JPS6072807A - Bactericidal treatment for water system and composition therefor - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the treatment of water to inhibit the growth of submerged kerosene microorganisms.

%l(Pseudomonaa aaruginos
a) Bacteria such as Oscilladria (Oacillat)
Oria) and Saccharomyces Q. cerevisi x (8aoharomyaesc@rebisia
Yeast bacteria such as e) are used in industrial plants, chemical plants,
or grow into water or water-based products for injection into various water systems and oil fields, such as steel plants, power or paper plants, marine engines, central heating equipment.

It is desired to suppress the growth of

[Means for solving problems]

It has been found that phosphine or phosphonium compounds having one or more than λ hydroxyalkyl groups bonded to a phosphorus atom are extremely effective in inhibiting water spray microorganisms. It is particularly effective in the absence of long chain alkyl groups, which cause foaming problems in prior art fungicides, and is also cost effective. Furthermore, it is found less.

The present invention provides a percussion method comprising adding at least one phosphorus compound containing at least seven hydroxyalkyl groups bonded to a phosphorus atom to water that is likely to be contaminated with hydrophilic microorganisms containing M hydrogen or hydrophilic microorganisms. The present invention relates to a method for treating hydrogen containing aqueous microorganisms or hydrogen that is easily contaminated by water-borne microorganisms.

The above phosphorus compound contains one phosphorus atom and has the general formula (HO
RPR'nOm) 7XX (wherein n is ko or 3, m is O or 1, and n0m is ko or 3, X
is 0 or f, and n-4-x is ko or zhen, and y
is equal to the valence of X and R is an alkylene group of /-4' carbon atoms, preferably 1 carbon atom, l, co, 3
It also has a hydroxy group bonded to the carbon atom at the V position, and %R1 may be the same or different, preferably an alkyl or alkenyl group or a group of /~d carbon atoms. is a group represented by 2HOR- (where R has the same meaning as above), and X is an anion that makes the phosphorus compound water-soluble. In this way (-
The ROH) group is a l-hydroxyalkyl group or a dihydroxyalkyl group such as a hydroxymethyl group or a l-hydroxyalkyl group.
or -monohydroxyethyl group or l- or co-hydroxyprobyl group or l- or co-hydroxyptyl group, preferably at least one R1 is ROM
However, it may also be, for example, a methyl, ethyl, propyl, isopropyl or n-, iso- or tertiary-butyl group. and group (bisulfite), bisulfate residue (bisulfate),
or organic sulfonic acid residues such as methosulfate or benzene, toluene, xylene sulfonate, or cohydrogen phosphate (salt) residues or divalent anions such as sulfate or sulfite or/hydrogen phosphate residues or Trivalent groups such as phosphoric acid ester (
salt) residues or organic carboxylic acid residues having one or more carboxyl groups, such as citric acid residues. The phosphorus compound may be a phosphine oxide. Alternatively, the phosphorus compound may be at least o, s i
7. It may contain 2 or 3 or more phosphorus atoms as long as it has water solubility at a concentration of t. Such phosphorus compounds usually contain at least 7, preferably at least one hydroxyalkyl group per phosphorus atom. Such hydroxyalkyl groups preferably have the formula ROH (R
has the same meaning as above). One or more bonding groups that bond phosphorus atoms to each other have the formula 2R-
, -R-0-, -R-own- or -R-NH'-
R- or -R-R'-R (in these formulas R has the same meaning as above, R'' removes (rt) one hydrogen atom bonded to the nitrogen from the diamide or polyamide or diamine or polyamine) 2 or more, for example 3, hydroxyalkyl groups per phosphorus atom. A compound like this has 3 to 1 phosphorus atom.
Self-condensation of compounds to which one or more hydroxyalkyl groups are attached, such as the formula (HORPR'nOm) yXx, or condensation of said compounds with compounds of the formula R''H, (R- has the meaning given above), such as urea. The condensation can be carried out by heating at I'0-/-0°C.

Preferably the phosphorus compound contains only one phosphorus atom and 3 or V 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 acid, sulfuric acid or phosphoric acid. Depending on the proportions of the reactants, the product can be a trishydroxyalkylphosphine or a tetrakis(hydroxyalkyl)phosphonium salt. However, the latter is a dimeric compound or n-co, with two phosphorus atoms and an ROR bridging group under aqueous alkaline conditions.

There is a tendency for conversion to the former with formation of small amounts of m-/X=Q phosphine oxide or both. The product may contain up to 10 parts by weight of free aldehyde or ketone, such as formaldehyde, and up to 10 parts by weight of acid. Phosphorus compounds are usually /
It has a pH of '-A. Compounds in which one or more R, is an alkyl group can be prepared by reaction of the corresponding alkyl-substituted phosphine with an aldehyde or ketone. To avoid foaming, any alkyl or alkenyl groups present should be

Those with up to 5 carbon atoms are preferred. However, compounds having 1 or 1 alkyl or alkenyl group carbon atoms per molecule are effective biocides and are used according to the invention in applications where foaming is not a problem. Mokiru.

Examples of biocides according to the invention are tetrakis(hydroxymethyl)phosphonium sulfate, tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate and tris(
hydroxymethyl)phosphonium chloride or oleyltris(hydroxymethyl)phosphonium sulfate, although oleyltris(hydroxymethyl)phosphonium sulfate is less preferred than the others.

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, preferably 20 to 20 parts by weight. For example, tetrakis(hydroxymethyl)phosphonium groups o, b per 1 million parts by weight of water
~'yoo parts by weight, preferably 3 to ioo parts by weight, especially io to 30 parts by weight, or 1 phosphorus-bonded hydroxyalkyl group (especially hydroxymethyl group) per million parts by weight of water; 1I-aoo parts by weight preferably,
Add 2 to 60 parts by weight, especially g-20 parts by weight.

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, 6-9, typically 6-7 or tJ-9.

The book contains scale or corrosion inhibitors such as phosphonates (including aminomethylene phosphonates), polymerates, polyacrylates, polymethacrylates as scale inhibitors. Polyphosphates, or phosphoric esters, in the amounts conventionally used, inorganic corrosion inhibitors such as water-soluble zinc salts, nitrites or sulfites or organic corrosion inhibitors such as benzoates (esters), phosphonates (esters). , tannin, likunin, benzotriazole or mercaptobenzotriazole can also be used in amounts conventionally used. It is preferred that the phosphorus compounds according to the invention are not used together with chromates.

The scale inhibitor or corrosion inhibitor or scale inhibitor and corrosion inhibitor can be added separately or together with the phosphorus compound (15) according to the present invention.

It is also possible to add to the water to be treated oxygen scavengers, 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 composition for treating water containing water-storing microorganisms, the composition according to the present invention comprising a phosphorus compound containing at least 7 hydroxyalkyl groups bonded to a phosphorus atom; species or one or more other biocides and/or scale or corrosion inhibitors,
It consists of an oxygen scavenger, a flocculant, a dispersant and/or an antifoaming agent. The compositions of the invention may contain other biocides in addition to the phosphoric acid compound. The microorganisms to be treated are bacteria, molds, yeasts and algae that normally grow in aqueous environments. This classification includes sulfate root-reducing bacteria such as Desulfovibrio (D
esulphovibrio), iron-parasitic bacteria such as Gallionella and Slime (
(16) Bacteria such as Pssudomonas
), and this last type of bacteria is particularly troublesome in water systems. 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 water or brewing water. Oil field injection water or water used in reverse osmosis plants for example 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, industrial 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 in various solutions and emulsions such as paints, cutting oils, bituminous emulsions, tar emulsions, adhesives, weedicides and insecticides, and for adding water in the production of the above products. Can be added to solids and concentrates. Accordingly, the present invention provides a water-based product that is susceptible to microbial damage, to which a sterilizing or bactericidal amount of a phosphorus compound containing at least one hydroxyalkyl group bonded to a phosphorous atom is added. is to provide. Representative examples of such compositions consist of an aqueous liquid, suspension or emulsion containing at least t functional ingredients and a minor amount of a phosphorus compound of the invention in an amount sufficient to inhibit the growth of microorganisms. .

Particularly suitable systems for applying the invention are bacteria, especially P.
under conditions favorable to the growth of cold-resistant bacteria such as P. aeruginosa, such as conditions consisting of storing or periodically increasing the temperature of the water at an environmental temperature favorable to the growth of bacteria, or in an aqueous system. A system that circulates or stores large amounts of water under conditions that maintain nutrients for the bacteria.

〔Example〕

The present invention will be explained 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 5% by weight aqueous solution of tetrakis(hydroxymethyl)phosphonium sulfate, hereinafter referred to as THPS, which contains OAt% free formaldehyde;
frL, pH is V. Formaldehyde for comparison is (
A 70% aqueous solution was used. Dosages are as follows, unless otherwise specified:
All values are expressed in parts by weight of the aqueous biocide solution based on 7 million parts by weight of water to be treated.

Example 1 [Pseudomonas aeruginosa (Paeudo
activity against Pseudomonas aeruginosa] A lyophilized monoculture of Pseudomonas Q aeruginosa (No/B t2qs), supplied by Torrey Laboratories, was incubated in a nutrient broth at 30° C. for approximately -3 hours to form a turbid mass. caused.

(l?) Subsequently, λ fractional cultures were performed to confirm that the bacteria were in an active growth state. That is, Ringer's (Rlng
el ) was added to 5 ood of liquid to uniformly disperse the prosthesis. This inoculated solution was cultured at 3θ°C for 2 hours to obtain a standard test medium containing to'' bacteria per lig.

This test medium was divided into 5 otd sections.

- leave one section as a control, other sections receive various amounts of TH
A proprietary intiazolone-based biocide was administered for PS solution and comparative data.

After incubation for t6 hours at room temperature, the amount of bacteria in each section was counted by standard plate counting method.

The results are as follows: Concentration of viable bacteria per liter of biocide THPS Proprietary Intiazolone Q 10” 1
0″ 20 5x10s /θ7 30 600 / 07 'I Ob O/ 0''! 0 '0 / 0'' THPS is thus highly effective against P. 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 test. The microbiological population was observed to be mixed, but the predominant microorganisms were Gram-negative rod-shaped bacteria, and it was unclear.

A test medium containing 10" or more bacteria per day was preliminarily dechlorinated by adding a small excess of thiosulfate. The test medium was divided into sections of 50 d each, one section was left as a control, and the other sections received various amounts of water. T.H.
PS was administered. After incubation for 16 hours at room temperature, the amount of bacteria in each section was measured by the standard plate it method. The results are shown below: o to7 10 /Q' 20 2X10'' 3θ /10 ri0 2θ too.

Therefore, it can be seen that bacteria from industrial cooling water are effectively sterilized by THPS.

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 operations described in Example C, a similar test was conducted using the same medium as in Example λ and adding formaldehyde. The results obtained are as follows: 0 107 0, / / 07 0J 10" /, 0 /Q6 !, 0 /Q6 Theoretically 30 ppm THPS reacts completely with water, resulting in 3.3 ppm formaldehyde. generate.

j Oppm of THPS was shown to reduce bacterial counts from 107 per liter to /SO (see results in example λ). From the above results of this comparative example, even sp ppm formaldehyde only slightly reduces the number of bacteria, so THPS? It can be concluded that the activity of M bacteria is not due to free formaldehyde.

Example J (Effect of PH) A series of tests in this example were conducted on the effects of PH, which is commonly found in cooling water systems.
This was done to demonstrate that THPS has bacterial activity over a range of H values.

A sample of circulating water from an industrial cooling water system heavily contaminated with microorganisms was used as the microbial source for this study. The microbial population was observed to be a mixture, with the predominant microorganism being Bacillus 0ereus.
) was identified as

The contaminated circulating water was added to the nutrient broth and then incubated for approximately 2 q hours in Jo'C until turbidity occurred.
The above broth iow was added to 5 g of tap water from South Staff Ordshire, UK. This bacterial suspension was used as a test medium.

Test medium f! Divide into 0111 sections, take that group as a control, and calculate the pH values of these V controls by θ.
,/N sodium hydroxide or 0. The desired value was adjusted by dropwise addition of IN hydrochloric acid.

For other categories, add the specified amount of THPS to each category,
The pH value was quickly adjusted to a predetermined value. 30 total categories
l in °C? Cultured for hours. Bacterial load was then measured using standard plate counting. The results are shown below: THPS Dose Survival Ob per lll of solution
10' 2z b io' jθ b 10' 100 6 λ3θ 2q0 6 0 0 ? 107 λj, ? 10' so 7 3sO 1007/3θ Of 107 Koj t l is 10 II 50θ 100 t /6θ Oji lO7 debate te lol' IO9!00 100 ? / 70. 200 0 TUPS can thus prove to be effective as a disinfectant over the entire range of pH values normally found in cooling water systems.

EXAMPLE Activity against algae (A1gaθ) Tap water from South Staffordshire, UK was dechlorinated by adding a small excess of thiosulfuric acid I-U rum. A 5 Qd portion of this water was weighed into each of two screw-capped glass containers, each portion was inoculated with a mixed culture of unicellular rings and filamentous algae, and one glass container was filled with TH.
PS/tO];'I'm 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, untreated glass containers (
A cluster of green algae was formed in the control), but no living algae could be detected in the treated glass container.

Example 5 [Plant Test 1] A full-scale test was conducted on an industrial open type evaporative cooling system having the following parameters = (a) Equipment capacity it qq
, tpbgl, (λkoOθ0 gallons) calons/hour) (C) Cooling tower IIx induced draft (d) Temperature drop 6°C (61 concentration factor 1.! The cooling system is used continuously and the The amount of bacteria in the circulating water measured by the plate measurement method was approximately 10 per 1 at.
After 3 hours of injection of THPS i, the amount of bacteria in the circulating water decreased to about 0.0 mA'/7 mA'. \I
I did not experience any problems with KK foaming.

This example illustrates the effectiveness of THPS as a disinfectant in large industrial refrigeration systems.

Example 6 Another full-scale test was conducted on the first industrial open evaporative cooling device. The parameters of the equipment (27) are as follows;
(100,000 gallons/hour) (C) Cooling tower 3 x forced draft draft (d) Temperature drop 1°C (e) Concentration factor The chiller is for continuous use and was measured by standard plate measurement immediately prior to testing. The amount of bacteria in circulating water is / txl
The total was 1000 pieces. When 894 ppm of 'rHP was added to cooling water, the number of bacteria decreased to ioo bacteria//- within 7 hours. I wanted to experience the problem of foaming.

This example further illustrates the effectiveness of THPS as a bactericidal agent in industrial cooling water systems.

Example 7 Bactericidal activity of other THP salts THPC (tetrakis hydroxymethylphosphonium chloride) (added as a go-weight aqueous solution) and THPP
(Added in the form of an aqueous solution containing tetrakis(hydroxymethyl)phosphonium groups at a concentration corresponding to tri[tetrakis(hydroxymethyl)phosphonium]phosphate) (Tetrakishydroxymethylphosphonium phosphate (solution/Kpmsu7jO(, 2g>I) ) was tested against Pseudomonas aeruginosa using the test method described in Examples.The results obtained are shown below: Therefore, the THP components chloride and phosphate were tested at pH 4.6.
It has been shown to be at least as effective as biocides such as 'I'HP B against cooling water bacteria.

EXAMPLE Liquid Scouring Formulation A liquid scouring formulation was prepared according to the following formulation: Ingredients Weight: Gum Arabic 0.0 Hirosu Le 6°? 0 Active cultures of Pseudomonas aeruginosa are shown in Examples/
Produced in a nutritional process as described in . Add 0.1 rnl of the final culture process to the above formulation kOm and l-
A bacterial concentration of approximately 10 bacteria was obtained. Divide the infected formulation into three equal parts, use the first part as a control (i.e. no biocide added), and add THps-tz to the third and third parts.
(i.e., the 7! water solution of TH8P used in Example/) and check the rH3P level of each formulation!
r 00 ppm and l100 Opp.

All three compartments were incubated for 76 hours at 30°C and the amount of bacteria in the compartments was counted by standard plate counting. The results obtained are as follows.

Oko5OO 5OOθ 1000 0 Example Detergent Formulation A liquid detergent formulation was prepared according to the following formulation: Ingredients Weight - Water ? 0 The bactericidal test in Example 1 was repeated using the above formulation (31) and the results obtained are shown below: I'H
Number of viable bacteria per PS-75 concentration /- (ppm) Q 10 @ zoo.

Noooo.

Example 10 Adhesive paste formulation Adhesive paste formulations were made according to the following formulation.

Ingredients Weight - Water The bactericidal test method described in Example t was repeated using the above formulation and the results obtained are described below; (3) θ /, j 00 zoo .

1000 0 Example // Detergent formulation A detergent formulation was prepared according to the following formulation: Ingredients Weight - Water Dej The bactericidal test method described in Example g was repeated using this formulation and the The results are shown below: 0 10" gOq! x 10" 1000, 10 soo.

Examples j-// above demonstrate the effectiveness of compounds of the invention as biocides for use in aqueous-based formulations.

EXAMPLE/C Oxygen scavenging activity The compounds of the present invention have the ability to react with dissolved oxygen as shown in the following experiment: Aerated deionized/l was mixed with a stirrer and an oxygen electrode (EIL Lim1ted, UK). ), model lr//). To read the concentration of oxygen dissolved in water, use a dissolved oxygen meter (manufactured by Yale Limited, model /!;10) and x/
Provided by Y Recorder.

Experiment with temperature! ℃, set to 0. A sufficient amount of normal sodium hydroxide solution was added so that the pH of the solution would be approximately 0 when 200 ppm of THP8-7j was added.

'rHPS-? The concentration of dissolved oxygen at the time of addition of j is approximately /Oppm, and the pH? The reaction rate between dissolved oxygen and the scavenger was very slow. However, 0. / Normal hydrochloric acid solution was added to lower the pH to 7 and the reaction rate increased. When the pH was 6°λ, the concentration of oxygen dissolved in water decreased from /Oppm to Oppm within 50 seconds.

Comparative Example B-Activity example of long-chain alkylphosphonium salt-
A similar experiment was conducted simultaneously with the experiment described in , using the same test medium, to evaluate the activity of lauryltributylphosphonium chloride (LTBPC) as a fungicide.

For convenience, results are presented for a qsts solution of LTBP(!) to directly compare the activity of LTBPC and THPS.

0 10' /3. ,? 104 JA, 7 10'' From the above results and the results obtained in Example 1, it can be observed that on a weight/weight basis, THPS is more effective than LTBPC as a disinfectant against cooling water bacteria.

Several other alkylphosphonium salts were tested against chilled water bacteria according to the method described in Examples. The alkylphosphonium salts used in the above tests are described below: triphenylmethylphosphonium chlori-todriptylbenzylphosphonium chloridetriphthyl-J,4'-
Dichlorobenzylphosphonium chloride Tributylmethylphosphonium chloride All of the above compounds were observed to be completely inactive even at concentrations of 100 ppm.

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/J Activity against Ws Fungal spores isolated from an industrial cooling system were used in this test. The various fungi were not clearly identified (34). It appeared to be Aspergillus fungi.

A 5ol1 fraction of infected water was prepared. 7 sections were not treated as controls, and the other sections were treated at / 00 ppm and -〇
〇 ppm (7) Treated using THPS-75.

The above water classification at 30℃! After incubation for days, the extent of fungal infection was measured using standard plate counting methods.

The results obtained are described below: Q! ;00 ioo zo.

Cooos.

It was thus demonstrated that the rHP component is an active fungicide.

Other aqueous environments that can be treated using hydroxyalkyl phosphorus compounds according to the method of the invention include boat mills, fertilizer production,
Refineries, 7th metal production such as steel or copper, petrochemicals,
Heavy and light industry, including rubber manufacturing, textile and textile industry, industrial gas production, mineral recovery, glass and ceramic manufacturing, food industry, leather tanning, metal processing and automotive industry, furniture manufacturing, electronics industry, surface coatings and Cooling water or operating water for adhesive manufacturing and other manufacturing industries.

, -ko-\・-■ 73-

Claims (1)

[Claims] l General formula % formula % [wherein n is co or 3, m is O or l, but (
n+m) is ko or 3, X is O or t, and (
n-)x) is co or da, y is equal to the valence of an alkyl or alkenyl group of up to 1 carbon atoms or of the general formula HOR- (where R has the same meaning as above)
A group represented by the following formula, where X is an anion that makes the phosphorus compound water-soluble. spraying of water systems subject to water-borne microbial contamination, consisting essentially of a combination of a condensate of said compound with at least one other water treatment additive selected from agents, oxygen scavengers and biocides. A composition for use in a treatment method for inhibiting the growth of aqueous microorganisms. λ In a treatment method for suppressing the growth of water-sprinkling microorganisms in a water system that is contaminated with water-sprinkling microorganisms, at least one phosphorus compound containing at least one hydroxyalkyl group directly bonded to a phosphorus atom is added to the water system. A treatment method for inhibiting the growth of water-borne microorganisms in a water system. Yulin compound or general formula % formula %) [In the formula, n is kodan or 3, m is O or l, but (
n0m) is λ or 3, X is O or /, and (
nx) is co or V, y is equal to the valence of X, R is an alkylene group of /~c carbon atoms, and R1 may be the same or different . an alkyl or alkenyl group having up to 2V carbon atoms or a group represented by the general formula HOR- (where R has the same meaning as above), where X is an anion that makes the phosphorus compound water-soluble; ] The method according to claim 2, which is represented by: 4. The method according to claim 3, wherein 4+R is a methylene group. A method according to claim 2 or claim V, wherein j R' is a HOR- group. 1n-J, m=O, and X=/. 7. The method according to claim 6, wherein 2x is a sulfate anion, a chloride anion or a phosphate anion. g A phosphorus compound having at least 7 phosphorus atoms in one molecule, with the general formula %) [where n is λ or 3, m is O or X is O or 1, and (n 10x) is Ko or Hiro, y is equal to the valence of
an alkyl or alkenyl group having up to 3 carbon atoms or a group represented by the general formula HOR- (where R has the same meaning as above), and X is an anion that makes the phosphorus compound water-soluble; ] The method according to claim 2, which is produced by condensation of a compound represented by the above alone or by condensation of said compound in the presence of urea, dicyandiamide, thiourea or guanidine. 9 1J compound per 7 million parts by weight of water to be treated
The method according to any one of claims 2 to 1, wherein the θθθ weight is added in an amount of 1 part. IQ The method according to claim 1, wherein the concentration of phosphorus compounds in the aqueous system is maintained at between J and iso parts by weight per 10,000 parts by weight of water. /lM The method according to any one of claims 7 to 70, wherein the treated water is industrial cooling water or treated water. 1. The method according to claim 1 for treating cooling water of a power plant, a chemical plant, or a steel factory, or treated water of a paper factory or a brewery. A method according to claim 1 for treating injection water of an oil field. llA Claims for treating geothermal water or water for central heating or air conditioning equipment, or for treating water used for hydrostatic pressure tests or for water used in swimming pools or for cooling water for marine engines The treatment method according to any one of Items C to 1O. General formula % formula %) [In the formula, n is 0 or 3, m is O or (1') l, but (n0m) is 0 or 3, X is O or 1, and (n+x) is C or G, and y is X
R is an alkylene group of /-4 carbon atoms, and R' may be the same or different, but is an alkyl group of up to 4 carbon atoms, or an alkenyl group. or a group represented by the general formula HOR- (where R has the same meaning as above), where X is an anion that makes the phosphorus compound water-soluble] or a condensate thereof. and at least one other water treatment additive selected from corrosion inhibitors, flocculants, dispersants, defoamers, oxygen scavengers and biocides.
A method according to claim 1, comprising adding to water a composition consisting essentially of seeds. If no biocide is added, microbial contamination will occur, but this can be avoided by adding at least one phosphorus compound containing at least one hydroxyalkyl group directly bonded to a phosphorus atom to the water base. A water-based product consisting of an aqueous suspension or emulsion containing at least one functional ingredient that inhibits or inhibits the growth of microorganisms in a water-based material. 12. The water-based product according to claim 76, wherein the water-based product is a paint, a cutting oil, a bituminous emulsion, a -leumulsion, an N-contact agent, a weed killer, or an insecticide. product. /1 Functional components and general formula % formula %) [In the formula, n is co or 3, m is O or l, but (
n+m) is λ or J, X is O or /, and (
n+x) is co or g, y is equal to the valence of an alkyl group or an alkenyl group of a carbon atom or a general formula HOR- (where R has the same meaning as above)
A group represented by the formula (7), where X is an anion that makes the phosphorus compound water-soluble (7). Concentrated aqueous mixtures or solid mixtures for addition to ferrous water-based products to suppress or inhibit the growth of microorganisms in the base products. /f Concentrated aqueous mixture or solid mixture according to claim 1t, wherein the water-based product is a paint, a cutting oil, a solid emulsion, a tar emulsion, an adhesive, a weed killer or an insecticide. .