JP2006510713A - Pyrithione biocide enhanced by zinc metal ions and organic amines - Google Patents

Abstract

The present invention relates to a pyrithione or pyrithione complex in an amount of about 0.5 wt% to about 30 wt%, a zinc source in an amount of about 0.1% to about 10%, an organic amine in an amount of about 30% to about 80%. It relates to a stable and soluble antibacterial concentrate composition comprising the components (the% is based on the total weight of the composition concentrate). The present invention also relates to a method for controlling the growth of native microorganisms or biofilms using the antimicrobial composition of the present invention, and to products made using the antimicrobial composition of the present invention.

Description

  The present invention relates to pyrithione biocides, in particular pyrithione, pyrithione salts, or pyrithione adducts, zinc sources such as zinc alloys, zinc oxide, zinc hydroxide, or zinc salts, and 1,2-1, It relates to a stable and soluble biocidal composition showing an increased biocidal effect comprising an antibacterial effective combination with 3-alkanolamines and 1,2-1,3-alkyldiamines. The biocidal composition may be formulated directly into a functional fluid (e.g., metalworking fluid) or in the form of a biocidal concentrate composition suitable for incorporation into a functional fluid “masterbatch”. Given.

  Pyrithione (1-hydroxy-2-pyridinethione; 2-pyridinethiol-1-oxide; 2-pyridinethione; 2-mercaptopyridine-N-oxide; pyridinethione; and pyridinethione-N-oxide ) Are known to be effective biocides and are widely used as fungicides and bactericides in paints and metalworking fluids. Pyrithione is used in human care products such as anti-dandruff shampoos as well as fungicides and bactericides. The polyvalent metal salts of pyrithione are very slightly soluble in water, including ferric pyrithione, ferrous pyrithione, aluminum pyrithione, bismuth pyrithione, strontium pyrithione, copper pyrithione, zinc pyrithione, cadmium pyrithione, and Zirconium pyrithione is included. The most widely used divalent pyrithione salts are zinc pyrithione and copper pyrithione.

  Zinc and copper pyrithione are useful as antibacterial agents active against gram positive and negative bacteria, fungi, and yeast. Zinc pyrithione is used as an anti-dandruff component in shampoos, while industrial suspensions of zinc pyrithione and / or copper pyrithione are used as paint and polymer preservatives. These same salt powders are also used as biocidal aids in antifouling paints. The synthesis of polyvalent pyrithione salts is described in US Pat. No. 2,809,971 by Berstein et al. Other patents disclosing similar compounds and methods of making them include U.S. Pat. Nos. 2,786,847, 3,589,999, 3,590,035, and 3,773. No. 770 is included.

  Although pyrithione biocides have been found useful in a wide range of applications outlined above, the usefulness of these compounds is limited to the control of certain species and strains of fungi and bacteria. . Furthermore, while increasing the concentration of pyrithione or its salts has been observed to inhibit the growth of a wider range of organisms, the effective amount of pyrithione or its salts that can be added to commercial products is effective. Limited by economic considerations and, to a lesser extent, by environmental and toxicological issues.

  Inorganic zinc salts such as zinc chloride, zinc sulfate, and zinc oxide have been used as bacteriostatic and / or fungistatic compounds in a wide variety of products including paints, coatings, and preservatives. However, although zinc salts are less toxic than pyrithione or its salts, these compounds do not have the great biocidal efficacy desired in many commercial applications.

  Certain combinations of pyrithione and zinc are known in the art. By way of example, US Pat. Nos. 5,854,266 and 5,883,154 describe aqueous antimicrobial compositions protected against discoloration due to the presence of ferric or copper ions. In this case, the composition comprises pyrithione and an effective amount (0.001% to 10%) of an organic acid zinc salt, an inorganic acid zinc salt, zinc hydroxide, zinc oxide, and their Contains a zinc compound selected from the group consisting of combinations. However, this patent does not describe anything about the beneficial antibacterial effect between pyridione and zinc. Furthermore, at the concentrations used in this patent, the pyrithione and zinc composition was not soluble and could therefore not be sent together as a soluble biocide composition. As another example, U.S. Pat. No. 4,161,526 includes skin or hair containing 0.01% to 1% zinc salt of organic or inorganic acid, zinc hydroxide, zinc oxide, or combinations thereof. White to cream yellow pyrithione salts or dipyrithiones are described. However, this patent does not describe any beneficial effect between pyrithione and zinc salt, which would not form a soluble composition of pyrithione and zinc.

  Bacteria and fungi have provided microbial contamination problems for many years, but recently biofilms have been recognized as an important new source of microbial contamination. Biofilms are generally characterized as cell aggregates that adhere to each other or adhere to the surface by an extracellular mucus layer. Biofilms are generally found as contaminants in metalworking fluids. This is because these fluids contain a good carbon source for the growth of organisms found in biofilms. However, the presence of high concentrations of biofilm in metalworking fluids can result in rapid degradation of the fluid, which can cause equipment problems and failures.

  Biofilm growth on the surface may also increase the corrosion rate of the metal surface and increase the degradation rate of the paint, the surface coating, and the structural material under the coating. In the hull, the presence of biofilm will increase drag and may promote colonization by larger invertebrate biocontaminated organisms. Biofilms often cause both internal and skin infections. As biofilm resistance to antimicrobial treatment increases, biofilm-related infections are often more difficult to treat. Medical devices such as heart transplants and catheters, and medical instruments such as dialyzers and dental water pipes can also become contaminated with biofilms and spread infections.

  Efforts to control biofilm growth and reproduction have been made to date, but these efforts have met with little success. Studies have shown that biofilm cells are much more resistant to disinfection than free-living cells, largely due to the extracellular mucus layer that acts as a protective coating. To do. In addition, previous microbial contamination control measures are typically developed in the laboratory against native organisms, with little or no caution when determining the effectiveness of antimicrobial agents on biofilms. Was not paid. Unfortunately, resistant biofilms are generally unaffected by previously used antimicrobial agents. Biofilms, if not removed or destroyed, can cause many problems in working fluid applications such as corrosion, blockage, mucus surface build-up, malodor, fluid instability, machine downtime, etc. is there.

  Further representative patents and publications showing the current state of the microbial sterilization field are as follows.

In US Pat. No. 4,654,213, a water soluble salt of zinc increases the activity of MgSO ₄ adduct (MDS) of 2,2′-dithiopyridine-1,1′-dioxide. An antibacterial composition is described.

US Pat. No. 4,370,325 describes 2,2′-dithiopyridine-1,1 including MgSO ₄ (MDS) and Zn salts for treating eye and ear irritation and inflammation. Compositions containing '-dioxide or one of its metal salt adducts are described.

U.S. Pat. No. 4,235,873 describes 2,2′-dithiopyridine-1,1′-dioxide, or one of its metal salt adducts, including MgSO ₄ (MDS) and Zn salts. Deodorant compositions containing are described.

British Patent GB 2230190A describes a preservative composition containing isothiazolone and a ZnCl ₂ adduct of 2,2′-dithiopyridine-1,1′-dioxide. However, this patent states nothing about the beneficial effects between pyrithione and zinc salts.

  Japanese Patent Application No. 6-134227 describes an antibacterial filter in which ZnO or ZnO and zinc pyrithione are blended. However, this patent does not describe anything about the beneficial effects between pyrithione and zinc salts.

  Japanese Patent Application No. 7-118103 describes an antibacterial composition for coating a stainless steel washer drum to prevent contamination of the internal surface, in which ZnO is a carrier in a ZPT thermoplastic coating. It is used as. However, this patent does not describe anything about the beneficial effects between pyrithione and zinc salts.

  Technical journal has been found that the presence of 0.2% metallic copper or 0.2% metallic zinc reduces the biocidal activity of sodium pyrithione in 12 different metalworking fluids. It is described in the paper [E. O. Bennet et al., Int. Biodeterioration Bull. 18 [1]: 7-12 (1982)].

  Articles from another technical journal [M. M.M. Cutter (Khatter) and W. G. Salt, Journal of Antimicrobial Chemotherapy, 175-177 (1993)] describes an increase in pyrithione activity against Klebsiella pneumoniae bacteria. In particular, Figure 2 (a) of the Cutter and Salt paper shows a favorable increase in 0.1% pyrithione activity against the bacteria due to the use of 0.01% zinc chloride in combination with pyrithione. It is shown.

  Pending US patent application Serial No. filed June 22, 2000. 09 / 599,371 includes a biocidal composition comprising pyrithione, a pyrithione salt, or a pyrithione adduct, and a zinc or copper source, such as copper and / or zinc metal, oxide, hydroxide, or a combination thereof. Things are listed. However, the antibacterial composition described in this patent application has a concentration of pyrithione and zinc source as required to make a concentrated biocidal composition (ie, a “composition concentrate”). Increasing in the composition will tend to form insoluble precipitates. For example, a pyrithione-zinc composition having a concentration greater than 0.0005% pyrithione and 0.00001% zinc will tend to form insoluble precipitates. These insoluble precipitates reduce the effectiveness of the composition as antibacterial agents, pose problems for long-term storage of goods and cannot be used when soluble biocides are required. Furthermore, because it has not previously been possible to make soluble biocidal compositions rich in pyrithione and zinc sources, these components are not administered together at the site of application, but are costly and inefficient Needed to be done.

  In addition, some patents discuss the solubilization of pyrithione derivatives with certain organic compounds.

  US Pat. No. 3,636,213 describes the solubilization of heavy metal salts of pyrithione (eg, zinc pyrithione, copper pyrithione, etc.) using primary amines or polyalkyleneimines. However, this patent does not describe any of the resulting solubilized pyrithione salt for an increased antibacterial or anti-biofilm effect compared to pyrithione alone.

  U.S. Pat. No. 3,940,482 describes the solubilization of heavy metal salts of pyrithione with long chain polyamines used in human care products such as soaps, shampoos, hair dressings and the like. Yes. However, like the above patent, this patent does not describe any antibacterial or anti-biofilm effects of the resulting solubilized pyrithione salt compared to pyrithione alone.

  US Pat. No. 4,835,149 describes a method of solubilizing insoluble pyrithione metal salts (eg, zinc pyrithione, copper pyrithione, etc.) in the presence of certain amine compounds and certain aminocarboxylic acids. Has been. However, like the above patent, this patent does not describe any antibacterial or anti-biofilm effects of the resulting solubilized pyrithione salt compared to pyrithione alone.

  US Pat. No. 5,114,984 describes a method of imparting antibacterial and antifungal properties to polyurethane foams by dissolving a pyrithione salt in an alkanolamine that is miscible with a polyol. However, like the above patent, this patent does not describe any antibacterial or anti-biofilm effects of the resulting solubilized pyrithione salt compared to pyrithione alone.

  Therefore, what is required in the art is that pyrithione and zinc ions can be sent simultaneously at high concentrations to the application site, giving pyrithione and its derivatives increased biocidal efficacy against native microorganisms and biofilms. There is also a stable and soluble concentrated biocidal composition of pyrithione, pyrithione salts, or pyrithione adducts, and zinc sources. Such concentrated compositions are widely useful, have high potency, are cost effective, and can be used as “canned” preservatives and diluted to be used as functional fluids as “masterbatches”. Whether formed or directly diluted into a functional fluid, both have an increased biocidal effect. The present invention is considered to be an answer to that requirement.

  In one embodiment, the present invention provides a pyrithione, pyrithione salt, or pyrithione complex in an amount from about 0.05% to about 20% by weight, a zinc source in an amount from about 0.01% to about 5%, and It relates to a stable and soluble antibacterial concentrated composition containing an organic amine component in an amount of about 30% to about 80%, the% being based on the total weight of the concentrated composition. The organic amine component is a primary organic amine selected from the group consisting of 1,2-alkanolamine, 1,3-alkanolamine, and combinations thereof, alone or in a single amount of 1,2-alkyldiamine And secondary organic amines selected from the group consisting of monomeric and polymeric forms of 1,3-alkyldiamines, and combinations thereof. When a secondary organic amine is used, the primary organic amine must be present in the antimicrobial concentrate composition in an amount sufficient to ensure that the amine component is dissolved in the antimicrobial concentrate composition. Advantageously, the antimicrobial concentrate composition can also include a formaldehyde source to provide effective formaldehyde in the antimicrobial concentrate composition. The antimicrobial concentrate composition of the present invention can be appropriately diluted to form a functional fluid “masterbatch”, or it can be diluted directly into the functional fluid itself if desired.

In another aspect, the present invention provides a stable and soluble antimicrobial composition made by diluting the antimicrobial concentrate composition,
From about 0.05% to about 5% by weight of a pyrithione or pyrithione complex;
About 0.005% to about 1% by weight of a zinc salt, zinc oxide, zinc hydroxide, zinc borate, zinc sulfate, zinc chloride, zinc alloy, zinc complex, and combinations thereof A zinc source selected from:
A primary organic amine selected from the group consisting of 1,2-alkanolamine, and 1,3-alkanolamine, and combinations thereof, with about 0.5 wt% to about 40 wt% organic amine component alone Or in the form of 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers and polymers, and combinations thereof An amine component comprising in combination with a secondary organic amine, wherein the first organic amine is present in the antimicrobial composition in an amount sufficient to ensure that the amine component is dissolved in the antimicrobial composition;
Including
All weight percentages are based on the total weight of the antimicrobial composition, and the antimicrobial composition has an increased biocidal effect on native microorganisms or biofilms,
It relates to an antibacterial composition.

  In yet another aspect, the present invention provides a method for providing a stable and soluble antimicrobial concentrate comprising about 0.5% to about 20% pyrithione and a zinc source in an amount of about 0.01% to about 5%. About. The method comprises a primary organic amine selected from the group consisting of 1,2-alkanolamine, and 1,3-alkanolamine, and combinations thereof, alone or in combination with a single amount of 1,2-alkyldiamine. From the group consisting of those in the form of polymers and polymers, in the form of monomers and polymers of 1,3-alkyldiamines and in combination with secondary organic amines selected from the group consisting of combinations thereof Formulating at least one selected organic amine component into the concentrate in an amount effective for stabilization, provided that the first organic amine ensures that the amine component is in the antimicrobial composition. It should be present in the antimicrobial composition in an amount sufficient to dissolve. The effective amount for stabilizing the organic amine is preferably 30% to about 80% based on the total weight of the organic amine, the zinc source and the pyrithione.

In yet another aspect, the present invention provides a method for inhibiting the growth of native microorganisms or biofilms in metalworking fluids,
(A) The antibacterial concentrate composition is a metalworking fluid “masterbatch” concentrate:
(A) about 0.05 to about 5% pyrithione or pyrithione complex;
(B) about 0.005 to about 1% of a group consisting of zinc salt, zinc oxide, zinc borate, zinc hydroxide, zinc sulfate, zinc chloride, zinc alloy, zinc complex, and combinations thereof A zinc source selected from:
(C) about 0.5 to about 40% organic amine or mixture of organic amines, in this case selected from the group consisting of 1,2-alkanolamine, and 1,3-alkanolamine, and combinations thereof Primary organic amines alone or in the form of 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers and polymers, and combinations thereof An organic amine or mixture of organic amines present in combination with a secondary organic amine selected from the group consisting of:
Blending into a masterbatch concentrate comprising:
(B) diluting said “masterbatch” concentrate to provide an antibacterial effective metalworking fluid; and (C) contacting said antibacterial effective metalworking fluid with said native microorganism or biofilm. ;
Including,
The antimicrobial composition has an increased biocidal effect against native microorganisms or biofilms in metalworking fluids,
The present invention relates to a method for inhibiting proliferation.

  These and other aspects of the invention will become apparent upon reading the following detailed description of the invention.

Detailed Description of the Invention In accordance with the present invention, a soluble, stable concentrated biocidal composition with increased biocidal efficacy compared to the case of pyrithione or its derivatives alone is useful, effective, and cost effective. It has now been unexpectedly discovered that a solution to the problem of providing a composition that can be effectively delivered to each application is provided. The inventor has solved this problem by developing an antibacterial concentrate composition which is not only soluble in the antibacterial composition, but also exhibits stability against unwanted precipitation of the components of the concentrate. ing. This soluble and stable antimicrobial concentrate composition comprises a zinc source, such as a zinc salt, and certain 1,2-alkanolamines and 1,3-alkanolamines, and combinations thereof, alone or with A second organic amine selected from the group consisting of monomers and polymers in the form of 2-alkyldiamines and monomers and polymers in the form of 1,3-alkyldiamines, and combinations thereof; A pyrithione or pyrithione complex is included together with the combination. Particularly preferred organic amines are monoethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, and combinations thereof. The zinc source used in the present invention is selected from the group consisting of zinc salt, zinc oxide, zinc borate, zinc hydroxide, zinc sulfate, zinc chloride, zinc alloy, zinc complex, and combinations thereof. Is advantageous.

  The concentrate composition of the present invention is appropriately diluted to provide a so-called “masterbatch” for functional fluids such as metalworking fluid concentrates or other coating compositions such as fluids such as paint. The masterbatch suitably includes, for example, 0.05 wt% to 5 wt% pyrithione, and the other components of the concentrated composition are diluted proportionally when preparing the masterbatch.

  In antibacterial concentrate compositions, masterbatches, and final “working” functional fluids, the antibacterial combination of the present invention is compared to pyrithione alone against a broad range of microorganisms in both native and biofilm states, It also exhibits both “canned” preservative properties and an increased biocidal effect compared to those of pyrithione and zinc alone. This antibacterial performance is greater than expected based on the sum of the effects of the individual components of the composition. The increased biocidal effect associated with the composition of the present invention reduces the amount of pyrithione component used in the composition of the present invention compared to the amount of conventionally used pyrithione biocides. Can do.

  The term "increased biocidal effect" as defined herein refers to the interaction between a pyrithione or pyrithione salt component, a water-soluble zinc component, and an organic amine component, which is greater than any of those individually employed components. Also, the biocidal effect of the composition gives greater results. That is, the antimicrobial results of the composition exceed the expected biocidal effect of the combination based on the performance of the individual components.

  The present invention also makes it possible to produce a concentrated stable and soluble biocidal composition of pyrithione or pyrithione salt component and zinc component. Such compositions can effectively deliver solubilized pyrithione and zinc components simultaneously at high concentrations to the application site, and can increase the biocidal effect obtained.

  As another advantageous aspect, the present invention allows the use of pyrithione in applications involving iron. The presence of iron at the application site generally results in a decrease in the efficacy of pyrithione, and the formation of iron pyrithione results in a blue discoloration at the application site. Compared to pyrithione, for discoloration when used in the presence of iron, the present invention tends to decrease and exhibits greater efficacy.

  The following discussion details some of the special features of biofilm. The term “biofilm” as defined herein refers to an aggregate of cells fixed to each other by extracellular mucus or fixed to the surface. Most unicellular organisms produce a mucus protective coating, but cells that have aggregated into a biofilm are physically different from autologous cells and produce far more extracellular mucus than autologous cells. The mucus structure that forms part of a biofilm is extremely complex both biologically and architecturally. They are composed of aggregates (microcolonies) of individual microorganisms separated by water channels and can form large tower-type or mushroom-type structures. As the biofilm develops, autologous cells move away from the biofilm and move through its environment in search of new areas that will settle and form a new biofilm. In metalworking fluids, biofilm accumulation can cause a number of problems, including fluid degradation / degradation, odors, corrosion, and filters, transport pipes, nozzle clogging, clogged cleaves, machine surfaces Contamination, machine stoppage, reduced tool life, workpiece contamination and damage. As noted above, biofilms also increase the rate of degradation of other fluids such as paint or other surface coatings. Pharmaceutical equipment such as heart transplants, catheters, dialysis machines, dental water pipes, etc. can also become contaminated by biofilm and spread of infection.

  Biofilms have a wide range of physical and chemical heterogeneities not found in autologous cells that live in the fluid body. Because biofilm cells are in intimate contact with each other in the biofilm, the ecological interactions between individual organisms can be complex and extensive. Due to the high degree of complexity and heterogeneity present in biofilms, biofilm cells have dramatically different metabolic factors (eg, metabolic rate, growth rate, specific nutritional preferences, etc.) compared to autologous cells. In addition, cells found in biofilms generally exhibit species and organism types with a great diversity compared to autologous cells found in the fluid body. Each of the components of the composition of the present invention will be discussed in more detail below.

  Acid forms of pyrithione or pyrithione complexes can be used in the compositions of the present invention. The term “pyrithione complex” as defined herein refers to a combination of one or more pyrithione molecules and one or more metals, such as a pyrithione salt and a pyrithione adduct (eg, a combination of a metal ion such as magnesium. , 2′-dithiopyridine-1,1′-dioxide). Examples of pyrithione salts useful in the present invention include sodium pyrithione, bismuth pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, zinc pyrithione, copper pyrithione, calcium pyrithione, magnesium pyrithione, strontium pyrithione, silver pyrithione, gold pyrithione, manganese pyrithione. , And combinations thereof. Not only the organic amine salt of pyrithione but also magnesium disulfide salt is useful. The two most preferred pyrithione salts useful in the present invention are the sodium salt (ie, sodium pyrithione) and zinc pyrithione. Sodium pyrithione is a well-known commercial product. It is generally prepared by reacting 2-chloropyridine-N-oxide with NaSH and NaOH, which is exemplified in the disclosure of US Pat. No. 3,159,640. Zinc pyrithione can be prepared by reacting 1-hydroxy-2-pyridinethione (ie, pyrithionic acid) or a soluble salt thereof with a zinc salt (eg, zinc sulfate) to form a zinc pyrithione precipitate. It is exemplified in U.S. Pat. No. 2,809,971.

  In the concentrated compositions of the present invention, pyrithione or pyrithione complex is present in an amount ranging from about 0.05 to about 20% by weight, preferably from about 0.5 to about 15% by weight, more preferably from about 1 to about 10% by weight. Used appropriately. From this concentrated composition, from about 0.05% to about 5% by weight, based on the total weight percent of the composition. More preferably, a “masterbatch” is suitably prepared in which pyrithione or pyrithione properties are present in an amount ranging from about 0.01 wt% to about 2.5 wt%.

  Zinc sources useful in the composition of the present invention include, for example, zinc alloys, zinc salts, zinc oxide, zinc hydroxide, zinc sulfate, zinc chloride, zinc borate, and combinations thereof.

  Examples of zinc salts that can be used in the compositions of the present invention include zinc acetate, zinc oxide, zinc borate, zinc carbonate, zinc hydroxide, zinc chloride, zinc sulfate, zinc citrate, zinc fluoride, zinc iodide. , Zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, etc. included. Combinations of these salts can also be used in the compositions of the present invention.

  In the concentrated compositions of the present invention, the zinc source is generally present in the range of about 0.01 wt% to about 5 wt%, preferably about 0.05 wt% to about 3 wt%, based on the weight of the concentrate. . This means that the final “working” functional fluid is zinc in an amount in the range of 0.005 to 1% by weight, preferably 0.01 to 0.1% by weight, based on the total weight of the working fluid. Allowing to include sources.

The organic amine component has the following formula:
_{^{R 1 NH- (CHR 2) n}} -CHR 3 -OH ( Formula 1)
(Wherein n = 1 or 2 and R ¹ , R ² , and R ³ are hydrogen or a lower alkyl group having a total number of carbons less than or equal to 4)
It is preferred to include one or more of 1,2 and 1,3 alkanolamines contained by Most preferred are 1,2-alkanolamine and 1,3-alkanolamine in the following cases:

One or more alkanolamines contained in Formula 1 and the following formula:
NR ¹ R ² R ³ (Formula 2)
Any soluble combination with one or more alkanolamines contained in is useful as the amine component of the present invention. In the above formula,
1) R ¹ = R ² = R ³ = HO-CH ₂ -CH _2- ;
2) R ¹ = R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
3) R ¹ = R ² = CH ₃ -and R ³ = HO-CH ₂ -CH _2- ;
4) R ¹ = R ² = CH ₃ CH ₂ -and R ³ = HO-CH ₂ -CH _2- ;
5) R ¹ = R ² = CH ₃ CH ₂ CH ₂ -and R ³ = HO-CH ₂ -CH _2- ;
6) R ¹ = R ² = CH ₃ CH ₂ CH ₂ CH ₂ -and R ³ = HO-CH ₂ -CH _2- ;
7) R ¹ = R ² = CH ₃ -and R ³ = HO-CH (CH ₃ ) -CH _2- ;
8) R ¹ = R ² = CH ₃ CH ₂ -and R ³ = HO-CH (CH ₃ ) -CH _2- ;
9) R ¹ = R ² = CH ₃ CH ₂ CH ₂ -and R ³ = HO-CH (CH ₃ ) -CH _2- ;
10) R ¹ = R ² = CH ₃ CH ₂ CH ₂ CH ₂ -and R ³ = HO-CH (CH ₃ ) -CH _2- ;
11) R ¹ = R ² = CH ₃ -and R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
12) R ¹ = R ² = CH ₃ CH ₂ -and R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
13) R ¹ = R ² = CH ₃ CH ₂ CH ₂ -and R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
14) R ¹ = R ² = CH ₃ CH ₂ CH ₂ CH ₂ -and R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
15) R ¹ = CH ₃ -and R ² = R ³ = HO-CH ₂ -CH _2- ;
16) R ¹ = CH ₃ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH _2- ;
17) R ¹ = CH ₃ CH ₂ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH _2- ;
18) R ¹ = CH ₃ CH ₂ CH ₂ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH _2- ;
19) R ¹ = CH ₃ -and R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
20) R ¹ = CH ₃ CH ₂ -and R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
21) R ¹ = CH ₃ CH ₂ CH ₂ -and R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
22) R ¹ = CH ₃ CH ₂ CH ₂ CH ₂ -and R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
23) R ¹ = CH ₃ -and R ² = R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
24) R ¹ = CH ₃ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
25) R ¹ = CH ₃ CH ₂ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
26) R ¹ = CH ₃ CH ₂ CH ₂ CH ₂ -and R ² = R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
27) R ¹ = H- and R ² = R ³ = HO-CH ₂ -CH _2- ;
28) R ¹ = H- and R ² = R ³ = HO-CH (CH ₃ ) -CH _2- ;
29) R ¹ = H- and R ² = R ³ = HO-CH ₂ -CH ₂ -CH _2- ;
30) R ¹ = R ² = H and R ³ = HO-CH ₂ -C (CH ₃ ) _2- ;
31) R ¹ = H and R ² = CH ₃ -and R ³ = HO-CH ₂ -C (CH ₃ ) _2- ;
32) R ¹ = R ² = CH ₃ -and R ³ = HO-CH ₂ -C (CH ₃ ) _2- ;
33) R ¹ = R ² = H and R ³ = (HOCH ₂ ) ₂ C (CH ₂ CH ₃ );
34) R ¹ = R ² = H and R ³ = HO-CH ₂ -CH ₂ -O-CH ₂ -CH _2- ;
35) R ¹ = H and R ² = CH ₃ -and R ³ = HO-CH ₂ -CH ₂ -O-CH ₂ -CH _2- ;
36) R ¹ = R ² = CH ₃ -and R ³ = HO-CH ₂ -CH ₂ -O-CH ₂ -CH _2- ;

One or more amines included by Formula 1, and the formula:
^{R 1 R 2 N - [(} CH 2) n -CH 2 -NH-) m -H ( Formula 3)
(Where
n is 1 or 2, m is from about 1 to about 2000, and R ¹ and R ² are hydrogen or a lower alkyl group having a total number of carbons less than or equal to 4. )
Any soluble combination with one or more amines selected from the group consisting of monomers and polymers of alkyl diamines is useful as the amine component of the present invention. Examples of amine compounds that fall within Formula 3 are those having the following substituents:
1) R ¹ = R ² = CH _3- , n = 2, and m = 2;
2) R ¹ = R ² = CH ₃ CH ₂ , n = 2, and m = 1;
3) R ¹ = R ² = H, n = 1, and m = 1;
4) R ¹ H, n = 1, and m = 2;
5) R ¹ = R ² = H, n = 1, and m = 3.

Of the formulas 1, 2, and 3 described above, the following amines are particularly preferred:
(Formula 1)
Ethanolamine 1-amino-2-propanol 3-amino-1-propanol 2- (methylamino) ethanol 2- (ethylamino) ethanol 2 (propylamino) ethanol 2 (isopropylamino) ethanol

(Formula 2)
Diethanolamino triethanolamine diisopropanolamine triisopropanolamine mixed isopropanolamine (mono-, di-, and tri-isopropanolamine)
2-Amino-2-methyl-1-propanol (also called AMP)
2-Amino-2-ethyl-1,3-propanediol (also called AEPD)
2 (2-aminoethoxy) ethanol (also called diglycolamine)
N-methyldiethanolamine N, N-dimethylethanolamine N, N-diethylethanolamine N, N-dibutylaminoethanol N, N dimethylamino-2-propanol

(Formula 3)
1,3-diaminopropane diethylenetriamine triethylenetetraamine polyethyleneimine diethylaminopropylamine dimethylaminopropylamine

  The amount of organic amine suitably used in the concentrate composition of the present invention is suitably in the range of about 30 to about 80% by weight, preferably about 40 to about 70% by weight, based on the total weight of the concentrate. is there. For “masterbatch” dilutions or “working” functional fluids, the amount of organic amine is suitably about 0.5-40% by weight, based on the weight of the fluid.

  A solvent or combination of solvents may be included in the antimicrobial composition of the present invention. Suitable solvents include aqueous media such as water or a combination of water and one or more water-miscible organic solvents (one or many). Useful organic solvents include alcohols such as methanol and ethanol, ethers, esters, glycols and the like.

  The composition of the present invention may contain formaldehyde as an additional biocide. In the present invention, formaldehyde may be added directly or may be in the form of a formaldehyde releasing agent or donor, for example cis 1- (3-chloroallyl) 3,5,7-triaza-1-azonia adamantane chloride , Hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 4,4-dimethyloxazolidine, 5-hydroxymethoxymethyl-1-aza-3,7-dioxabicyclooctane, dimethylol Dimethyldantoin, N, N ″ -methylenebis [N ′-(hydroxymethyl) -2,5-dioxo-4-imidazolidinyl] urea, N- (hydroxymethyl) -N- (1,3-dihydroxymer-2, 5-dioxo-4-imidazolidinyl) -N ′-(hydroxymethyl) urea, and combinations thereof, which One useful formaldehyde release agent is TRIADINE 10 (Hexahydro-1,3, sold by Arch Chemicals, Inc., Norwalk, Conn.). 5-tris (2-hydroxyethyl) -s-triazine and omadine salt combination] In a concentrated composition of the invention, the formaldehyde is about 0.1 to about 0.1, based on the total weight of the composition. It is suitable to use in an amount ranging from 30% by weight, preferably from about 0.5% to about 15% by weight.

  As is known in the art, many formaldehyde release agents often release only a portion of the material to form formaldehyde. For example, about 31% of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine releases formaldehyde. In such cases, an appropriate conversion factor must be taken into account in order to provide the composition of the present invention with the above range of formaldehyde. As an illustrative example, 500 ppm of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine results in the release of about 160 ppm of formaldehyde. Similarly, 1500 ppm hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine results in the release of about 480 ppm formaldehyde.

  The composition of the invention first comprises one or more selected zinc sources, one or more organic 1,2- or 1,3-alkanolamines, and optionally 1,2- or 1,3-alkyl. The diamine monomer or polymer is advantageously prepared by mixing together in a suitable solvent or carrier and then adding the pyrithione or pyrithione complex. Alternatively, the compositions of the present invention may be prepared by separately adding the individual components to a solvent or functional mixture or fluid that has been treated to provide antimicrobial protection.

  The biocidal composition of the present invention is useful as an algicide, bactericides, and / or fungicides, and Gram-positive and Gram-negative bacteria, fungi (eg, yeast, mold, powdery mildew) It is particularly useful for inhibiting the growth of microorganisms such as algae, protozoa. This composition comprises Pseudomonas aeruginosa, Aspergillus niger, Fusarium, Cephalosporium, Pseudomonas fluorescens, Pseudomonas rubes It is particularly effective against Pseudomonas stutzeri, Pseudomonas olevorans, Alcaligenes faecalis, Escherichia coli, Citrobacter freundii, and the like. The biocidal composition of the present invention comprises industrial fluids (eg, metalworking fluids), paints, coatings, adhesives, wet preservatives, hard surface cleaners, textile protection products, wood products, plastic products, medical products, Fibers or other useful additives in applications where microbial growth, particularly biofilm growth, must be stopped or delayed.

  One important application for the antimicrobial compositions of the present invention is the use in functional fluids such as metal working fluids, cutting fluids and the like. The metalworking fluid is typically supplied as a “masterbatch” concentrate containing the antimicrobial composition and other ingredients. In the case of a concentrate, a sufficient amount of biocidal composition is provided such that the diluted “working” fluid contains a biocidal effective amount of the antimicrobial composition. In order to meet this requirement, it is typical to incorporate the antimicrobial agent into the concentrate of the metalworking fluid in an amount of about 10 to 100 times the required concentration in the diluted “working” fluid. Typical concentrations of pyrithione in metalworking concentrates range from about 0.05 to 1.0% pyrithione. At these pyrithione concentrations, even small amounts of zinc result in the formation of precipitates that are unacceptable for use in metalworking fluid concentrates.

  The biocidal composition of the present invention can be added with a combination of pyrithione and zinc in a concentration sufficient to be used in a metalworking fluid concentrate, but still as a biocidal concentrate or as a metalworking fluid concentrate. Even if formulated as a product, no precipitate is formed. In this manner, the increased biocidal effect afforded by the biocidal compositions of the present invention is effectively imparted using a thick soluble form of metalworking fluid concentrate. A particularly useful level of a prototypical biocide mixture in a metalworking concentrate is about 1-4%, which will be about 0.05-0.2% ppm in a diluted “working” metalworking fluid. I will. The diluted metalworking fluids obtained from these concentrates are 10-500 ppm active sodium pyrithione, 1-50 ppm divalent zinc, and 150-1500 ppm organic 1,2- and / or 1,3-alkanolamine, And optionally providing monomer and polymer concentrations of alkyl diamine, more preferably 25-250 ppm active sodium pyrithione, 5-25 ppm divalent zinc, and 150-1200 ppm organic 1, It will give concentrations of 2- and / or 1,3-alkanolamine, and optionally alkyldiamine monomers and polymers. A particularly useful ratio of components in the final “working” metalworking fluid is about 100 ppm active sodium pyrithione, about 10 ppm zinc, and about 600 ppm organic 1,2- and / or 1,3-alkanolamine, And optionally alkyl diamine monomers and polymers.

  The antimicrobial compositions of the present invention are coating compositions such as paints, adhesives, caulk, sealants, elastomers, and other coating compositions including aqueous liquid cleaning compositions such as liquid detergent compositions. Even things are useful. Suitable paints include indoor and outdoor household paints, industrial and commercial paints. The antimicrobial composition of the present invention, preferably in a total amount of about 0.01% to about 10% by weight, based on the weight of the coating composition, canned “wet” during storage of the coating composition and prior to use. Particularly advantageous results have been obtained when used as preservatives.

  Coating compositions comprising the antimicrobial combination of the present invention include, for example, adhesives, paints, coatings, sealants, wood and wood composites, wet preservative compositions, human care products, masonry construction and stone treatment compositions, It can be used in many end uses such as leather protection compositions, hard surface cleaners and disinfectants, fabric and fabric protection compositions, and other plastic and medical product applications. By way of example, antibacterial combinations include ingredients effective for treating substrates such as wood and wood composites, masonry construction and stone, leather, hard surfaces, fabrics, textiles, plastics, medical products, and combinations thereof. It is appropriate to blend in the functional fluid containing.

  The composition of the present invention can be used as a disinfectant and preservative, in any of the various applications described herein, in a liquid or sprayable solid state, alone or in water, liquid hydrocarbons, ethanol, isopropanol, etc. Used in combination with such an inert carrier. They can be used with conventional procedures to control bacteria and fungi in various substrates and are effective against antibacterials by conventional methods such as spraying, dipping, drenching impregnation, etc. The amount can be applied to bacterial or fungal organisms or their substrates.

  The present invention allows a reduced amount of the main biocide pyrithione to be used in combination with a zinc salt biocide aid that is less expensive than the main biocide, thereby making it cheaper to manufacture, Antibacterial compositions having the above-mentioned properties of increased antibacterial efficacy against various organisms can be provided. In addition, the amine component of the composition of the present invention not only provides significant solubility to the composition, but also increases stability without forming a precipitate, leaving the composition commercially active over time. It is thought that it can be maintained. Furthermore, the present invention provides an enhanced potency killing comprising a pyrithione biocide, a zinc salt, and 1,2- and 1,3-alkanolamines alone or in combination with alkyldiamine monomers and polymers. It allows the biological composition to be delivered to the application site as a stable and thick soluble composition.

  The following examples are for purposes of illustration and are not intended to limit the scope of the invention in any way. All parts and percentages are by weight and all temperatures are in degrees Celsius unless explicitly stated otherwise.

Examples 1-40
Of sodium pyrithione, ZnCl _2, and mixtures of amines, constitute a Erlenmeyer flask 250ml were placed in an autoclave having an effective cheesecloth stopper against microorganisms in metalworking fluids, in each flask were next diluted ( 1:20) 100 ml of one of the metalworking fluid solutions was placed: (1) soluble oil, (2) semi-synthetic fluid, or (3) synthetic fluid. Each of these fluids was designed to resemble commercial soluble, semi-synthetic, and synthetic oils available from the manufacturer.

Soluble oil was composed of the following ingredients:
100SUS naphthenic petroleum basic raw material 82.5%
62% active sodium sulfonate 11.0%
Oleic acid 1.5%
Triethanolamine (TEA) 1.0%
Methyl tallowate 3.0%
Glycol ether 1.0%

The semi-synthetic fluid was composed of the following components:
100SUS naphthenic petroleum base material 5.0%
62% Sodium sulfonate 10.0%
TEA 15.0%
Oleic acid 15.0%
Carboxylic acid type corrosion inhibitor 10.0%
Water 45.0%

The synthetic concentrate fluid was composed of the following components:
Water 63.0%
Polyalkylene glycol (water-soluble type) 7.0%
Heptanoic acid 1.0%
TEA 15.0%
Carboxylic acid type corrosion inhibitor 14.0%

In addition to the untreated controls, for each type of metalworking fluid, 100 PPM sodium pyrithione (NaPT) alone, 21 PPM ZnCl ₂ alone, and 600 PPM amine alone (monoethanolamine, 1-amino-2-propanol, or A flask containing either 3-amino-1-propanol was prepared. A flask was also set up to test a mixture of 100 PPM NaPT and 21 PPM ZnCl ₂ and a mixture of 21 PPM ZnCl ₂ and 600 PPM of one of the three amine compounds. For each type of fluid, three treatment flasks were set up and treated with a mixture A, B, or C composed of NaPT, ZnCl ₂ and one type of amine to a final concentration of 1000 PPM. Mixture A consisted of 10% NaPT, 1.8% ZnCl ₂ , and 60.5% monoethanolamine. Mixture B 10% NaPT, consisted of 1.8% ZnCl _2, and 60.5% of 1-amino-2-propanol. Mixture C 10% of NaPT, consisted of 1.8% of ZnCl _2, and 60.5% of 3-amino-1-propanol. For control, all concentrations given above are the final concentration of the compound in the test flask. The final concentration of the mixed components in the treated test flask was 100 PPM NaPT, 18 PPM ZnCl ₂ , and 605 PPM amine.

The pH of each flask was determined. Addition of amine to the soluble oil flask increased the pH of the fluid to about 9.9. For any such flask, the pH was adjusted to the pH of the untreated control by adding HCl. This was done to eliminate or minimize the effect of the biocide on the test organism due to pH. For semi-synthetic or synthetic fluids, the increase in pH by the amine relative to the untreated control was 0.3 or less. The pH of the soluble oil, semi-synthetic, and synthetic flasks were 8.5-8.7, 8.2-8.5, and 8.1-8.5, respectively. Bacteria were added to each flask to a final concentration of 10 ⁷ bacteria / ml. Bacterial inoculation sources include Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201, Pseudomonas rubescens 12202, and Pseudomonas rubescens 12 It consisted of cells. Fungal spores were added to each flask to a final concentration of 10 ⁵ spores / ml. The fungal addition consisted of an equal number of spores from Fusarium sp. And Cephalosporium sp., Metalworking fluid field isolate.

  The flask was incubated at room temperature (23 ° C. ± 2 ° C.) on a shaker at 130 rpm. After 1 day and 4 days of culture, fluid samples were obtained from the flasks. Samples were serially diluted with sterile deionized water (1:10) and spread on plates for bacterial and fungal viability counts. Plates were incubated at 28 ° C. for 2-3 days and then counted for colony forming units. The experimental results are shown in Table 1.

As shown in Table 1, a mixture A (10% of the NaPT, 1.8% of the ZnCl _2, and 60.5% of monoethanolamine), mixture B (10% of the NaPT, 1.8% of the ZnCl ₂ , and 60.5% of 1-amino-2-propanol), or a mixture C (10% of NaPT, 1.8 percent of ZnCl _2, and 60.5% of 3-amino-1-1000PPM by propanol) Treatment at the final concentration was very effective against soluble oils and fungi in semi-synthetic fluids. No fungus was detected in the flask after 4 days of treatment with these mixtures. The control treatment showed little difference in the number of fungi exhibited by the soluble oil and synthetic fluid compared to the untreated control. The three mixtures A, B, and C all reduce the number of bacteria in soluble oil by at least 1/100 within 4 days compared to untreated, and within a day in semi-synthetic fluids. Was reduced to zero. Compared to the untreated one, the number of bacteria was not significantly affected by the control treatment in soluble oil and semi-synthetic fluid. Mixtures A and C reduced the number of bacteria in the synthesis fluid by approximately at least 1/500 and 1/10, respectively. In the synthetic fluid, the control containing only zinc was very effective against bacteria. None of the mixtures had a significant effect on fungi in the synthesis fluid.

Examples 41-51
Sodium pyrithione, of ZnCl _2, and mixtures of amines, metal processing flow biocidal efficacy two five gallon glass aquarium tank for microorganisms involved in native microorganisms and biofilms in metalworking fluids and disinfected with bleach, circulates It was set to be similar to the system. One aquarium pump was attached to each tank as a means of circulating fluid through the tank. To provide a sampling surface for biofilm growth, a stainless steel washer sample (surface area 1.2 cm ² ) and a polycarbonate disc sample piece (surface area 3.8 cm ² ) were glassed with double-sided adhesive cloth tape. It was attached to the specimen holder on the side. Two steel and polycarbonate specimens were placed on each cage. To each tank was added 12.5 liters of diluted (1:20) semi-synthetic metalworking fluid.

Tank 1 was used as an untreated control. Mixture D (16% of the NaPT, 2% of the ZnCl _2, 20% of monoethanolamine, 20% of 3-amino-1-propanol) was added to a final concentration of 1250PPM in the tank 2, whereby the 200 PPM NaPT to yield ZnCl _2, 250 ppm of monoethanolamine 25PPM, and a final activity concentration of 3-amino-1-propanol 250 ppm in 12.5 liters of diluted metalworking fluid. The pH of tank 1 and tank 2 was 7.8 and 8.3, respectively. The pH of tank 1 was adjusted to 8.3 with HCl. Bacteria were added to each tank to a final concentration of 10 ⁶ bacteria / ml. Bacterial inoculation sources are Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201, Pseudomonas rubescens 12202, and Pseudomonas rubescens 12 It consisted of cells. Fungal spores were added to each tank to a final concentration of 10 ⁴ spores / ml. The fungal addition consisted of Fusarium sp. And Cephalosporium sp., Equal numbers of spores from metalworking fluid field isolates. The addition of bacteria and fungi was repeated three times per week. The tanks were circulated at room temperature (23 ° C. ± 2 ° C.).

Bulk metalworking fluid and biofilm samples were obtained after 19 days. For the main fluid, samples were serially diluted (1:10) with disinfected deionized water, spread on plates, Tryptic Soy Agar + 90 PPM cyclohexamide, and malt agar + 900 PPM streptomycin + 550 PPM The number of bacterial and fungal survivors on each of the penicillins G was examined. For biofilm samples, the sample strip holder was removed from the bottom and sides of the tank. The sample pieces were removed from the cage, rinsed in sterile water, and transferred to a 25 mm × 150 mm disposable glass culture tube containing 10 ml of sterile deionized water. The biofilms left the specimen pieces and were resuspended by rotating the tubes at maximum speed for 30 seconds. The resuspended biofilm was then serially diluted and spread on plates as described for the main fluid sample and examined for bacterial and fungal counts. Sludge material was collected from the side of the tank at the fluid / air interface with a 0.5 ml disinfecting needleless syringe and resuspended by rotation in sterile deionized water. The number of bacteria and fungi in each sludge sample was determined as previously described for the main fluid sample. Plates were incubated at 28 ° C. for 2-3 days and then counted for colony forming units (cfu). For biofilm samples, excluding sludge material, colony forming units / ml were converted to colony forming units / cm ² . Table 2 shows the results of this experiment.

As shown in Table 2, tanks treated with Mixture D showed at least 200 times less bacteria in the main fluid than untreated tanks. There was little difference in the number of fungi in the main fluid between the treated and untreated tanks. Bacteria present in the biofilms of tanks treated with Mixture D were at least 1/3000 to 1/1000 less than untreated tanks and at least 1/25 to 1/250 less for fungi. Although 10 ⁵ bacteria / ml were present in 1 ml of sludge material from the air / fluid interface of the untreated tank, neither bacteria nor fungus could be detected from the sludge material in the tank treated with Mixture D.

Example 52
Biocidal efficacy of a mixture of sodium pyrithione, ZnCl ₂ , amine, and formaldehyde-releasing biocide against microorganisms in metalworking fluid Experiments have shown that sodium pyrithione, ZnCl ₂ , monoethanolamine and hexahydro-1,3,5 A metalworking fluid of a mixture of tris (2-hydroxyethyl) -s-triazine (formaldehyde releasing agent) and a mixture of sodium pyrithione and hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine This was done to compare the biocidal efficacy in the medium.

Disinfection glass culture tubes (16 mm x 150 mm) containing 3 ml of 5% soluble oil MWF or 5% semi-synthetic metal working fluid were set up. In those tubes, 40% sodium pyrithione, 78.5% hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, or mixture A (10% sodium pyrithione, 1.8% ZnCl ₂ , and 60.5% monoethanolamine) were added in appropriate amounts to form various mixtures of the biocides and controls for each of the biocides. Bacteria and fungi were added to each tube to a total final concentration of 10 ⁷ bacteria / ml and 10 ⁵ fungal spores / ml, respectively. The bacterial inoculum is an equal number of cells from Pseudomonas aeruginosa, Escherichia coli, Pseudomonas fluorescens, Pseudomonas rubescens, and Pseudomonas putida It was. The fungal addition consisted of an equal number of spores from Fusarium sp. And Cephalosporium sp. Tubes were incubated at 28 ° C. for 3 days and then counted for the number of viable bacteria on trypto soybean agar + 90 PPM cycloheximide and the number of viable fungi on malt agar + 900 PPM streptomycin + 550 PPM penicillin G. The experimental results are shown in Table 3.

  In Table 3, it should be noted that the triazine used was a 78.5% aqueous solution of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine. Hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine is in equilibrium with free formaldehyde and is about 31 when used as a formaldehyde release agent in metalworking fluids at the concentrations used. % Formaldehyde is known to be liberated. The relationship between the triazines, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazines of Examples 52, 53, and 54 and formaldehyde is shown in Table 4.

The experimental results shown in Table 3 show that mixture A (10% sodium pyrithione, 1.8% ZnCl ₂ , 60.5% monoethanolamine) and hexahydro-1,3,5-tris (2-hydroxyethyl) ) Illustrates that a mixture of -s-triazines has better performance against fungi than a mixture of sodium pyrithione and hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine . For example, to produce a biocidal efficacy comparable to that of a mixture of sodium pyrithione and 250-500 PPM hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, a mixture A When used together with 250-500 PPM of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, only about 75% less active sodium pyrithione is required. Furthermore, increasing the concentration of mixture A also allows for a reduction in the amount of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine required to eliminate fungal growth. For example, 500 PPM of Mix A can reduce the amount of hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine required by a factor of 4 to reduce fungal levels. When Mixture A is used at a concentration of about 1000 PPM, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine is unnecessary to eliminate microbial contamination.

Example 53
Sodium pyrithione, ZnCl _2, monoethanolamine, and mixtures of formaldehyde-releasing biocides, the efficacy of sodium pyrithione for preventing microbial contamination during metalworking fluids, ZnCl _2, monoethanolamine, and hexahydro-1,3, The efficacy of a mixture of 5-tris (2-hydroxyethyl) -s-triazine to prevent microbial contamination of metalworking fluids was examined. The efficacy was compared against the efficacy of a mixture of sodium pyrithione and hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine.

A disinfected 250 ml Erlenmeyer flask was set up with 100 ml of 5% semi-synthetic metal working fluid. In these flasks, 40% sodium pyrithione, 78.5% hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, or mixture A (10% sodium pyrithione, 1.8% ZnCl ₂ , and 60.5% monoethanolamine) were added in appropriate amounts to form various mixtures of the biocides and controls for each of the biocides. Bacteria and fungi were added to each flask to a total final concentration of 10 ⁷ bacteria / ml and 10 ⁵ fungal spores / ml, respectively. Bacterial inoculation sources are equal numbers of cells from Pseudomonas aeruginosa, Escherichia coli, Pseudomonas fluorescens, Pseudomonas rubescens, and Pseudomonas putida It was. The fungal addition consisted of an equal number of spores from Fusarium sp. And Cephalosporium sp. Bacteria and fungus addition was repeated three times per week. The flasks were incubated at 28 ° C. and after several weeks the number of viable bacteria on trypto soybean agar + 90 PPM cycloheximide and the number of viable fungi on malt agar + 900 PPM streptomycin + 550 PPM penicillin G were determined. The experimental results are shown in Table 5.

  In this semi-synthetic fluid, mixture A and hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine are mixed with NaPT and hexahydro-1,3,5-tris (2-hydroxyethyl). Provides longer term protection against microbial contamination than mixtures with s-triazines. Furthermore, the mixture of mixture A and hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine is sodium pyrithione and hexahydro-1,3,5-tris (2-hydroxyethyl) -s- It is also possible to use less sodium pyrithione or hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine than the mixture with triazine while maintaining the same period of efficacy. Yes.

Example 54
Sodium pyrithione in metalworking fluids, the ZnCl _2, and mixtures of amines, the influence of iron ions of the iron ions to discoloration and biocidal efficacy is present, is known to cause blue discoloration of metalworking fluids containing sodium pyrithione Yes. Furthermore, iron ions reduce the biocidal efficacy of sodium pyrithione. Experiments were conducted to determine whether a mixture of sodium pyrithione, ZnCl ₂ , and monoethanolamine would also show reduced potency against microorganisms and would cause a blue discoloration in the presence of iron.

100 ml of 5% metalworking fluid was filled into a disinfected 250 ml Erlenmeyer flask with a cheesecloth stopper. The fluids examined included soluble oil, two semi-synthetics, and synthetics. The water used to make the 5% fluid contained various concentrations of Fe ions (FeCl ₃ .6H ₂ O) ranging from 0 PPM to 200 PPM. Mixture A consists of 10% NaPT, 1.8% ZnCl ₂ , and 60.5% monoethanolamine, which is added to a suitable flask to a final concentration of 1000 PPM and fluid During this, final active concentrations of NaPT and Zn (II) of 100 PPM and 8.6 PPM, respectively, were produced. Untreated controls and controls treated with 100 PPM NaPT alone were also prepared. Three times per week, bacteria and fungi were added to their flasks to a total final concentration of 10 ⁷ bacteria / ml and 10 ⁵ fungal spores / ml. Bacterial inoculation sources include Pseudomonas aeruginosa 9027, Escherichia coli 8739, Pseudomonas fluorescens 12201, Pseudomonas rubescens 12202, and Pseudomonas putida equal number of Pseudomonas putida It consisted of cells. The fungal addition consisted of an equal number of spores from Fusarium sp. And Cephalosporium sp. The flask was incubated at 120 rpm on a shaker at room temperature (23 ° C. ± 2 ° C.). The initial color of the metal working fluid was determined by visual inspection. Surviving bacteria and fungal counts were determined by spreading on malt agar containing tryptoid soy agar containing 90 PPM cycloheximide and 900 PPM streptomycin and 550 PPM penicillin G for two weeks, respectively. The color of the fluid was examined. Table 6 shows the experimental results.

  The results in Table 6 show that Mixture A is generally much less prone to blue discoloration of metalworking fluids than NaPT. The intensity of blue varies with the fluid, but no blue coloration was observed in three of the four fluids containing Fe ions up to 100 PPM. With 200 PPM Fe, three of the fluids showed some blue color. However, one fluid did not show a blue color even in the presence of 200 PPM Fe ions. The results also show that the biocidal efficacy against bacteria and fungi is hardly affected by Fe ions at concentrations below 100 PPM. In two of the four fluids, efficacy was reduced in the presence of 200 PPM Fe ions. The remaining two fluids showed no change in potency.

Example 55
Preparation of a stable and soluble concentrated mixture of sodium pyrithione, zinc oxide, and organic amine A mixture of sodium pyrithione, ZnCl ₂ , and various organic amines was prepared in a 100 ml clear glass bottle at room temperature (23 ° C. ± 2 ° C.) Put it on. The mixtures were measured for the presence of precipitates at 24 and 72 hours after manufacture, or for other physical instabilities.

Table 7. Sodium pyrithione, zinc oxide, and organic amines [single amine (A
Part))) and the solubility and stability of amine mixtures (see part B)
Mixture% by weight 24 hours 72 hours
Appearance at Part A- Single amine NaPT 10.00
ZnCl ₂ 1.74
Organic amine 60.50
Wed 27.76
1,2 and 1,3 alkanolamines: Formula 1
Ethanolamine 60.50 SS
NH ₂ -CH ₂ -CH ₂ -OH

3-Amino-1-propanol 60.50 SS
_{NH 2 -CH-CH 2 -CH 2} -OH
2- (Methylamino) ethanol 60.50 SS
_{CH 3 -NH 2 -CH 2 -CH 2} -OH
Propyl ethanolamine 60.50 SP
CH ₃ —CH ₂ —CH ₂ —NH ₂ —CH ₂ —CH ₂ —OH
1,2 and 1,3 alkanolamines: Formula 2
Diethanolamine 60.50 PP
HO—CH ₂ —CH ₂ —NH ₂ —CH ₂ —CH ₂ —OH

2- (2-aminoethoxy) ethanol 60.50 PP
NH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —OH

Mixed isopropanolamine 60.50 SP
(44% di, 44% tri, and 12% mono)

Alkyldiamine: Formula 3
1,3-diaminopropane 60.50 SS
NH ₂ —CH ₂ —CH ₂ —CH ₂ —NH ₂
Diethylenetriamine 60.50 SS
NH ₂ —CH ₂ —CH ₂ —NH—CH ₂ —CH ₂ —NH ₂
Triethylenetetramine 60.50 SS
NH ₂ (CH ₂ —CH ₂ —NH) ₃ —H
Polyethyleneimine 60.50 SS
NH ₂ (CH ₂ —CH ₂ —NH) _n —H


Part B- amine mixture NaPT 10.00
ZnCl ₂ 1.74
Organic amine 60.50
Wed 27.76
1,2 and 1,3 alkanolamines: Formula 1 + Formula 2
Ethanolamine 30.00 SS
2-Amino-2-methyl-1-propanol 30.50
Ethanolamine 20.00 SS
2-Amino-2-methyl-1-propanol 40.50
Ethanolamine 10.00 PP
2-Amino-2-methyl-1-propanol 50.50
Ethanolamine 20.00 SS
Diethanolamine 40.50
Ethanolamine 20.00 SS
Triethanolamine 40.50
Ethanolamine 30.00 SS
2-Amino-2-ethyl-1.3-propanediol 40.50
Ethanolamine 20.00 PP
Diglycolamine 40.50

P = precipitate formed in the mixture.
S = soluble and stable mixture.

  As shown in Table 7, the soluble and stable mixture was mixed with 1-amino-2-propanol, 3-amino-1-propanol, 2- (methylamino) ethanol, 1,3-diaminopropane, diethylenetriamine, ethanolamine. , Triethylenetetramine, and polyethyleneimine were observed after 24 and 72 hours. The three amines, propylethanolamine, mixed isopropanolamine, and 3-methoxypropylamine showed a soluble mixture after 24 hours, but not after 72 hours. AMP95, diethanolamine, AEPD85, 2 (2-aminoethoxy) ethanol, N-methyldiethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethanolamine, ethylenediamine, triethylamine, triisopropanolamine, and di Isopropanolamine showed a precipitate after 24 and 72 hours. Part B of Table 7 shows that certain amine mixtures give adequate solubility when used in combination.

  While the invention has been described and illustrated in connection with exemplary embodiments thereof, it will be understood by those skilled in the art that various aspects of the invention and details thereof may be obtained without departing from the spirit and scope of the invention as set forth in the appended claims. It should be appreciated that changes, omissions, and additions can be made.

Claims (38)

  A pyrithione or pyrithione complex in an amount from about 0.05% to about 20% by weight, a zinc source in an amount from about 0.01% to about 5%, an organic amine component in an amount from about 30% to about 80% (the% Is based on the total weight of the composition concentrate) and the organic amine component is selected from the group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof Organic amines, alone or in the form of 1,2-alkanolamine, 1,3-alkanolamine, 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers And in the form of a polymer, and in combination with a secondary organic amine selected from the additional group consisting of combinations thereof, wherein the primary organic amine ensures that the amine component is in the antimicrobial concentrate composition. To dissolve Present in the antimicrobial concentrate composition in an amount min, antimicrobial concentrate composition.   The antimicrobial composition according to claim 1, wherein the pyrithione complex is selected from the group consisting of pyrithione salts and pyrithione adducts.   The pyrithione salt is sodium pyrithione, bismuth pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, zinc pyrithione, copper pyrithione, calcium pyrithione, magnesium pyrithione, strontium pyrithione, silver pyrithione, gold pyrithione, manganese pyrithione, organic amine pyrithione, and their The antimicrobial composition according to claim 2, which is selected from the group consisting of combinations.   The antimicrobial composition according to claim 2, wherein the pyrithione adduct is 2,2'-dithiopyridine-N-oxide.   Zinc salt is zinc acetate, zinc borate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, phosphorus Claims selected from the group consisting of zinc acid, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, and combinations thereof. 1. The antibacterial composition according to 1. The primary organic amine has the formula:
_{^{R 1 NH- (CHR 2) n}} -CHR 3 -OH ( Formula 1)
(Wherein n = 1 or 2 and R ¹ , R ² and R ³ are hydrogen or a lower alkyl group having a total number of carbons less than or equal to 4)
The antibacterial concentrate composition of claim 1 comprising a compound of:   The primary organic amine is ethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2- (methylamino) ethanol, 2- (n-propylamino) ethanol, 2- (ethylamino) ethanol The antibacterial concentrated composition according to claim 6, which is at least one compound selected from the group consisting of 2-, isopropylamino) ethanol, and combinations thereof. The secondary organic amine has the formula:
NR ¹ R ² R ³ (Formula 2)
[Wherein R ¹ represents H, CH ₃ —, CH ₃ CH ₂ —, CH ₃ CH ₂ CH ₂ —, CH ₃ CH ₂ CH ₂ CH ₂ —, HO—CH ₂ —CH ₂ —, and HO— CH (CH ₃ ) —CH ₂ — and R ² is H, CH ₃ —, CH ₃ CH ₂ —, CH ₃ CH ₂ CH ₂ —, CH ₃ CH ₂ CH ₂ CH ₂ —, HO—CH _{2. -CH 2 -, HO-CH 2} -CH 2 -CH 2 -, HO-CH (CH 3) -CH 2 -, and _{HO-CH 2 -C (CH 3} ) 2 - a and, ^{R 3} is, HO _{-CH 2 -CH 2 -, HOCH 2} -CH 2 -CH 2 -, HOCH (CH 3) -CH 2 -, HOCH 2 -C (CH 3) 2 -, (HOCH 2) 2 C _(CH 2 CH 3), and _{HO-CH 2 -CH 2 -O-} CH 2 -CH 2 - der Comprising a compound of], antimicrobial concentrate composition of claim 1.   The secondary organic amine is diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, mixed isopropanolamine, 2-amino-2-methyl-1-propanol (also called AMP), 2-amino-2- Ethyl-1,3-propanediol (also called AEPD), 2- (2-aminoethoxy) ethanol (also called diglycolamine), n-methyldiethanolamine, n, n-dimethylethanolamine, 9. The antimicrobial concentrate composition according to claim 8, wherein the composition is selected from the group consisting of n, n-diethylethanolamine, n, n-dibutylaminoethanol, n, n-dimethylamino-2-propanol, and combinations thereof. . A secondary organic amine is added to the adduct, formula:
R ¹ R ² N — [(CH ₂ ) _n —CH ₂ —NH—] _m —H (Formula 3)
(Where
n is 1 or 2, m is from about 1 to about 2000, and R ¹ and R ² are hydrogen or a lower alkyl group having a total number of carbons less than or equal to 4. )
The antibacterial concentrated composition according to claim 1, comprising:   The secondary organic amine is selected from the group consisting of 1,3-diaminopropane, n, n-diethylenetriamine, triethylenetetraamine, polyethyleneimine, diethylaminopropylamine, dimethylaminopropylamine, and combinations thereof. Item 11. The antibacterial concentrated composition according to Item 10.   The antimicrobial concentrate composition of claim 1, wherein the pyrithione, pyrithione salt, pyrithione complex comprises about 5 to about 20 wt% of the antimicrobial composition, based on the total weight of the antimicrobial concentrate composition.   The antimicrobial concentrate composition of claim 1, wherein the zinc source comprises about 0.5 to about 5 wt% of the antimicrobial composition, based on the total weight of the antimicrobial concentrate composition.   2. The antimicrobial concentrate composition of claim 1, wherein the combination of organic amine and organic amine comprises about 40 to about 70% by weight of the antimicrobial composition, based on the total weight of the antimicrobial concentrate composition.   The antibacterial concentrated composition according to claim 1, further comprising water or a water-miscible organic solvent.   The antimicrobial concentrate composition of claim 1 further comprising a formaldehyde source to provide effective formaldehyde in the antimicrobial concentrate composition.   The formaldehyde source is cis 1- (3-chloroallyl) -3,5,7-triaza-1-azoniaadamantane chloride, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 4, 4-dimethyloxazolidine, 5-hydroxymethoxymethyl-1-1aza-3,7-dioxabicyclo-octane, dimethyloldimethyldantoin, N, N "-methylenebis [N '-(hydroxymethyl) -2,5 -Dioxo-4-imidazolidinyl] urea, N- (hydroxymethyl) -N- (1,3-dihydroxymethyl-2,5-dioxo-4-imidazolidinyl) -N ′-(hydroxymethyl) urea, hexahydro-1, Selected from the group consisting of 3,5-tris (2-hydroxyethyl) -s-triazine, and combinations thereof It is, antimicrobial concentrate composition of claim 16.   17. The antimicrobial concentrate composition of claim 16, wherein the formaldehyde source comprises about 0.5 to about 30% by weight of the antimicrobial composition, based on the total weight of the antimicrobial concentrate composition. In a method for inhibiting the growth of native microorganisms or biofilms in a metalworking fluid,
(A) The antibacterial concentrated composition according to claim 1 is blended, and “master batch”:
(A) about 0.05 to about 5% pyrithione or pyrithione complex;
(B) about 0.005 to about 1% of a group consisting of zinc salt, zinc borate, zinc oxide, zinc hydroxide, zinc sulfate, zinc chloride, zinc alloy, zinc complex, and combinations thereof A zinc source selected from:
(C) a primary organic amine selected from the essential group consisting of 1,2-alkanolamine, 1,3-alkanolamine, and combinations thereof, with about 0.5 to about 40% organic amine component; Alone or in the form of 1,2-alkanolamine, 1,3-alkanolamine, 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers and polymers In combination with a secondary organic amine selected from the additional group consisting of, and combinations thereof, wherein the primary organic amine ensures that the amine component is dissolved in the antimicrobial concentrate composition. Providing a masterbatch comprising: an organic amine component which is present in the antimicrobial concentrate composition in an amount sufficient for
(B) diluting the “masterbatch” to provide an antibacterial effective metalworking fluid; and (C) contacting the antibacterial effective metalworking fluid with a native microorganism or biofilm;
Including,
The antibacterial effective metalworking fluid has an increased biocidal effect on native microorganisms or biofilms,
Proliferation prevention method.   20. The method of claim 19, wherein the pyrithione complex is selected from the group consisting of pyrithione salts and pyrithione adducts.   The group wherein the pyrithione salt is sodium pyrithione, potassium pyrithione, bismuth pyrithione, lithium pyrithione, ammonium pyrithione, zinc pyrithione, copper pyrithione, calcium pyrithione, magnesium pyrithione, strontium pyrithione, silver pyrithione, gold pyrithione, manganese pyrithione, and combinations thereof 21. The method of claim 20, wherein the method is selected from:   21. The method of claim 20, wherein the pyrithione adduct is 2,2'-dithio-pyridine-N-oxide.   Zinc salt is zinc acetate, zinc borate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, phosphorus 21. selected from the group consisting of zinc acid, zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, and combinations thereof. The method described in 1.   21. The method of claim 19, wherein the native microorganism or biofilm comprises a microbial component selected from the group consisting of gram positive bacteria, gram negative bacteria, yeast, fungi, and combinations thereof.   Microbial components include Pseudomonas aeruginosa, Aspergillus niger, Fusarium, Cephalosporium, Pseudomonas fluorescens, Pseudomonas rubescens, Pcenudomonas rubes Selected from the group consisting of Stutzeri (Pseudomonas stutzeri), Pseudomonas olevorans, Alcaligenes faecalis, Citrobacter freundii, Escherichia coli, and combinations thereof 20. The method of claim 19, wherein   20. The method of claim 19, further comprising 0.05 to about 5% formaldehyde source.   The formaldehyde source is cis 1- (3-chloroallyl) -3,5,7-triaza-1-azoniaadamantane chloride, hexahydro-1,3,5-tris (2-hydroxyethyl) -s-triazine, 4, 4-dimethyloxazolidine, 5-hydroxymethoxymethyl-1-1aza-3,7-dioxabicyclo-octane, dimethyloldimethyldantoin, N, N "-methylenebis [N '-(hydroxymethyl) -2,5 -Dioxo-4-imidazolidinyl] urea, N- (hydroxymethyl) -N- (1,3-dihydroxymethyl-2,5-dioxo-4-imidazolidinyl) -N ′-(hydroxymethyl) urea, hexahydro-1, Selected from the group consisting of 3,5-tris (2-hydroxyethyl) -s-triazine, and combinations thereof The method of claim 26.   20. A method for inhibiting the growth of a native microorganism or biofilm comprising the step of contacting said native microorganism or biofilm with an antimicrobial composition comprising the antimicrobial composition produced by the method of claim 19. In a stable and soluble antimicrobial composition formed by diluting the concentrate of claim 1,
From about 0.05% to about 5% by weight of a pyrithione or pyrithione complex;
Selected from the group consisting of about 0.005 wt% to about 1 wt% zinc salt, zinc oxide, zinc hydroxide, zinc sulfate, zinc chloride, zinc alloy, zinc complex, and combinations thereof A primary organic amine selected from the group consisting of a zinc source; and about 0.5 wt% to about 40 wt% amine component, 1,2-alkanolamine, 1,3-alkanolamine, and combinations thereof; , Alone or in the form of 1,2-alkanolamine, 1,3-alkanolamine, 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers and polymers And in combination with a secondary organic amine selected from the additional group consisting of combinations thereof, wherein the primary organic amine ensures that the amine component is dissolved in the antimicrobial composition. Enough An amine component that is present in the antimicrobial composition;
Wherein all percentages are based on the total weight of the antimicrobial composition, and the antimicrobial composition has an increased biocidal effect on native microorganisms or biofilms.   30. The stable and soluble antimicrobial composition of claim 29, further comprising about 0.05% to 5% formaldehyde or a formaldehyde source.   In a method of providing a stable and soluble antimicrobial concentrate comprising about 0.05% to about 20% pyrithione and a zinc source in an amount of about 0.1% to about 10%, the stabilization into the concentrate In an effective amount of at least one organic amine component, a primary organic amine selected from the group consisting of 1,2-alkanolamines, 1,3-alkanolamines, and combinations thereof, alone, or 1, 2-alkanolamine, 1,3-alkanolamine, 1,2-alkyldiamine monomers and polymers, 1,3-alkyldiamine monomers and polymers, and those In combination with a secondary organic amine selected from the group consisting of: wherein the primary organic amine is in the antimicrobial composition in an amount sufficient to ensure that the amine component is dissolved in the antimicrobial composition. Present And shall include the step of blending an organic amine component, a method for providing antimicrobial concentrate.   32. The method of claim 31, wherein an effective amount for stabilizing the organic amine is from 30% to about 80%, based on the total weight of the organic amine + zinc source + pyrithione.   32. The method of claim 31, wherein the stable and soluble antimicrobial concentrate further comprises about 0.5% to 30% formaldehyde or a formaldehyde source.   30. The composition of claim 29, which further inhibits the blue discoloration caused by the iron ions as compared to a composition comprising iron ions and no zinc and amine components.   30. The composition of claim 29 comprising formulating into a functional fluid selected from the group consisting of a paint, an adhesive, a coating, and a sealant to impart antimicrobial efficacy to the functional fluid. Method.   The functional fluid is effective to treat a substrate selected from the group consisting of wood and wood composites, masonry construction and stone, leather, hard surfaces, fabrics, textiles, plastics, medical products, and combinations thereof. 36. The method of claim 35, comprising a component.   A concentrated composition according to claim 1, comprising formulating a functional fluid selected from the group consisting of paint, adhesive, coating, and sealant to impart antimicrobial efficacy to the functional fluid. The method to use.   The functional fluid is effective to treat a substrate selected from the group consisting of wood and wood composites, masonry construction and stone, leather, hard surfaces, fabrics, textiles, plastics, medical products, and combinations thereof. 38. The method of claim 37, comprising a component.