A turbid body was formed by culturing for 24 hours. Two separate cultures were subsequently carried out to confirm that the bacteria were in an active growth state. That is, 2 ml of the final broth was added to 500 ml of sterile 0.25% Ringel solution to uniformly disperse the broth. This inoculated solution was cultured at 30° C. for 24 hours to obtain a standard test medium containing 10 ⁸ bacteria per ml. This test medium was divided into sections of 50 ml each. One section was left as a control, and the other sections were given various amounts of
A proprietary isothiazolone-based biocide was administered in THPS solution and for comparative data. at room temperature
After 16 hours of incubation, the amount of bacteria in each section was counted using standard plate counting methods. The results are as follows:

[Table] Thus, THPS is extremely effective against Pseudomonas aeruginosa and, in fact, proves to have better performance than proprietary isothiazolone-based biocides in this test. Example 2 (Activity against cooling water bacteria) A sample of circulating water from an industrial cooling system heavily contaminated with microorganisms was used as the microbial source in this study. The microbiological population was observed to be mixed, but the predominant microorganisms were Gram-negative rod-shaped bacteria that could not be identified. A test medium containing ¹⁰⁷ bacteria per ml was prepared with tap water from South Staflordshire, UK, previously dechlorinated by adding a small excess of sodium thiosulfate. It was made by mixing with the above-mentioned contaminated cooling water. The test medium was divided into 50 ml sections, one section was left as a control, and the other sections were administered various amounts of THPS. After 16 hours of incubation at room temperature, the bacterial load in each section was measured by standard plate counting method. The results are shown below: THPS dose (ppm) Amount of viable bacteria per ml 0 10 ⁷ 10 10 ⁶ 20 2 x 10 ³ 30 150 50 20 100 0 Therefore, bacteria from industrial cooling water are effective against THPS. It can be seen that it is sterilized. Comparative Example Comparison with Formaldehyde Since THPS is known to react slowly with water to form formaldehyde under certain conditions, it is necessary to demonstrate that formaldehyde is not an agent that acts as a disinfectant. Therefore, at the same time as the operation described in Example 2, a similar test was conducted using the same medium as in Example 2 and adding formaldehyde. The results obtained are as follows: Formaldehyde dose (ppm) Amount of viable bacteria per ml 0 10 ⁷ 0.1 10 ⁷ 0.5 10 ⁶ 1.0 10 ⁶ 5.0 10 ⁶ Theoretically, if 30 ppm of THPS reacts completely with water.
Produces 3.3ppm formaldehyde. 30ppm
of THPS was shown to reduce the bacterial count from 10 ⁷ to 150 per ml (see results in Example 2). Also, from the above results of this comparative example, even 5 ppm formaldehyde only slightly reduces the number of bacteria.
It can be concluded that the bacterial activity of THPS is not due to free formaldehyde. Example 3 (PH Effect) A series of tests in this example were conducted to demonstrate the bacterial activity of THPS over the range of PH values commonly found in cooling water systems. A sample of circulating water from an industrial cooling water system heavily contaminated with microorganisms was used as the microbial source for this study. Although the microbial population was observed to be a mixture, the predominant microorganism was identified as Bacillus Cereus. Add several ml of contaminated circulating water to the nutrient broth,
The mixture was then incubated at 30° C. for about 24 hours until turbidity occurred. Add 10 ml of the above broth to 5 ml of tap water from South Staffordshire, UK, previously dechlorinated with a small excess of sodium thiosulfate. This bacterial suspension was used as a test medium. Divide the test medium into sections of 50 ml each, take the four sections as controls, and calculate the PH values of these four controls.
The desired values were adjusted by dropwise addition of 0.1N sodium hydroxide or 0.1 hydrochloric acid. For the other categories, a predetermined amount of THPS was added to each category, and the PH value was immediately adjusted to the predetermined value. All sections were incubated at 30°C for 19 hours. Bacterial load was then measured using standard plate counting. The results are shown below:

[Table] In this way, commonly found in cooling water systems (equipment)
THPS can prove effective as a fungicide over the entire range of PH values. Example 4 Activity against Algae Tap water from South Staffordshire, UK was dechlorinated by adding a small excess of sodium thiosulfate. Weigh 50ml portions of this water into each of two screw-top glass containers, inoculate each portion with a mixed culture of unicellular and filamentous algae, and inoculate one glass container with a mixed culture of unicellular and filamentous algae.
150 ppm of THPS was administered, and the other was left untreated as a control. Both glass containers were capped and exposed to light for 7 days. At the end of this period, there was green, growing algae in the untreated glass containers (control), but no viable algae could be detected in the treated glass containers. Example 5 [Plant Test 1] A full-scale test was conducted on an industrial open evaporative cooling system with the following parameters: (a) System capacity 99,968 (22,000 gallons) (b) Circulation rate 327,168/hour (72,000 gallons) /hour) (c) Cooling tower 4 x induced draft (d) Temperature drop 6°C (e) Concentration factor 1.5 The cooling system is used continuously and the temperature in the circulating water, measured by standard plate measurement immediately before the test is carried out, is The amount of bacteria was approximately 10 ⁶ per ml. When 120 ppm of THPS was injected into the water of this cooling system, the amount of bacteria in the circulating water decreased to about 200 per ml after 3 hours. I did not experience any problems with foaming. This example is used as a disinfectant in large industrial cooling systems.
This explains the effectiveness of THPS. Example 6 Another full-scale test was conducted on a second industrial open evaporative cooling system. The parameters of the device are as follows. (a) Equipment capacity 45440 (10000 gallons) (b) Circulation rate 454400/hour (100000 gallons/hour)
time) (c) Cooling tower 3 x forced draft draft (d) Temperature drop 5°C (e) Concentration factor 2 The cooling system is for continuous use, and the bacteria in the circulating water measured by standard plate counting immediately before the test. The amount was 2000 pieces per ml. When 96ppm of THPS was added to cooling water, the amount per ml within 1 hour
The number of bacteria decreased to 100. I have experienced problems with foaming. This example is used as a bacterial agent in industrial cooling water systems.
This further explains the effectiveness of THPS. Example 7 Bactericidal activity of other THP salts THPC (tetrakis hydroxymethylphosphonium chloride) (added as 80% by weight aqueous solution) and THPP (tetrakis hydroxymethylphosphonium phosphate {750 g of tri[tetrakis(hydroxymethyl)phosphonium] per 1 Kg of solution)
(added in the form of an aqueous solution containing a concentration of tetrakis(hydroxymethyl)phosphonium groups corresponding to the phosphate) was tested against Pseudomonas aeruginosa according to the test method described in Example 1. The results obtained are shown below.

[Table] Therefore, THP components chloride and phosphate have a PH
6.6 to prove at least as effective as biocides such as THPS against cooling water bacteria. Example 8 Liquid Scouring Formulation A liquid scouring formulation was prepared according to the following formulation: Ingredients wt % Synthetic Viscosity (trade name Laponite B ^R , Laporte Industries, UK)
(LaponiteB ^R )] 0.67 Gum arabic 0.04 Fatty acid diethanolamide [trade name Empiran from Albright & Willson, UK]
Sold as CDE ^R (EMPILA CDE ^R )]
2.30 Ground Calcium Carbonate 30.09 Water 66.90 Shoud Water Monas aeruginosa active cultures were prepared in a nutrient broth as described in Example 1. 0.2 ml of the final culture process was added to 50 ml of the above formulation to obtain a concentration of approximately 10 bacteria per ml. The infected formulation was divided into three equal parts, with the first part used as a control (i.e., no biocide added) and the second and third parts containing THPS-75 (i.e., 75% of the THPS used in Example 1). (aqueous solution) was added to bring the THSP level of each formulation to 500 ppm and 1000 ppm. All three compartments were incubated for 16 hours at 30°C and the amount of bacteria in the compartments was counted by standard plate counting method. The results obtained are as follows. THPS−75 concentration Number of viable bacteria per ml (ppm) Number of viable bacteria per ml 0 2500 500 0 1000 0 Example 9 Detergent formulation A liquid detergent formulation was prepared according to the following formulation: Ingredients wt % nonylphenol ethoxylate [Al] Trade name Empiran from Bright End Wilson
Sold as NR9 ^R (EMPILANNR9 ^R )]
10 Water 90 The bactericidal test in Example 8 was repeated using the above formulation and the results obtained are shown below: THPS-75 Concentration (ppm) Number of viable bacteria per ml 0 10 ⁸ 500 0 1000 0 Example 10 Adhesive Paste Formulation An adhesive paste formulation was prepared according to the following formulation. Ingredients Weight % Sodium Carboxymethyl Cellulose (Courtaulds Limited, UK)
Courlose ^R (Trade name: Courlose ^R )
3 Water 97 The bactericidal test method described in Example 8 was repeated using the above formulation and the results obtained are listed below: THPS-75 Concentration (ppm) Number of viable bacteria per ml 0 1500 500 0 1000 0 Example 11 Detergent formulation A detergent formulation was prepared according to the following formulation: Ingredients wt % Sodium ligninsulfonate (Trade name Borresperse ^{N R} from Borrgaard, Norway) 5 Water 95 The bactericidal test method described in Example 8 was repeated using this formulation and the results obtained are shown below: THPS-75 Concentration (ppm) Viable Bacteria per ml 0 10 ⁸ 500 5x 10 ³ 1000 10 1500 0 Examples 8-11 above demonstrate the effectiveness of the compounds of the present invention as biocides for use in aqueous-based formulations. Example 12 Oxygen scavenging activity The compounds of the invention have the ability to react with dissolved oxygen as shown in the following experiment: Aerated deionized 1 was mixed with a stirrer and an oxygen electrode (manufactured by EIL Limited, UK).
model 1511) in a sealed glass container. To read the concentration of oxygen dissolved in water, use a dissolved oxygen meter (manufactured by Yale Limited, model
1510) and X/Y recorders. In the experiment, the temperature was set at 25° C., and 0.1N sodium hydroxide solution was added in an amount sufficient to bring the pH of the solution to about 9 when 500 ppm of THPS-75 was then added. The concentration of dissolved oxygen at the time of addition of THPS-75 was about 10 ppm, and at pH 9, the reaction rate between dissolved oxygen and the removing agent was extremely slow. But 0.1
The reaction rate increased when normal hydrochloric acid solution was added to lower the pH to 7. When the pH was 6.2, the concentration of dissolved oxygen in water decreased from 10 ppm to 0 ppm within 50 seconds. Comparative Example B Activity of Long-Chain Alkylphosphonium Salts Simultaneously with the experiment described in Example 2, a similar experiment was conducted using the same test medium to evaluate the activity of lauryltributylphosphonium chloride (LTBPC) as a fungicide. Ta. For convenience, results are presented for a 75% solution of LTBPC to directly compare the activity of LTBPC and THPS. LTBPC concentration (ppm) Number of viable bacteria per ml 0 10 ⁷ 13.3 10 ⁶ 26.7 10 ⁵ Based on the above results and the results obtained in Example 2, on a weight/weight basis, THPS is LTBPC as a disinfectant against cooling water bacteria. It can be observed that it is more effective than Comparative Example C Activity of Other Alkylphosphonium Salts Some other alkylphosphonium salts were used in Example 2.
Tests on chilled water bacteria were conducted according to the method described in . The alkylphosphonium salts used in the above tests are listed below: Triphenylmethylphosphonium chloride Tributylbenzylphosphonium chloride Tributyl-3,4-dichlorobenzylphosphonium chloride Tributylmethylphosphonium chloride All of the above-mentioned compounds were completely absorbed even at a concentration of 200 ppm. Observed to be inert. These examples demonstrate that short chain phosphonium salts without a hydroxyalkyl group attached to the central phosphorus atom tend to be inactive as disinfectants against cooling water bacteria. Example 13 Activity against fungi Fungal spores isolated from an industrial refrigeration system were used in this test. The various fungi were not clearly identified. It was thought to be Aspergillus fungi. Prepared 50 ml aliquots of infected water. One section was not treated as a control, and the other sections were treated with 100 ppm and
Treated with 200 ppm THPS-75. The water sections described above were incubated for 5 days at 30°C and the extent of fungal infection was measured using standard plate counting methods. The results obtained are listed below: THPS-75 Concentration (ppm) Number of viable bacteria per ml 0 500 100 500 200 50 It was thus proved that the THP component is an active bactericidal agent. Other aqueous environments that can be treated using the hydroxyalkyl phosphorus compounds according to the process of the invention are boat mills, fertilizer production, oil refineries, primary metal production such as steel or copper, petrochemicals, rubber production, the textile and textile industry, industrial gas production, mineral recovery, glass and ceramic production, food industry, leather tanning, metal 2
Heavy and light industry, including further processing and automobile industry;
Cooling water or operating water in furniture manufacturing, electronics industry, surface coating and adhesive manufacturing and other manufacturing industries.

Claims (1)

[Claims] 1 General formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, (n+m) is 2 or 3, and x is 0 or 1 and (n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(where R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] Growth inhibitor of aqueous microorganisms. 2. The aqueous microorganism growth inhibitor according to claim 1, wherein R is a methylene group. 3. The aqueous microorganism growth inhibitor according to claim 1 or 2, wherein R' is a HOR- group. 4. The aqueous microorganism growth inhibitor according to claim 3, wherein n=3, m=0, and x=1. 5. The aqueous aqueous microorganism growth inhibitor according to claim 4, wherein X is a sulfate anion, a chloride anion, or a phosphate anion. 6 Phosphorus compounds have the general formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, (n+m) is 2 or 3, and x is 0 or 1 and (n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(wherein R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] or a homocondensate of the phosphorus compound, or urea, dicyandiamide, The growth inhibitor of aqueous microorganisms in an aqueous system according to claim 1, which is a compound containing at least two phosphorus atoms per molecule, which is a condensation product in the presence of thiourea or guanidine. 7. A patent in which the growth inhibitor of aqueous microorganisms in a water system contains at least one water treatment additive selected from scale inhibitors, corrosion inhibitors, flocculants, dispersants, antifoaming agents, oxygen scavengers, and biocides. The growth inhibitor of aqueous microorganisms in an aqueous system according to any one of claims 1 to 6. 8. The growth inhibitor of aqueous microorganisms in a water system according to any one of claims 1 to 7, wherein the water system is industrial cooling water or treated water. 9. The aqueous aqueous microorganism growth inhibitor according to claim 8, wherein the industrial cooling water is cooling water in a power plant, chemical plant, steel mill, paper mill, or brewery. 10. The aqueous aqueous microorganism growth inhibitor according to claim 8, which is aqueous oil field injection water. 11 Claims 1 to 7 in which the water system is any one of geothermal water, water for central heating equipment, water for air conditioning equipment, water for hydrostatic pressure testing, water for swimming pools, and engine cooling water for ships. The aqueous aqueous microorganism growth inhibitor according to any one of the above. 12. The aqueous aqueous microorganism growth inhibitor according to any one of claims 1 to 7, wherein the water used for swimming is water from a water-based product. 13 Water-based products include paints, cutting oils, bituminous emulsions, tar emulsions, adhesives,
Claim 1 which is a weedicide or insecticide
The growth inhibitor of aqueous microorganisms according to item 2. 14 In the method of suppressing the growth of aqueous microorganisms in water systems, the general formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, and (n+m) is 2 or 3, x is 0 or 1, and (n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(where R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] 1. A method for inhibiting the growth of aqueous microorganisms in an aqueous system, which comprises adding a microbial growth inhibitor in an amount of 1 to 5,000 parts by weight per 1 million parts by weight of water to be treated. 15 Claim 1 in which R is a methylene group
The method for inhibiting the growth of aqueous microorganisms according to item 4. 16 Claim 1 in which R' is a HOR- group
The method for inhibiting the growth of aqueous microorganisms in an aqueous system according to item 4 or 15. 17. The method for inhibiting the growth of aqueous microorganisms in a water system according to claim 16, wherein n=3, m=0, and x=1. 18. The method for inhibiting the growth of aqueous microorganisms in a water system according to claim 17, wherein X is a sulfate anion, a chloride anion, or a phosphate anion. 19 Phosphorus compounds have the general formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, (n+m) is 2 or 3, and x is 0 or 1 and (n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(wherein R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] or a homocondensate of the phosphorus compound, or urea, dicyandiamide, 15. The method for inhibiting the growth of aqueous microorganisms in an aqueous system according to claim 14, which is a compound containing at least two phosphorus atoms per molecule, which is a condensation product in the presence of thiourea or guanidine. 20. A method for inhibiting the growth of aqueous microorganisms in an aqueous system according to any one of claims 14 to 19, which comprises adding an aqueous microorganism growth inhibitor to industrial cooling water or treatment water. 21. The method for inhibiting the growth of aqueous microorganisms in a water system according to claim 20, which comprises adding an aqueous microorganism growth inhibitor to cooling water in a power plant, chemical plant, steel mill, paper mill, or brewery. 22. A method for inhibiting the growth of aqueous microorganisms in a water system according to claim 20, which comprises adding an aqueous microorganism growth inhibitor to oil field injection water. 23 Claim 14: Adding an aqueous microbial growth inhibitor to any one of geothermal water, water for central heating equipment, water for air conditioners, water for hydrostatic pressure tests, water for swimming pools, and engine cooling water for ships. The method for inhibiting the growth of aqueous microorganisms in an aqueous system according to any one of Items 1 to 19. 24 Claims 14 to 1 which involve adding an aqueous microbial growth inhibitor to a water-based product
The method for inhibiting the growth of aqueous microorganisms in an aqueous system according to any one of items 9 to 9. 25. Addition of an aqueous microbial growth inhibitor to a water-based product selected from paints, cutting oils, bituminous emulsions, tar emulsions, adhesives, weedicides or insecticides Claim 24 A method for inhibiting the growth of aqueous microorganisms in an aqueous system as described in . 26. A method for inhibiting the growth of aqueous microorganisms in an aqueous system according to any one of claims 14 to 19, which comprises adding an aqueous microorganism growth inhibitor to water. 27. The method for inhibiting the growth of aqueous microorganisms in an aqueous system according to any one of claims 14 to 26, wherein the phosphorus compound is added in an amount of 1 to 1000 parts by weight per 1 million parts by weight of water in an aqueous system. 28. The method for inhibiting the growth of aqueous microorganisms in a water system according to claim 27, wherein the concentration of phosphorus compounds in the water system is maintained at 5 to 150 parts by weight per 1 million parts by weight of water. 29 Functional components and general formula [HORPR′ _o O _n ] _y X _x [where n is 2 or 3, m is 0 or 1, (n+m) is 2 or 3, and x is 0 or 1 and (n+x) is 2 or 4, and y
is equal to the valence of General formula HOR−
(wherein R has the same meaning as above), and X is a group that makes the phosphorus compound water-soluble] Aqueous microbial growth containing the phosphorus compound or its condensate as the main component A concentrated aqueous or solid mixture for inhibiting the growth of microorganisms in water systems, comprising: an inhibitor;