Biocidal compositions and methods

Abstract

Generally, the present disclosure relates to biocidal compositions that include an isothiazolone biocidal active compound in combination with a guanidine accelerator. These compositions can demonstrate highly effective inhibition of deterioration and decay that can be caused by microbial contamination using low concentrations of the biocidal active compound. The guanidine accelerator can be crystallized around an inert inorganic mineral.

Description

[Technical Field]

[0001] Related applications

[0001] This application is based on and claims priority of U.S. Provisional Patent Application No. 63 / 163279, filed on 19 March 2021, which is incorporated herein by reference. [Background technology]

[0002]

[0002] Biocides are used in many fields to control the growth of harmful microorganisms and to prevent deterioration and decay, microbial slime deposits, and biofilms caused by microbial contamination. As used herein, the term “biocide” is intended to include, but is not limited to, fungicides, mycicides, and / or algaecides, and “biocidal activity” refers to both the elimination and inhibition of the growth of bacteria, fungi, and / or algae.

[0003]

[0003] Isothiazolones (4-isothiazolinone-3-ones, a term used interchangeably herein) are highly effective biocides and are widely used in various industries as biocides with a broad therapeutic range. Two of the most widely used isothiazolone biocides are 5-chloro-2-methyl-4-isothiazolinone-3-one (chloromethylisothiazolinone or CMIT) and 2-methyl-4-isothiazolinone-3-one (methylisothiazolinone or MIT), which are also often used together in a 3:1 mixture (CMIT:MIT). However, MIT is allergenic and cytotoxic, which has led to some concerns about the use of MIT. Due to the increased use of these isothiazolinone preservatives in recent years, there have been reports of an increase in the number of reported cases of contact allergies to mixtures of MIT and CMIT. 4-Isothiazolin-3-one derivative, 1,2-benzisothiazolin-3-one (BIT), exhibits a broad spectrum of antimicrobial activity against bacteria, fungi, and yeasts, and also shows high chemical and thermal stability. However, a maximum dose of 500 ppm is required for reliable and rapid biocide activity. N-(n-butyl)-1,2-benzisothiazolin-3-one (BBIT) is another biocide widely used in polymers, metal cutting fluids, paints, and coatings for its antimicrobial and antifungal properties, and typically requires a dose of 1.5-2 ppm to exert sufficient resistance against common bacteria or fungi, such as Aspergillus niger.

[0004]

[0004] To broaden the effectiveness of biocidal compositions, isothiazolones have also been combined with various other biocidal agents. For example, biocidal compositions containing pyrithione and 2-alkylisothiazolin-3-one have been widely used in the past. Zinc pyrithione (ZPT) is a broad-spectrum antimicrobial and antifungal agent. Due to its low solubility in water (8 ppm at neutral pH), zinc pyrithione is suitable for use in outdoor paints and other products that provide protection against white mold and algae. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005]

[0005] Restrictions on the use of isothiazolone biocides are increasing, and the use of this class of compounds will likely have to be further reduced in the future. Similarly, recent potential restrictions on pyrithione salts, which are typically used in similar applications, will also result in a decrease in the number of pyrithione biocides available. Therefore, it has become essential to identify biocides that offer equivalent or improved performance without the known drawbacks. [Means for solving the problem]

[0006]

[0006] Generally, this disclosure is directed toward compositions having biocidal properties that exhibit appropriate biocidal activity against microorganisms such as bacteria and / or fungi, which can be used to protect technical materials (e.g., paints, coatings, or surfaces) from degradation and decay caused by contamination by these microorganisms. Biocidal compositions may be incorporated into various products to protect against or reduce microbial growth in the product. Thus, exemplary embodiments of this disclosure may include biocidal compositions, biocidal products incorporating biocidal compositions, and methods for protecting a material or part of a material using such biocidal compositions.

[0007]

[0007] For example, one exemplary embodiment of the present disclosure may include a biocidal composition comprising a 4-isothiazolin-3-one biocidal compound and a guanidine enhancer, which is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine. The results demonstrated that the addition of such exemplary guanidine enhancers may result in an adjuvant effect that improves the effectiveness of known biocidal compounds, while on the other hand, they do not exhibit significant biocidal activity alone. This surprising result allows for the formulation of biocidal compositions containing smaller amounts of the 3-isothiazolin-3-one biocidal substance, mitigating at least some of the environmental concerns associated with such products.

[0008]

[0008] Another exemplary embodiment of the present disclosure may include a product incorporating a biocidal composition. In manufacturing and production, certain biocidal compositions may be incorporated at concentrations higher than required for effective protection. An exemplary product incorporating a biocidal composition may contain an effective concentration of a guanidine promoter and / or a 4-isothiazolin-3-one biocidal compound to achieve effective protection. Furthermore, the concentration of the 3-isothiazolin-3-one biocidal substance may be present at a reduced concentration such that the product exhibits limited environmental or other safety concerns.

[0009]

[0009] Another exemplary aspect of the present disclosure may include a method for forming a biocide composition having a guanidine accelerator. This method may include the step of dispersing an inert inorganic mineral and one or more cyanoguanidines, such as 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine, in a liquid. The cyanoguanidine can crystallize around the inert inorganic mineral to form a guanidine accelerator. Thus, the guanidine accelerator may contain cyanoguanidine crystallized on the inert inorganic mineral.

[0010]

[0010] One further example of the present disclosure may include a method for formulating a product incorporating a biocide composition. These, along with other features and aspects of the present disclosure, will be discussed in more detail below.

[0011]

[0011] A complete and practical description of this disclosure is further elaborated in the remainder of this specification, including by reference to the accompanying figures. [Brief explanation of the drawing]

[0012] [Figure 1]

[0012] Figure 1 shows an example biocidal composition that may be combined with the product to produce a biocidal product according to an example embodiment of the present disclosure. [Modes for carrying out the invention]

[0013]

[0013] The repeated use of reference characters in this specification and the drawings is intended to represent the same or similar features or elements of the present invention.

[0014]

[0014] It should be understood by those skilled in the art that this disclosure is merely an illustration of exemplary embodiments and is not intended to limit the broader aspects of the present disclosure.

[0015]

[0015] This disclosure is generally directed to compositions having biocidal properties that exhibit suitable biocidal activity against microorganisms and may be used to protect materials from degradation and / or spoilage caused by contamination by such microorganisms. In an exemplary embodiment, the biocidal composition may include at least one 4-isothiazolin-3-one biocidal active compound and at least one guanidine promoter. In another exemplary embodiment, the biocidal composition may be incorporated into a carrier to produce a biocidal product. For example, the biocidal product may include a fluid carrier (e.g., a liquid, suspension, emulsion, or other similar fluid) that can be mixed with the biocidal composition to incorporate an effective amount of the biocidal composition to produce the biocidal product. In a further exemplary embodiment, the biocidal composition and / or the biocidal product may be applied to or incorporated into a region of the material as a treatment to protect at least that region of the material from degradation and / or spoilage.

[0016]

[0016] In an implementation according to this disclosure, an exemplary biocidal composition may include at least one isothiazolin-3-one biocidal active compound and at least one guanidine promoter having the structure of Compound I, and Compound I has the formula: HR2N-(C=NHR3)-NR1H

[0017]

Chemical formula

[0018] (wherein, R3 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -alkynyl, C7-C 30 -alkylaryl, or C6-C 12 -aryl; R1 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -alkynyl, C7-C 30 -alkylaryl, or C6-C 12 -aryl; R2 is H, CN, C1-C 30 -alkyl, C1-C 30 -alkenyl, C1-C 30 -alkynyl, C7-C 30 -alkylaryl, or C6-C 12 -aryl; and at least one of R3, R1, or R2 is CN).

[0019]

[0017] As used herein, references to chemical formulas use standard elemental symbols according to the periodic table (e.g., C represents carbon, N represents nitrogen, etc.). Further, since references to chemical formulas are based on standard bonds, carbon can form four bonds and nitrogen can form three bonds unless otherwise specified. Thus, the reference to CN should be understood to indicate a cyano group, in which carbon contains a triple bond with nitrogen and the remaining carbon bonds represent the attachment of the cyano group to the chemical structure.

[0020]

[0018] In some embodiments, the guanidine accelerator is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine (also called dicyandiamide), and a salt of 2-cyanoguanidine. Both 1-cyanoguanidine and 2-cyanoguanidine are derivatives of compound I, where R2 or R1 is CN and R3 is H, respectively; and R1 and R2 are H and R3 is CN. As should be understood, conversion between 1-cyanoguanidine and 2-cyanoguanidine may occur by tautomerization in aqueous solution or exposure to other proton-donating solvents, so a composition containing only one tautomer may show conversion to a mixture of the two over time. Furthermore, tautomer forms of species derived from compound I in general, although exemplified using 1-cyanoguanidine and 2-cyanoguanidine, may be included as guanidine accelerators in embodiments that exemplify the present disclosure. The tautomer form of compound I is given by formula:

[0021] [ka]

[0022] (In the formula, R3 is H, CN, C1~C) 30 -Alkyl, C1~C 30 - Alkenil, C1~C 30 -Alkinyl, C7~C 30 -Alkylaryl, or C6~C 12 - is aryl; R1 is H, CN, C1~C 30 -Alkyl, C1~C 30 - Alkenil, C1~C 30 -Alkinyl, C7~C 30 -Alkylaryl, or C6~C 12 - is aryl; R2 is H, CN, C1~C 30 -Alkyl, C1~C 30 - Alkenil, C1~C 30 -Alkinyl, C7~C 30 -Alkylaryl, or C6~C 12- comprising structures (a) and (b) having an aryl group; at least one of R3, R1, or R2 is CN.

[0023]

[0019] Generally, guanidine compounds can react with proton donors to form salts having a positively charged guanidinium cation paired with a negatively charged anion. Thus, in a particular biocide composition, the guanidine accelerator may be a salt of compound I, such as a salt of 1-cyanoguanidine and / or a salt of 2-cyanoguanidine.

[0024]

[0020] Some examples of anions that may be included as salts of 1-cyanoguanidine or 2-cyanoguanidine include inorganic anions such as halide ions (e.g., chloride ions, bromide ions, fluoride ions, iodide ions, etc.), nitrate ions, and sulfate ions. Alternatively or further, the anions may include organic anions, such as acetate anions, or carboxylic acid anions derived from fatty acids such as octanoic acid, decanoic acid, or dodecanoic acid.

[0025]

[0021] Generally, at least one 4-isothiazolin-3-one biocide compound of the present invention may be any 4-isothiazolin-3-one derivative known in the art that exhibits biocide activity. For example, at least one 4-isothiazolin-3-one biocide compound may be one or more of the following: 1,2-benzisothiazolin-3-one (BIT), N-(n-butyl)-1,2-benzisothiazolin-3-one (BBIT), 5-chloro-2-methyl-2H-isothiazolin-3-one (CMIT), 2-methyl-2H-isothiazolin-3-one (MIT), 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MTI), 2-octyl-3(2H)-isothiazolon (OIT), dichloro-n-octyl-2H-isothiazolin-3-one (DCOIT), N-methyl-1,2-benzisothiazolin-3-one (nMBIT), and 2,2-dithiobis(N-methylbenzamide) (DTMB).

[0026]

[0022] In a particular embodiment, at least one 4-isothiazolin-3-one biocide compound is 1,2-benzisothiazolin-3-one (BIT), N-(n-butyl)-1,2-benzisothiazolin-3-one (BBIT), or a mixture thereof. In some embodiments, BIT is the only 4-isothiazolin-3-one biocide compound in the biocide composition. Alternatively, in some embodiments, BBIT is the only 4-isothiazolin-3-one biocide compound in the biocide composition. In addition to at least one 4-isothiazolin-3-one biocide compound, the biocide composition of the present disclosure may contain at least one compound I guanidine promoter.

[0027]

[0023] As used herein, the term “auxiliary agent” refers to an additive that, when used in combination with an active compound, may affect the performance of the active compound but which itself exhibits no biocidal activity and / or significant biocidal activity in the compositions of the present invention. Although not bound by one particular theory, the guanidine promoters of the present invention are thought to enhance the biocidal efficacy of the biocidal compounds by assisting in the solubilization of these active compounds or by acting as a carrier for the active compounds. As a result, a smaller amount of isothiazolone may be used in the biocidal compositions of the present invention to obtain the desired biocidal activity, so that these biocidal compositions result in robust protection and preservation of products or parts protected from harmful bacteria and fungi.

[0028]

[0024] In the biocidal compositions according to this disclosure, the relative amounts of at least one 4-isothiazolin-3-one biocidal compound and at least one guanidine promoter may vary, for example, depending on the properties of the biocidal compound and the properties of the guanidine promoter. Advantageously, however, the weight ratio of the guanidine promoter to the 4-isothiazolin-3-one biocidal compound is about 800:1 or less and about 1:1 or more, for example, about 750:1 or less and about 1:1 or more, about 650:1 or less and about 25:1 or more, about 580:1 or less and 50:1 or more, or about 400:1 or less and 100:1 or more. In some implementations, the weight ratio of guanidine promoter to 4-isothiazolin-3-one biocide compound is approximately 800:1 or less and approximately 500:1 or more, for example, approximately 750:1 or less and approximately 550:1 or more, or approximately 700:1 or less and approximately 600:1 or more.

[0029]

[0025] In particular, in example biocidal compositions, the weight ratio of guanidine promoter to 4-isothiazolin-3-one biocidal compounds may be specified based on the total amount of each 4-isothiazolin-3-one biocidal compound, the individual amount of each 4-isothiazolin-3-one biocidal compound, or both. For example, in an embodiment comprising two types of 4-isothiazolin-3-one biocidal compounds (e.g., BIT and BBIT), the ratio of guanidine promoter to 4-isothiazolin-3-one biocidal compounds may be specified for each 4-isothiazolin-3-one biocidal compound. Furthermore or alternatively, the ratio of guanidine promoter to 4-isothiazolin-3-one biocidal compounds may be specified for the composition as a whole. For example, biocidal compositions according to this disclosure may have weight ratios of guanidine promoter to 4-isothiazolin-3-one biocidal compounds of about 800:1 or less and about 500:1 or more. Examples of biocidal compositions include 4-isothiazolin-3-one biocidal compounds, which are mixtures of BIT and BBIT, with BIT to 4-isothiazolin-3-one biocidal compounds having a ratio of approximately 650:1 or less and approximately 25:1 or more.

[0030]

[0026] The weight ratio of guanidine promoter to 4-isothiazolin-3-one biocide compound used herein should be read based on the guanidine promoter. For example, about 800:1 or less is used to indicate that there are 800 or fewer units by weight of guanidine promoter per unit by weight of the 4-isothiazolin-3-one biocide compound. As another example for illustrative purposes, about 1:1 or more is used to indicate that there are 1 or more units by weight of guanidine promoter per unit by weight of the 4-isothiazolin-3-one biocide compound.

[0031]

[0027] One exemplary embodiment of the present disclosure may include a biocidal composition having a 4-isothiazolin-3-one biocidal substance which is BIT, with a weight ratio of guanidine accelerator to BIT of about 800:1 or less and about 1:1 or more. In another exemplary embodiment, the biocidal composition may include a 4-isothiazolin-3-one biocidal substance which is BIT and / or BBIT, with a weight ratio of guanidine accelerator to BIT, BBIT, or both of them of about 800:1 or less and about 1:1 or more. In yet another exemplary embodiment, the biocidal composition may include a 4-isothiazolin-3-one biocidal substance which is BIT and / or BBIT, with a weight ratio of guanidine accelerator to BIT, BBIT, or both of them of about 800:1 or less and about 500:1 or more.

[0032]

[0028] In another example embodiment, the biocidal composition may include a guanidine promoter which is 1-cyanoguanidine and / or 2-cyanoguanidine, and a 4-isothiazolin-3-one biocidal compound which is BIT. In the biocidal composition, the weight ratio of the guanidine promoter to BIT is about 800:1 or less and about 1:1 or more.

[0033]

[0029] In another example embodiment, the biocidal composition may include a guanidine promoter which is 1-cyanoguanidine and / or 2-cyanoguanidine, and a 4-isothiazolin-3-one biocidal compound which is BBIT. In the example biocidal composition, the weight ratio of the guanidine promoter to BBIT is about 800:1 or less and about 1:1 or more.

[0034]

[0030] In a further exemplary embodiment, the biocidal composition may include a 4-isothiazolin-3-one biocidal compound which is a mixture of BIT and BBIT, and the guanidine promoter is 1-cyanoguanidine and / or 2-cyanoguanidine. In an exemplary biocidal composition, the weight ratio of 1-cyanoguanidine and / or 2-cyanoguanidine to BIT is about 400:1 or less and about 1:1 or more, and the weight ratio of 1-cyanoguanidine and / or 2-cyanoguanidine to BBIT is about 350:1 or less and about 1:1 or more.

[0035]

[0031] As used herein, relative ratio or weight ratio refers to weight / weight (w / w) ratio. When a w / w ratio is disclosed herein with respect to a salt such as a guanidinium salt, it is calculated with respect to the free base, for example, with respect to the guanidinium portion of the guanidinium salt. This means that when a relative ratio is calculated, the molecular weight of the counterion to the guanidinium cation is not taken into consideration. As used herein, parts per million (ppm) similarly refers to weight / weight ratio, i.e., 1 ppm is 1 × 10⁻⁶ per weight -6 This means 0.000001, or 0.0001 by weight percent.

[0036]

[0032] The biocidal compositions of the present invention are particularly effective against bacteria and / or fungi. Exemplary microorganisms include one or more species belonging to one or both of the following groups:

[0037]

[0033] Bacteria: Alcaligenes, e.g., Alcaligenes faecalis; Acinetobacter, e.g., Acinetobacter calcoaceticus; Bacillus, e.g., Bacillus subtilis; Citrobacter, e.g., Citrobacter freundii; Corynebacterium, e.g., Corynebacterium ammoniagenes; Enterobacter, e.g., Enterobacter aerogenes or Enterobacter cloaca Enterococcus species (e.g., Enterococcus hirae), Escherichia species (e.g., Escherichia coli), Proteus species (e.g., Proteus hauseri), Pseudomonas species (e.g., Pseudomonas aeruginosa, Pseudomonas fluorescens, or Pseudomonas stutzeri), Salmonella species (e.g., Salmonella enterica), Staphylococcus species (e.g., Staphylococcus aureus);

[0034] Fungi: Acremonium, e.g., Acremonium strictum; Alternaria, e.g., Alternaria tenuis or Alternaria alternata; Aspergillus, e.g., Aspergillus niger or Aspergillus brasiliensis; Candida, e.g., Candida albicans; Chaetomium, e.g., Chaetomium globosum; Fusarium, e.g., Fusarium solanii solani, etc., genus Geotrichum, for example Geotrichum candidum, genus Lentinus, for example Lentinus tigrinus, genus Penicillium, for example Penicillium glaucum, Penicillium funiculosum, or Penicillium pinophilum, genus Rhodotorula, for example Rhodotorula rubra or Rhodotorula mucilaginosa, genus Stachybotrys, for example Stachybotrys Trichoderma species, such as Trichoderma chartarum, and Trichoderma virens.

[0038]

[0035] The biocidal compositions of this disclosure may further contain biocidal compounds. Examples of such further biocidal compounds include bronopol, benzyl hemiformal, tetramethylazodicarboxamide (TMAD), 1,3-bis(hydroxymethyl)-5,5-dimethylimidazolidine-2,4-dione (DMDMH), tris-hydroxymethylnitromethane (THNM), dimethyloxazolidine (DMO), p-chloro-m-cresol, dimethylolurea, 1,2-dibromo-2,4-dicyabutane, 2,2-dibromo-3-nitrilopropionamide, glutardialdehyde, ethylene glycol hemiformal, ethylene glycol-bis-hemiformal, N-methylolurea, bis(tetrakishydroxymethyl)phosphoni Ummonium sulfate (THPS), thiabendazole, carbendazim, zinc pyrithione, sodium pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, calcium pyrithione, magnesium pyrithione, organic pyrithione amine, barium pyrithione, pyrithione strontium, copper pyrithione, cadmium pyrithione, 2-phenoxyethanol, phenoxypropanol, o-phenylphenol, benzyl alcohol, sodium dithiocarbamate, chlorophene, quaternary ammonium salts, e.g., N-alkyl-N,N-dimethylbenzylammonium chloride, or tri-n-butyltetradecylphosphonium chloride, C8~C 16 Examples include alkylamines, as well as organic acids such as benzoic acid, dehydroacetic acid, sorbic acid, and salicylic acid.

[0039]

[0036] However, in some embodiments of the present disclosure, the biocidal composition and / or biocidal product may be limited to containing only the 4-isothiazolin-3-one biocidal compound and not containing any further biocidal compounds as described above. In particular, exemplary biocidal compositions of the present disclosure can satisfy the requirements for preservative effect without employing pyrithione or pyrithione salts as described above. For example, some embodiments may include biocidal compositions that do not contain pyrithione or pyrithione salts.

[0040]

[0037] Furthermore, in some embodiments of the present disclosure, the biocidal compositions and / or biocidal products may be limited to not containing biguanidine or polymeric biguanidine having a cyano group covalently bonded to one or more nitrogen atoms of the biguanidine or polymeric biguanidine. In these compounds, although not attributable to one particular theory, the biguanidine or polymer can carry multiple positive charges and therefore can act as a disruptor to the cell membrane. Thus, these compounds can act as biocidal compounds rather than as adjuvants, and their use in particular embodiments of the present disclosure may be limited.

[0041]

[0038] In one exemplary embodiment, a biocide composition and / or biocide product having a guanidine accelerator may contain, in addition to the guanidine accelerator, one or more biocide compounds including at least one 4-isothiazolin-3-one biocide compound. For example, a biocide composition and / or biocide product may be prepared by dispersing an inert inorganic mineral in a liquid and dissolving the guanidine accelerator in it. For example, the guanidine accelerator may be dissolved in the liquid first, and the inert inorganic mineral may then be dispersed in the liquid. Alternatively, the inert inorganic mineral may be dispersed in the liquid first, and then a guanidine accelerator in a certain liquid may be dissolved in that liquid. The guanidine accelerator can then crystallize around the inert inorganic mineral to form a guanidine accelerator for a biocide composition and / or biocide product. Thus, a guanidine accelerator can crystallize around an inert inorganic mineral in a particular exemplary embodiment.

[0042]

[0039] The liquid may be any suitable liquid that dissolves the guanidine accelerator, such as one or more of the guanidine accelerators having the structure of compound I. For example, the solvent may include water for dissolving 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and / or a salt of 2-cyanoguanidine. The liquid may be heated to help dissolve the guanidine accelerator. For example, the liquid may be heated to 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, or 100°C or higher to help dissolve the guanidine accelerator. Heating the liquid also helps crystallize the guanidine accelerator around the inert inorganic mineral. For example, after dispersing an inert inorganic mineral in a heated liquid and dissolving the guanidine accelerator and / or one or more biocide compounds, the guanidine accelerator may crystallize around the inert inorganic mineral as the liquid cools. Therefore, the liquid temperature may decrease as the guanidine accelerator crystallizes around the inert inorganic mineral.

[0043]

[0040] Inert inorganic minerals may be materials suitable for dispersion in liquids. For example, inert inorganic minerals may be one or more of silicate, chalk, diatomaceous earth, calcium carbonate, magnesium carbonate, dolomite, magnesium oxide, calcium sulfate, clay, calcium bentonite, kaolin, Chinese clay, talc, perlite, mica, vermiculite, silica powder, montmorillonite, attapulgite, lime clay, loess, limestone, and lime. By dispersing inert inorganic minerals in liquids, they may advantageously provide nucleation sites for the crystallization of guanidine promoters.

[0044]

[0041] The inert inorganic mineral may be selectively sorted by size to provide a desired particle size for the guanidine accelerator. For example, after the guanidine accelerator has crystallized around the inert inorganic mineral, the inert inorganic mineral may be milled such that the particle size of the guanidine accelerator is approximately equal to the particle size of one or more biocidal compounds, including at least one 4-isothiazolin-3-one biocidal compound. Thus, the particles of the guanidine accelerator and the particles of one or more biocidal compounds, including at least one 4-isothiazolin-3-one biocidal compound, dispersed in an aqueous dispersion may both be approximately equivalent. As another example, after the guanidine accelerator has crystallized around the inert inorganic mineral, the inert inorganic mineral may be milled such that the particle size of the guanidine accelerator facilitates the dispersion of the guanidine accelerator in a biocidal composition and / or biocidal product having the guanidine accelerator. Controlling the milling size of the inert inorganic mineral may be advantageously more precise than milling the guanidine accelerator.

[0045]

[0042] The biocidal compositions of the present invention have many applications and may be used in any suitable industry or field. The biocidal compositions of the present invention may be in the form of microencapsulated in a solution, emulsion, suspension, dust, powder, foam, paste, granular material, resin, or polymer material. The type of formulation will depend on the specific intended purpose and should generally ensure a fine and uniform distribution of the biocidal composition according to the present invention.

[0046]

[0043] For example, the biocidal composition may be used in the paints and coatings industry, the building chemistry field, the polymer chemistry field, the mineral oil industry, the textile industry, or the photochemical industry. The degree of increase in biocidal activity observed in the biocidal compounds of the biocidal composition of the present invention also makes the biocidal composition potentially useful as a disinfectant. The biocidal composition is particularly useful for preserving cans or dry films, or for treating industrial process water.

[0047]

[0044] More specifically, the biocidal compositions of the present disclosure may include a solvent for dispersing the components of the biocidal composition. The solvent can act to disperse the components throughout the solvent so that any volume of solvent will have substantially equal concentrations of each component (e.g., guanidine accelerator) contained in the biocidal composition. In one example embodiment, the solvent may include water, but other solvents or mixtures of solvents known in the art may be incorporated into the biocidal composition.

[0048]

[0045] In some embodiments, the solvent does not need to dissolve all components of the biocidal composition to a clearly discernible degree. In these compositions, surfactants or other phase stabilizers may be used to produce a dispersion. For example, some exemplary embodiments may include a biocidal composition that is an aqueous dispersion. The aqueous dispersion may be characterized by a water content of 95% or less and 20% or more based on the weight of the biocidal composition. Accordingly, exemplary embodiments of the present disclosure may include a biocidal composition that is an aqueous dispersion containing a guanidine accelerator and a 4-isothiazolin-3-one biocidal compound.

[0049]

[0046] The biocidal compositions of the present invention may be added to a product or site to which microorganisms are to be controlled. The biocidal compounds and guanidine promoters may also be in the form of essential raw materials, namely, concentrates ("biocidal concentrates") containing at least one 4-isothiazolin-3-one biocidal compound and at least one compound I guanidine promoter, which may then be added to the product. The concentrates may also be diluted with a suitable solvent or carrier before being added to the product, or suspended, dissolved, or emulsified in a suitable solvent or carrier. Addition of the biocidal composition to the product to be protected may be used to produce a biocidal product.

[0050]

[0047] Accordingly, this disclosure further intends to include biocidal products comprising the biocidal compositions according to this disclosure.

[0051]

[0048] In the biocidal product, at least one 4-isothiazolin-3-one biocidal compound and at least one guanidine promoter are present in biocidal effective amounts. The amounts of at least one 4-isothiazolin-3-one biocidal compound and at least one guanidine promoter in the biocidal product may vary based on various factors such as the biocidal compound or the guanidine promoter.

[0052]

[0049] In an example of a biocidal product, the biocidal product may contain a certain amount of biocidal composition according to various embodiments of the present disclosure, such that at least one 4-isothiazolin-3-one biocidal compound is present in the biocidal product at a concentration of about 1 ppm or more and about 500 ppm or less, for example, about 400 ppm or less, 300 ppm or less, 200 ppm or less, 150 ppm or less, 100 ppm or less, 50 ppm or less, or 25 ppm or less.

[0053]

[0050] For example, a biocidal product may include a biocidal composition provided in this disclosure. The biocidal composition may include at least one 4-isothiazolin-3-one biocidal compound, which is BIT, BBIT, or a mixture thereof. BIT may be present in the biocidal product in amounts of 1 ppm or more and 100 ppm or less, and / or BBIT may be present in the biocidal product in amounts of about 1 ppm or more and 130 ppm or less. For example, BBIT may be present in the biocidal product in amounts of about 1 ppm or more and 130 ppm or less, for example 90 ppm or less, 80 ppm or less, 70 ppm or less, or 60 ppm or less (for example, about 10 ppm, about 20 ppm, about 30 ppm, about 40 ppm, about 50 ppm, etc.). Furthermore, or alternatively, BIT may be present in the biocidal product in amounts of approximately 10 ppm or more and approximately 130 ppm or less, for example, approximately 20 ppm or more and approximately 120 ppm or less, approximately 30 ppm or more and approximately 110 ppm or less, approximately 40 ppm or more and approximately 100 ppm or less, approximately 50 ppm or more and approximately 100 ppm or less, approximately 60 ppm or more and approximately 100 ppm or less, approximately 70 ppm or more and approximately 100 ppm or less, approximately 80 ppm or more and approximately 100 ppm or less, or approximately 90 ppm or more and approximately 100 ppm or less (for example, approximately 25 ppm, approximately 40 ppm, approximately 50 ppm, approximately 60 ppm, approximately 70 ppm, approximately 80 ppm, approximately 90 ppm, approximately 100 ppm, or approximately 110 ppm).

[0054]

[0051] More specifically, the example biocidal product may contain a 4-isothiazolin-3-one biocidal compound which is one or both of 1,2-benzisothiazolin-3-one and N-(n-butyl)-1,2-benzisothiazolin-3-one. BIT may be present in the example biocidal product in amounts of 20 ppm or more and 60 ppm or less, and BBIT may be present in the example biocidal product in amounts of 40 ppm or more and 100 ppm or less, or both.

[0055]

[0052] As should be understood, by adding a biocidal composition to a product to produce a biocidal product, the ratio of at least one 4-isothiazolin-3-one biocidal compound and the ratio of at least one guanidine promoter in the biocidal product is generally about the same as the ratio of these components in the biocidal composition according to the present disclosure.

[0056]

[0053] Therefore, the guanidine accelerator is present in concentrations of approximately 1 ppm or more and approximately 40,000 ppm or less, for example, approximately 38,000 ppm or less, approximately 36,000 ppm or less, approximately 34,000 ppm or less, approximately 32,000 ppm or less, approximately 30,000 ppm or less, or approximately 25,000 ppm or less (for example, approximately 15,000 ppm, approximately 16,000 ppm, approximately 18,000 ppm, approximately 20,000 ppm, approximately 22,000 ppm, etc. It may be present in the biocidal product in amounts of 00 ppm, approximately 24,000 ppm, approximately 26,000 ppm, approximately 28,000 ppm, approximately 30,000 ppm, approximately 32,000 ppm, approximately 34,000 ppm, approximately 36,000 ppm, approximately 37,000 ppm, approximately 38,000 ppm, approximately 39,000 ppm, approximately 39,500 ppm, approximately 39,600 ppm, approximately 39,700 ppm, or approximately 39,800 ppm.

[0057]

[0054] In particular, example biocidal products may contain a 4-isothiazolin-3-one biocidal compound, which is 1,2-benzisothiazolin-3-one, and 1,2-benzisothiazolin-3-one is present in the product in amounts of 10 ppm or more and 90 ppm or less. Example biocidal products may also contain a guanidine accelerator, which is 1-cyanoguanidine, 2-cyanoguanidine, or a mixture thereof, and the guanidine accelerator is present in the product in amounts of 500 ppm or more and 7,000 ppm or less.

[0058]

[0055] In one example embodiment, the biocidal product may include a biocidal composition incorporated into the product, such as paints, coatings, sealants, gypsum, starch solutions, aqueous inorganic slurries, dispersions, caulking materials, colored pigment slurries, inorganic fillers and colored pigment slurries, building chemical products, glues or adhesives, polymer dispersions, emulsion polymers, detergents or cleaning agents, mineral oils or mineral oil products, cooling lubricants, auxiliaries for the leather industry and / or textile industry and / or photochemical industry, chemical industry semi-finished products or intermediates, waxes and / or clay emulsions, inks, cleaning agents, and disinfectants.

[0059]

[0056] The biocidal compositions of the present invention can demonstrate improved biocidal efficacy in aqueous solvent systems. Accordingly, one exemplary embodiment may include the pH of the biocidal composition or the pH of the biocidal product.

[0060]

[0057] The pH of the biocidal composition or biocidal product of the present invention may vary over a considerable range. Preferably, the pH of the biocidal composition and biocidal product of the present invention is greater than about 5.0, greater than about 5.5, greater than about 6.0, greater than about 6.5, greater than about 7.0, greater than about 7.5, greater than about 8.0, or greater than about 8.5. More preferably, the pH is greater than about 7.0, greater than about 7.5, greater than about 8.0, or greater than about 8.5. Most preferably, the pH is greater than about 8.5 and less than 12.0. In particular embodiments, the biocidal composition or biocidal product may contain a buffer. Examples of suitable buffers are known in the art. Generally, increased hydrolysis of the guanidine accelerator of the present invention (i.e., decreased chemical stability) is observed under acidic conditions (i.e., pH less than about 7.0).

[0061]

[0058] Another example of the present disclosure may include a method for inhibiting the growth of bacteria and fungi in a site that may be exposed to or is prone to bacterial and fungal contamination. For example, this method may include the step of incorporating the biocidal composition according to the present disclosure into the site in an amount effective in adversely affecting the growth of bacteria and fungi. Generally, the site may be a place or site, a surface, a material, a factory, or equipment.

[0062]

[0059] The foregoing description is illustrative and is not intended to limit the scope, applicability, or configuration of the Disclosure. Various modifications to the embodiments described may be made to the functions and arrangements of the elements described herein without departing from the scope of the Disclosure.

[0063]

[0060] As used herein, the terms “about,” “approximately,” or “generally,” when used to modify a value, indicate that the value may be increased or decreased by 10%, for example, 7.5%, 5%, 4%, 3%, 2%, 1%, or any range or value in between, and still remain within the scope of the disclosed embodiments. Furthermore, the term “substantially absent,” when used to describe the amount of a substance in a material, should not be limited to being completely or entirely absent, but may correspond to the absence of any recognizable or detectable amount of the enumerated substance in the material. Thus, for example, if the amount of a substance in a material is less than the accuracy of an industrially acceptable apparatus or test for measuring the amount of a substance in a material, the material is “substantially absent” of the substance. In a particular example embodiment, if the amount of substance in the material is less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1% by weight, less than 0.5% by weight, or less than 0.1% by weight, the material may be said to be "substantially free" of the substance.

[0064]

[0061] As used in this specification and in the claims, the singular forms "a," "an," and "the" include the plural form unless otherwise clearly indicated in the context. Furthermore, the term "includes" means "comprises." The methods and compositions of this disclosure include, consist of, or essentially consist of, the essential elements and limitations of the embodiments described herein, as well as any additional or optional raw materials, components, or limitations described herein or useful in nutritional compositions.

[0065]

[0062] Unless otherwise specified, any quantities of raw materials, any numbers representing properties, such as molecular weight, percentage, etc., used herein or in the claims should be understood to be modified with the term "approximately." Thus, unless implicitly or explicitly specified otherwise, the numerical parameters shown are estimates that may depend on the desired properties to be sought and / or the detection limits under standard test conditions / methods. To directly and explicitly distinguish embodiments from the prior art described herein, the number of embodiments is not an estimate unless the word "approximately" is enumerated.

[0066]

[0063] As used herein, “optional” or “optionally” means that the material, event, or environment described thereafter may or may not be present or occur, and that the description includes both instances in which the material, event, or environment is present or occurs and instances in which it is not present or occurs. As used herein, “w / w%” and “wt%” mean weight as a percentage of the total weight or weight relative to another component in the composition.

[0067]

[0064] The term "effective amount" means the amount of a compound that promotes, improves, stimulates, or acts upon a response to a particular disease or disorder, or to a particular symptom of a disease or disorder.

[0068]

[0065] Referring to the drawings, Figure 1 shows some exemplary embodiments of the present disclosure. As shown, the exemplary biocidal composition 10 may comprise a 4-isothiazolin-3-one biocidal compound 12 and a guanidine accelerator 14. In some exemplary embodiments, the biocidal composition 10 can be combined with or incorporated into a product 20 (e.g., a paint, coating, or carrier) to produce a biocidal product 30. The biocidal product 30 may comprise an effective amount of the 4-isothiazolin-3-one biocidal compound 12 and a guanidine accelerator 14 according to an exemplary embodiment of the present disclosure.

[0069]

[0066] This disclosure can be better understood by referring to the following embodiments. [Examples]

[0070]

[0067] Various formulations were prepared in accordance with this disclosure and tested for their performance. In one challenge test, the effectiveness of dicyandiamide as an adjuvant to BIT was evaluated using an improved ASTM D2574-97 “Standard Test Method for Resistance of Emulsion Paints in the Container to Attack by Microorganisms,” which uses higher inoculation volumes and frequencies. Three different samples were inoculated using standard communities of four bacterial populations: Pseudomonas eruginosa, Escherichia coli, Enterobacter cloaca, and Acinetobacter chalcaceticus, with sample sizes of 10%, 5%, or 2.5%. A portion of each sample was streaked onto trypsin-soybean agar 24 hours and 72 hours after each inoculation. Dilution plates were counted at the final 72-hour mark. The results of this challenge are shown in Table 1.

[0071] [Table 1]

[0072]

[0068] As shown in Table 1, the inclusion of dicyandiamide alone (not in combination with BIT) did not show a significant difference compared to a blank without dicyandiamide or a 4-isothiazolin-3-one biocide compound such as BIT. However, the combination of dicyandiamide and BIT demonstrated a significant enhancement of the efficacy of BIT in the challenge tests of the examples. Repeated challenge tests were performed using the same conditions to confirm the efficacy, and the results are summarized in Table 2.

[0073] [Table 2]

[0074]

[0069] As shown in Table 3, further challenge tests were conducted to evaluate the effectiveness of dicyandiamide as an adjuvant in MIT.

[0075] [Table 3]

[0076]

[0070] As shown in Table 3, the efficacy of samples containing MIT alone (e.g., without using guanidine enhancers such as dicyandiamide) is satisfactory at concentrations of 30 ppm or higher (e.g., 35 ppm) (indicated by *). However, the use of a combination of MIT and dicyandiamide can enable effective microbial control at low MIT concentrations of as low as 20 ppm. Furthermore, higher concentrations of dicyandiamide appear to improve the efficacy of MIT, demonstrating that even lower concentrations of MIT (e.g., less than 20 ppm) can demonstrate effective microbial control depending on the concentration of dicyandiamide.

[0077]

[0071] Unless otherwise specified, the data of the examples shown in Tables 1, 2, and 3 should be understood to represent the degree of microbial growth observed at a given data point. In particular, each plate was ranked from 0 to 5c (i.e., one of 0, 1, 2, 3, 4, 5, or 5c) according to the degree of microbial growth observed, where rank "0" indicates no growth; rank "1" indicates 1 to 5 observed colony-forming units (cfu), i.e., the plate is very lightly contaminated; rank "2" indicates 6 to 15 cfu, i.e., the plate is lightly contaminated; rank "3" indicates 16 to 30 cfu, i.e., the plate is moderately contaminated; rank "4" indicates 31 to 45 cfu, i.e., the plate is heavily contaminated; rank "5" indicates more than 45 cfu, i.e., the plate is severely contaminated; and rank "5c" indicates dense growth, i.e., the plate is very severely contaminated. Therefore, for example, Challenge 1 for BIT 50 ppm over 24 hours in Table 1 has a value of 5, indicating that more than 45 cfu were observed. As another example for illustrative purposes, Table 1 shows that Challenge 1 for 5,000 ppm dicyandiamide + 50 ppm BIT over 24 hours had a value of 1, and 1 to 5 cfu were observed.

[0078]

[0072] Without departing from the spirit and scope of the invention as described in more detail in the appended claims, these and other modifications and variations of the present disclosure can be practiced by those skilled in the art. Furthermore, it should be understood that the various embodiments may be interchangeable, either whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is merely illustrative and is not intended to limit the invention as described further in such appended claims. The following is a description of the claims as they were at the time of filing the application. [Claim 1] The steps include: dispersing inert inorganic minerals in a liquid; The steps include: dissolving the guanidine promoter in the liquid; The steps include: crystallizing the guanidine promoter around the inert inorganic mineral; A method for forming a biocidal composition, comprising: The method wherein the guanidine promoter is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine. [Claim 2] The method according to claim 1, wherein the liquid includes water. [Claim 3] The method according to claim 1 or 2, wherein the liquid is heated to 70°C or higher before the guanidine accelerator is crystallized around the inert inorganic mineral. [Claim 4] The method according to any one of claims 1 to 3, wherein the liquid is heated to 80°C or higher before the guanidine accelerator is crystallized around the inert inorganic mineral. [Claim 5] The method according to any one of claims 1 to 4, wherein the temperature of the liquid decreases while the guanidine accelerator crystallizes around the inert inorganic mineral. [Claim 6] The method according to any one of claims 1 to 5, wherein the inert inorganic mineral comprises one or more of silicate, chalk, diatomaceous earth, calcium carbonate, magnesium carbonate, dolomite, magnesium oxide, calcium sulfate, calcium bentonite, kaolin, Chinese clay, talc, perlite, mica, vermiculite, silica powder, montmorillonite, attapulgite, lime clay, loess, limestone, and lime. [Claim 7] The method according to any one of claims 1 to 6, wherein the inert inorganic mineral is milled before being dispersed in the liquid. [Claim 8] The method according to any one of claims 1 to 7, further comprising the step of dispersing a 4-isothiazolin-3-one biocide compound in the liquid. [Claim 9] 4-Isothiazolin-3-one biocide compound; Guanidine promoter and A biocidal composition containing, The guanidine promoter is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine. The guanidine promoter crystallizes around the inert inorganic mineral. Biocidal composition. [Claim 10] The biocide composition according to claim 9, wherein the 4-isothiazolin-3-one biocide compound is one or both of 1,2-benzisothiazolin-3-one and N-(n-butyl)-1,2-benzisothiazolin-3-one. [Claim 11] The biocidal composition according to claim 9 or 10, wherein the weight ratio of the guanidine promoter to the 4-isothiazolin-3-one biocidal compound in the biocidal composition is about 800:1 or less and about 1:1 or more. [Claim 12] The biocidal composition is an aqueous dispersion, and the aqueous dispersion has a water content of 20% by weight or more and 95% by weight or less of the biocidal composition, any of claims 9 to 11 A biocidal composition as described in any one of the items. [Claim 13] A product comprising the biocidal composition according to any one of claims 9 to 12. [Claim 14] The product according to claim 13, wherein the 4-isothiazolin-3-one biocide compound is present in an amount of about 1 ppm or more and about 400 ppm or less. [Claim 15] The product according to claim 13 or 14, wherein the guanidine promoter is present in an amount of 1 ppm or more and 32,000 ppm or less. [Claim 16] The product according to any one of claims 13 to 15, which is a paint, coating, sealant, gypsum, starch solution, aqueous inorganic slurry, dispersion, caulking material, slurry of colored pigments, inorganic filler and slurry of colored pigments, building chemical products, glue or adhesive, polymer dispersion, emulsion polymer, detergent or cleaning agent, mineral oil or mineral oil product, cooling lubricant, auxiliaries for the leather industry and / or textile industry and / or photochemical industry, semi-finished or intermediate products of the chemical industry, wax, clay emulsion, ink, or disinfectant. [Claim 17] The product according to claim 16, which is a paint, coating, emulsion polymer, or aqueous inorganic slurry.

Claims

1. The steps include: dispersing inert inorganic minerals in a liquid; The steps include: dissolving the guanidine accelerator in the liquid; The steps include: dispersing the 4-isothiazolin-3-one biocide compound in the liquid; The steps include: crystallizing the guanidine promoter around the inert inorganic mineral; A method for forming a biocidal composition, comprising: The method wherein the guanidine promoter is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine.

2. The method according to claim 1, wherein the liquid contains water.

3. The method according to claim 1 or 2, wherein the liquid is heated to 70°C or higher before the guanidine accelerator is crystallized around the inert inorganic mineral.

4. The method according to any one of claims 1 to 3, wherein the liquid is heated to 80°C or higher before the guanidine accelerator is crystallized around the inert inorganic mineral.

5. The method according to any one of claims 1 to 4, wherein the temperature of the liquid decreases while the guanidine accelerator crystallizes around the inert inorganic mineral.

6. The method according to any one of claims 1 to 5, wherein the inert inorganic mineral comprises one or more of silicate, chalk, diatomaceous earth, calcium carbonate, magnesium carbonate, dolomite, magnesium oxide, calcium sulfate, calcium bentonite, kaolin, Chinese clay, talc, perlite, mica, vermiculite, silica powder, montmorillonite, attapulgite, lime clay, loess, limestone, and lime.

7. The method according to any one of claims 1 to 6, wherein the inert inorganic mineral is milled before being dispersed in the liquid.

8. 4-Isothiazolin-3-one biocide compound; Guanidine promoter and A biocidal composition containing, The guanidine promoter is one or more of 1-cyanoguanidine, a salt of 1-cyanoguanidine, 2-cyanoguanidine, and a salt of 2-cyanoguanidine. The guanidine promoter is crystallized around an inert inorganic mineral. Biocidal composition.

9. The biocidal composition according to claim 8, wherein the 4-isothiazolin-3-one biocidal compound is one or both of 1,2-benzisothiazolin-3-one and N-(n-butyl)-1,2-benzisothiazolin-3-one.

10. The biocidal composition according to claim 8 or 9, wherein the weight ratio of the guanidine promoter to the 4-isothiazolin-3-one biocidal compound in the biocidal composition is 800:1 or less and 1:1 or more.

11. The biocidal composition is an aqueous dispersion, and the aqueous dispersion has a water content of 20% by weight or more and 95% by weight or less of the biocidal composition, according to any of claims 8 to 10. A biocidal composition as described in any one of the items.

12. A product comprising the biocidal composition according to any one of claims 8 to 11.

13. The product according to claim 12, wherein the 4-isothiazolin-3-one biocide compound is present in amounts of 1 ppm or more and 400 ppm or less.

14. The product according to claim 12 or 13, wherein the guanidine promoter is present in an amount of 1 ppm or more and 32,000 ppm or less.

15. The product according to any one of claims 12 to 14, which is a paint, coating, sealant, gypsum, starch solution, aqueous inorganic slurry, dispersion, caulking material, slurry of colored pigments, inorganic filler and slurry of colored pigments, building chemical products, glue or adhesive, polymer dispersion, emulsion polymer, detergent or cleaning agent, mineral oil or mineral oil product, cooling lubricant, auxiliaries for the leather industry and / or the textile industry and / or the photochemical industry, semi-finished or intermediate products of the chemical industry, wax, clay emulsion, ink, or disinfectant.

16. The product according to claim 15, which is a paint, coating, emulsion polymer, or aqueous inorganic slurry.

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