Preservative blend with increased efficacy

Abstract

A preservative composition is disclosed containing a mixture of isothiazolinones comprising 1,2-benzoisothiazoline-3-one (BIT), 2-methyl-2H-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-2H-isothiazolin-3-one (CMIT) in combination with at least one antimicrobial ingredient. In one aspect, the antimicrobial ingredient can operate synergistically in conjunction with the isothiazolinones. In this regard, the preservative composition and the end use products incorporating the preservative composition can contain the isothiazolinones in a total concentration of less than about 50 ppm, such as less than about 45 ppm, such as less than about 43 ppm.

Description

PRESERVATIVE BLEND WITH INCREASED EFFICACYCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to the benefit of U.S. Provisional Application No. 63 / 660693, filed June 17, 2024, which is expressly incorporated herein by reference in its entirety.BACKGROUND

[0002] Biocidal agents are used in many fields to control the growth of harmful microorganisms and to prevent deterioration and decay caused by microbial contamination, microbial slime deposits and biofilms.

[0003] For example, microbial contamination of home care products, industrial products and other similar products is a matter of great importance to the industry and can become a major cause of both product losses of end-use formulations and economic losses. Preservative agents and preservative compositions for protecting and preserving end-use formulations against microbial attack from bacterial or fungal growth are known in the art. These preservative agents and compositions have a wide variety of applications in fields such as personal care products, cosmetics, home care products, and health and hygiene products. Conventional preservative agents and compositions have used traditional active ingredients which provide good bacterial and fungicidal properties against microbial attack.

[0004] Ideally, a preservative agent or composition has a broad-spectrum of activity against all types of microorganisms at various pH levels. The preservative agent or composition should also have high efficacy so that a minimum amount of the preservative can be used to save cost and to avoid or reduce any possible adverse effects caused by the preservative agent or preservative agents in the preservative composition. Also, it is desirable that the preservative agent or composition is stable to any changes in temperature encountered during manufacturing, packaging, and shipping as well as during storage of the endformulation in which the preservative agent or compositions is placed. Further, an ideal preservative agent or components of a preservative composition are physically and chemically compatible with ingredients present in various end-useformulations so that one preservative agent or preservative composition can suitably be incorporated in various products.

[0005] Isothiazolones (4-isothiazolin-3-ones, terms used interchangeably herein) are highly effective biocides and widely used as broad-spectrum biocides in various industries. Two of the most widely used isothiazolone biocides are 5- chloro-2-methyl-4-isothiazolin-3-one (chloromethylisothiazolinone or CM IT) and 2- methyl-4-isothiazolin-3-one (methylisothiazolinone or MIT), which are also often used together in a 3:1 mixture (CMIT:MIT). The 4-isothiazolin-3-one derivative 1 ,2- benzisothiazolin-3-one (BIT) exhibits a broad antimicrobial activity spectrum against bacteria, fungi and yeast and also exhibits a high degree of chemical and thermal stability. Recently, however, CMIT, MIT and BIT have been the subject of governmental scrutiny. Thus, there is increasing pressure to reduce the amount of these antimicrobials in end use formulations.

[0006] Consequently, there has been considerable effort to find compounds that will synergistically interact with biocides in order to boost the efficacy of the biocides. For instance, isothiazolones have been combined in the past with polyglycerol esters and guanidines as disclosed in WO2021 / 214237 and U.S. Patent Publication No. 2021 / 0235699, which are both incorporated herein by reference.

[0007] Although the above publications provide great advances in the art, further improvements are still needed. For instance, a need currently exists for a biocidal composition that exhibits a high degree of biocidal activity while keeping isothiazolones at very low concentrations.SUMMARY

[0008] In general, the present disclosure is directed to a preservative composition containing a blend of 4-isothiazolin-3-one compounds in combination with at least one antimicrobial ingredient that, when blended together, can provide synergistic effects. In this way, the amount of isothiazolinones can be minimized while providing excellent efficacy against many different microorganisms, including bacteria, viruses, fungi, and the like.

[0009] In one embodiment, the present disclosure is directed to a preservative composition comprising a mixture of isothiazolinones. The mixture of isothiazolinones comprises 1 ,2-benzisothiazolin-3-one (BIT), 2-methyl-2H-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-2H-isothiazolin-3-one (CMIT). The mixture of isothiazolinones is combined with at least one antimicrobial ingredient. The antimicrobial ingredient can comprise an aromatic alcohol, an organic acid, a chelator, an enzyme, a quaternary ammonium compound, a pyrithione, a formaldehyde donor, bronopol, a carbamate, or salts thereof, or mixtures therof. The antimicrobial agent increases the efficacy of the preservative composition against at least one microorganism in comparison to a similar composition only containing the mixture of isothiazolinones. In particular, the increase in efficacy can be greater than the additive effect of the biocidal activity of the antimicrobial ingredient and the mixture of isothiazolinones taken alone.

[0010] In one aspect, the 1 ,2-benzisothiazolin-3-one (BIT) is present in the composition in an amount of from about 1 to about 40 ppm. In addition, the total amount of 2-methyl-2H-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-2H- isothiazolin-3-one (CMIT) present in the composition is less than 2 ppm, such as less than about 1 .5 ppm.

[0011] In one embodiment, the antimicrobial ingredient comprises an aromatic alcohol. The aromatic alcohol can comprise phenoxyethanol, benzyl alcohol, 3- phenyl-1 -propanol, or mixtures thereof. The mixture of isothiazolinones can be present in the preservative composition in relation to the aromatic alcohol at a weight ratio of from about 1 : 10 to about 1 :5,000, such as from about 1 : 15 to about 1 :3,000, such as from about 1 :20 to about 1 :2,000.

[0012] When the antimicrobial ingredient comprises an organic acid, the organic acid can comprise benzoic acid, sorbic acid, lactic acid, itaconic acid, citric acid, levulinic acid, salicylic acid, gluconic acid, dehydroacetic acid, formic acid, glycolic acid or salts thereof, or mixtures thereof. Dehydroacetic acid is an organic compound having a chemical formula of CsHsCM and, as used herein, is defined as an organic acid. The mixture of isothiazolinones can be present in the preservative composition in relation to the organic acid or salts thereof at a weight ratio of from about 1 :5 to about 1 :5,000, such as from about 1 : 10 to about 1 :2,000, such as from about 1 : 15 to about 1 :500.

[0013] In one embodiment, the antimicrobial ingredient comprises a pyrithione, such as sodium pyrithione, zinc pyrithione, or mixtures thereof. The pyrithione can be present in the preservative composition in relation to the mixture ofisothiozolinones such that the weight ratio between the mixture of isothiazolinones to the one or more pyrithione compounds is from about 1 :100 to about 100:1 , such as from about 1 : 10 to about 10:1 , such as from about 1 :5 to about 5: 1 .

[0014] In still another embodiment, the antimicrobial ingredient can comprise a quaternary ammonium compound having the following general formula:[R1R2R3R4N+]rYr- wherein R1is an optionally substituted benzyl group or an optionally substituted alkyl or aryl-substituted alkyl group; R2and R3are independently optionally substituted alkyl groups; R4is selected from the group consisting of an optionally substituted alkyl or aryl-substituted alkyl group, benzyl group, and -[(CH2)2-O]n- R5, wherein n is an integer from 1 to 20 and R5is selected from the group consisting of hydrogen, phenyl, and alkyl-substituted phenyl groups; Y- is a chlorine ion, bromine ion, phosphate, carbonate, bicarbonate, carboxylate, saccharinate, ethosulfate, sulfate, sulfonate, or nitrate; and r is 1 , 2 or 3. For instance, the quaternary ammonium compound can comprise an alkyl dimethyl benzyl ammonium chloride or can comprise at least one dialkyl dimethyl ammonium chloride. The one or more quaternary ammonium compounds can be present in the preservative composition in relation to the mixture of isothiazolinones such that the weight ratio between the mixture of isothiazolinones to the one or more quaternary ammonium compounds is from about 1 :100 to about 100: 1 , such as from about 1 : 10 to about 10:1 , such as from about 1 :5 to about 5: 1.

[0015] The antimicrobial ingredient can also comprise a formaldehyde donor, wherein the formaldehyde donor comprises a hydantoin such as dimethylol dimethyl hydantoin (DMDMH), oxazolidine, sodium N-(hydroxymethyl)glycinate, 2,2',2-(hexahydro-1 ,3-5-triazine-1 , 3, 5-triyl-)triethanol (HHT), (ethylenedioxy)dimethanol (EDDM), or salts thereof, or mixtures thereof. The formaldehyde donor can be present in the preservative composition in relation to the mixture of isothiazolinones such that the weight ratio between the mixture of isothiazolinones to the one or more formaldehydes donors is from about 1 :100 to about 100: 1 , such as from about 1 : 50 to about 50: 1 , such as from about 1 : 10 to about 10:1.

[0016] In one embodiment, the antimicrobial ingredient can comprise a chelator. The chelator can comprise ethylenediaminetetraacetic acid, glutamic acid, N,N-diacetic acid, methylglycinediacetic acid, diethylenetriaminepenta(methylene phosphonic acid) (DTPMP), Etidronic acid (HEDP), Amino tris(methylene phosphonic acid (ATMP), ethylenediamine tetra(methylene phosphonic acid)(EDTMP), gluconic acid, gluconolactone, or salts thereof, or mixtures thereof. When a chelator is included in the composition, the weight ratio between the mixture of isothiazolinones to the one or more chelators is from about 2: 1 to about 1 :10, such as from about 1 : 1 to about 1 :8, such as from about 1 :1 to about 1 :5.

[0017] In one aspect, the antimicrobial ingredient can be a carbamate. The carbamate, for instance, can comprise iodopropynyl butyl carbamate (IPBC). The carbamate can be present in the preservative composition in relation to the mixture of isothiazolinones such that the weight ratio between the mixture of isothiazolinones to carbamate can be from about 1 :5,000 to about 50:1 , such as from about 1 :2,000 to about 10:1 , such as from about 1 :1 ,000 to about 1 :1.

[0018] In yet another aspect, the antimicrobial ingredient can be bronopol or an enzyme. The weight ratio between the mixture of isothiazolinones to bronopol can be from about 5,000: 1 to about 10: 1 , such as from about 1 : 1 ,000 to about 2: 1 , such as from about 1 :500 to about 1 :1. The weight ratio between the mixture of isothiazolinones to one or more enzymes can be from about 1 :2,000 to about 500: 1 , such as from about 1 : 1 ,000 to about 200: 1 , such as from about 1 :250 to about 1 :2.

[0019] The antimicrobial composition of the present disclosure can also contain various other components. For instance, the composition can contain at least one of a solvent, a surfactant, a complexing agent, a corrosion inhibitor, an alkalinity builder, a pH adjusting agent, an auxiliary, an acid, a foaming agent, a perfume, an enzyme, a colorant, a humectant, an emulsifier, a thickener, an antioxidant, a UV blocking agent, a wax, a natural extract, or an oil.

[0020] The preservative composition of the present disclosure can be incorporated into various products at the concentration of isothiazolinones as described above. In one aspect, for instance, the preservative composition can be incorporated into a home care product. The home care product can comprise ahand soap, a dish soap, a machine dish soap, a machine dish rinse-aid, a laundry detergent, a laundry fabric conditioner, a clothing fragrance, a wrinkle treatment, an ironing aid, an all-purpose cleaner, a polish such as a car polish or furniture polish, a cleaning wipe, a floor cleaner, a carpet cleaner, a toilet cleaner, a bathroom cleaner, a hard surface cleaner, a kitchen cleaner, or the like.

[0021] The preservative composition can also be incorporated into an industrial product. The industrial product can comprise a paint, a coating, a varnish, a sealing composition, a leather auxiliary, a paper coating agent, a plaster, an adhesive, a sealant, a caulk, a mineral slurry, a pigment dispersion, a pigment slurry, a concrete, a polymer emulsion, a polymer dispersion, an ink, a size, or the like.

[0022] In still another embodiment, the preservative composition can be incorporated into an agricultural chemical product. The agricultural chemical product can comprise a pesticide such as a biopesticide, a biostimulant, a fertilizer, a micronutrient, a mineral slurry, a colorant, a dye, an adjuvant, a seed coating, a pesticide formulation, or the like.

[0023] The present disclosure is also directed to a method of protecting a product subject or susceptible to infestation or destruction or deterioration by one or more microorganisms. The method includes incorporating into the product an effective amount of a preservative composition as described above. When incorporated into a product, in accordance with the present disclosure, the BIT concentration is maintained below 40 ppm and the total amount of MIT and CMIT is maintained below 2 ppm.

[0024] Other features and aspects of the present disclosure are discussed in greater detail below.DETAILED DESCRIPTION

[0025] It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present disclosure.

[0026] In general, the present disclosure is directed to a composition having biocidal properties that exhibits appropriate biocidal activity against microorganisms and may be used to protect materials against deterioration and / or decay caused by contamination from microorganisms. The biocidal orpreservative composition of the present disclosure contains a blend of isothiazolinones in conjunction with at least one antimicrobial ingredient that enhances the overall biocidal properties of the composition.

[0027] Although isothiazolinones display excellent antimicrobial properties, there is currently increased pressure to reduce the amount of these types of biocides in various compositions. For instance, there is increased governmental scrutiny over home care products that contain isothiazolinones. Minimizing the amount of isothiazolinones in a preservative composition can provide numerous benefits in handling and labeling the product. In accordance with the present disclosure, the amount of isothiazolinones is minimized by combining a blend of isothiazolinones with an antimicrobial ingredient that increases the efficacy of the composition against at least one microorganism.

[0028] The blend of components according to the present disclosure is particularly well suited for use as a preservative composition. As used herein, a “preservative” means a biocidal agent or biocidal composition which is intended to be blended with or into an end use formulation, such as a home care product, an agricultural product, or an industrial product, to prevent microorganisms from destroying or degrading the end use formulation or making the end use formulation unuseful for the particular purpose that the end use formulation was developed.

[0029] The preservative composition of the present disclosure, as described above, can contain at least one isothiazolinone, such as at least two isothiazolinones and, in one embodiment, contains at least three isothiazolinones. Isothiazolinones having biocidal activity include 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)-isothiazolone (OIT), dichloro-n-octyl-2H- isothiazolin-3-one (DCOIT), N-methyl-1 ,2-benzisothiazolin-3-one (nMBIT), and 2,2- dithiobis(N-methylbenzamide) (DTMB).

[0030] In one aspect, for instance, the preservative composition of the present disclosure contains a combination of BIT, MIT, and CMIT. As described above, combining the mixture of isothiazolinones with an antimicrobial ingredient allows for excellent efficacy against many microorganisms while maintaining isothiazolinone concentrations at extremely low levels. For instance, BIT can bepresent in the preservative composition and in products containing the preservative composition of about 40 ppm or less, such as from about 1 to about 40 ppm. For instance, the BIT concentration in the preservative composition or end use product can be less than about 38 ppm, such as less than about 35 ppm, and greater than about 5 ppm, such as greater than about 10 ppm, such as greater than about 15 ppm, such as greater than about 20 ppm.

[0031] The combined amount of MIT and CMIT in the preservative composition and in an end use product containing the preservative composition can be less than about 5 ppm, such as less than about 3 ppm, such as less than about 2 ppm, such as less than about 1 .8 ppm, such as less than about 1 .6 ppm. The total concentration of MIT and CMIT in the preservative composition and / or the end use formulation can be greater than about 0.4 ppm, such as greater than about 0.6 ppm, such as greater than about 0.8 ppm, such as greater than about 1 ppm.

[0032] In accordance with the present disclosure, the mixture of isothiazolinones are combined with at least one antimicrobial ingredient in a way that increases the efficacy of the preservative composition while minimizing the amount of isothiazolinones in the composition. For instance, in one aspect, an antimicrobial ingredient is added to the composition that has a synerginic effect when combined with the mixture of isothiazolinones such that the increase in efficacy against at least one microorganism is greater than the additive effect of the biocidal activity of the antimicrobial ingredient and the mixture of isothiazolinones taken alone.

[0033] The antimicrobial ingredient combined with the mixture of isothiazolinones in accordance with the present disclosure can vary depending upon the particular application and the desired result. For instance, selection of the antimicrobial ingredient can depend upon the end use product, the type of microorganisms to be controlled, and the synergistic effect of the combination of components. Examples of antimicrobial ingredients include aromatic alcohols, organic acids, chelators, enzymes, quaternary ammonium compounds, pyrithiones, aldehydes, bronopol, a carbamate, salts thereof, or mixtures thereof.

[0034] In one aspect, for instance, the antimicrobial ingredient can comprise an aromatic alcohol. The aromatic alcohol, for instance, can comprise phenoxyethanol, benzyl alcohol, phenylpropanol, 2,4-dichlorophenyl methanol,chlorphenesin, benzyl hemiformal, and mixtures thereof. One or more aromatic alcohols can be present in the preservative composition and in the end use composition in an amount generally less than about 2% by weight, such as in an amount less than about 1 .5% by weight, such as in an amount less than about 1 .2% by weight, such as in an amount less than about 1 % by weight, such as in an amount less than about 0.8% by weight, such as in an amount less than about 0.5% by weight. The one or more aromatic alcohols can be present in the preservative composition or the end use formulation in an amount greater than about 0.001 % by weight, such as in an amount greater than about 0.01 % by weight, such as in an amount greater than about 0.1 % by weight.

[0035] In one aspect, one or more aromatic alcohols can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more aromatic alcohols is from about 1 : 10 to about 1 :5,000, such as from about 1 : 15 to about 1 :3,000, such as from about 1 :20 to about 1 :2,000.

[0036] In another aspect, the antimicrobial ingredient can comprise an organic acid or salt thereof. The organic acid, for instance, can comprise lactic acid, itaconic acid, citric acid, levulinic acid, dehydroacetic acid, benzoic acid, salicylic acid, sorbic acid, or mixtures thereof. As used herein, the term “organic acid” refers to an organic compound with acidic properties and includes dehydroacetic acid. Salts of organic acids include, for instance, metal salts, such as alkali or alkaline earth metal salts of benzoic acid. Such salts can include, for instance, sodium benzoate, potassium sorbate, and the like. One or more organic acids or salts thereof can be present in the preservative composition or in the end use formulation in an amount generally less than about 4% by weight, such as in an amount less than about 3% by weight, such as in an amount less than about 2% by weight, such as in an amount less than about 1 .5% by weight, such as in an amount less than about 1 % by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.2% by weight, such as in an amount less than about 0.1 % by weight. One or more organic acids or salts thereof can generally be present in an amount greater than about 0.0001 % by weight, such as in an amount greater than about 0.01 % by weight, such as in anamount greater than about 0.1 % by weight, such as in an amount greater than about 0.2% by weight.

[0037] In one aspect, one or more organic acids or salt thereof can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more organic acids or salt thereof is from about 1 :5 to about 1 :5,000, such as from about 1 :10 to about 1 :2,000, such as from about 1 : 15 to about 1 :500.

[0038] In another aspect, the antimicrobial ingredient can comprise one or more chelators. Chelators or chelating agents are capable of binding to metal ions, such as calcium, magnesium, iron, copper, or the like, to form stable complexes. It was discovered that chelating agents can have a synergistic effect when combined with low levels of isothiazolinones.

[0039] Examples of chelators that may be incorporated into the preservative composition of the present disclosure include ethylene diamine tetraacetic acid (EDTA), glutamic acid, N,N-diacetic acid (GLDA), methylglycine diacetic acid (MGDA), diethylene triamine penta(methylene phosphonic acid) (DTPMP), sodium gluconate, and the like. In one aspect, the chelator can be biodegradable, such as GLDA and / or MGDA. One or more chelators can be present in the preservative composition or in the end use formulation in an amount less than about 1 % by weight, such as in an amount less than about 0.75% by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.25% by weight, such as in an amount less than about 0.1 % by weight, such as in an amount less than about 0.01 % by weight. One or more chelators can be present in the preservative composition and the end use formulation in an amount greater than about 1 ppm, such as in an amount greater than about 10 ppm, such as in an amount greater than about 50 ppm, such as in an amount greater than about 100 ppm.

[0040] In one aspect, one or more chelators can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more chelators is from about 2:1 to about 1 :10, such as from about 1 : 1 to about 1 :8, such as from about 1 : 1 to about 1 :5.

[0041] In still another aspect, the antimicrobial ingredient comprises a quaternary ammonium compound. In one aspect, for instance, the quaternary ammonium compound can have the following general formula:[R1R2R3R4N+]rYr- wherein R1is an optionally substituted benzyl group or an optionally substituted alkyl or aryl-substituted alkyl group; R2and R3are independently optionally substituted alkyl groups; R4is selected from the group consisting of an optionally substituted alkyl or aryl-substituted alkyl group, benzyl group, and -[(CH2)2-O]n- R5, wherein n is an integer from 1 to 20 and R5is selected from the group consisting of hydrogen, phenyl, and alkyl-substituted phenyl groups; Y- is a chlorine ion, bromine ion, phosphate, carbonate, bicarbonate, carboxylate, saccharinate, ethosulfate, sulfate, sulfonate, or nitrate; and r is 1 , 2 or 3.

[0042] In one embodiment, the quaternary ammonium compound may comprise a dialkyl ammonium compound, such as a dimethyl dialkyl ammonium compound. In one embodiment, the dimethyl dialkyl ammonium compound may have between about 8 and about 12 carbon atoms, such as from about 8 to about 10 carbon atoms in each of the alkyl groups.

[0043] Examples of dimethyl dialkyl ammonium compounds which may be used include dimethyl dioctyl ammonium compounds such as dimethyl dioctyl ammonium chloride, dimethyl didecyl ammonium compounds such as dimethyl didecyl ammonium chloride and the like. Mixtures of dimethyl dialkyl ammonium compounds may also be used and other anions, such as those described above may also be used. Commercially available dimethyl dialkyl ammonium compounds include, for example, compositions marketed and sold under the BARDAC™ tradename by Arxada AG.

[0044] In an alternative embodiment, the antimicrobial agent may comprise a benzyl ammonium compound, such as an alkyl dimethyl benzyl ammonium compound. In general, the alkyl group may contain from about 10 to about 18 carbon atoms, such as from about 12 to about 16 carbon atoms.

[0045] Examples of alkyl dimethyl benzyl ammonium compounds include C12 alkyl dimethyl benzyl ammonium chloride, C14 alkyl dimethyl benzyl ammonium chloride, and C16 alkyl dimethyl benzyl ammonium chloride. In addition, a mixtureof these alkyl dimethyl benzyl ammonium compounds can be used. Commercially available alkyl dimethyl benzyl ammonium compounds include, for example, compositions marketed and sold under the BARQUAT® tradename by Arxada AG. These commercially available alkyl dimethyl benzyl ammonium compounds are blends of C12, C14, and C16 alkyl dimethyl benzyl ammonium chlorides.Generally, it is preferable that the alkyl dimethyl benzyl ammonium compound, when a blend, contains higher concentrations of C12 alkyl and C14 alkyl components than C16 alkyl components. It is noted that other anions, including those mentioned above, may also be used.

[0046] In still another embodiment, the quaternary ammonium compound may comprise a quaternary ammonium propionate. The quaternary ammonium propionate, for instance, may comprise a poly(oxyalkyl)ammonium propionate. In one particular embodiment, for instance, the first biocide may comprise N,N- didecyl-N-methyl- poly(oxyethyl)ammonium propionate.

[0047] In one aspect, the antimicrobial agent(s) comprises a carbonate / bicarbonate salt of a quaternary ammonium cation. For example, the antimicrobial agent contained in the composition can comprise a di C8-C12 alkyl ammonium carbonate / bicarbonate. In one particular embodiment, the composition contains didecyl dimethyl ammonium carbonate and / or didecyl dimethyl ammonium bicarbonate.

[0048] In other embodiments, however, the carbonate / bicarbonate salts of quaternary ammonium cations may be selected from dioctyldimethylammonium carbonate, decyloctyldimethylammonium carbonate, benzalkonium carbonate, benzethonium carbonate, stearalkonium carbonate, cetrimonium carbonate, behentrimonium carbonate, dioctyldimethylammonium bicarbonate, decyloctyldimethylammonium bicarbonate, benzalkonium bicarbonate, benzethonium bicarbonate, stearalkonium bicarbonate, cetrimonium bicarbonate, behentrimonium bicarbonate, and mixtures of one or more such carbonate salts.

[0049] In another aspect, the quaternary ammonium compound can comprise an alkyl trimethyl ammonium compound, such as an alkyl trimethyl ammonium chloride. The alkyl group, for instance, can have a carbon chain length of from about 8 carbon atoms to about 20 carbon atoms. In one particular embodiment,the quaternary ammonium compound can be a trimethyl hexadecyl ammonium ion, such as a trimethyl hexadecyl ammonium chloride.

[0050] One or more quaternary ammonium compounds can be present in the preservative composition and the end use formulation at relatively low amounts, such as less than about 0.1 % by weight. For instance, one or more quaternary ammonium compounds can be present in the preservative composition and in the end use formulation in an amount less than about 0.08% by weight, such as in an amount less than about 0.05% by weight, and in an amount greater than about 1 ppm, such as greater than about 10 ppm, such as greater than about 50 ppm.

[0051] In one aspect, one or more quaternary ammonium compounds can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more quaternary ammonium compounds is from about 1 : 100 to about 100: 1 , such as from about 1 : 10 to about 10:1 , such as from about 1 :5 to about 5: 1 .

[0052] In still another aspect, the antimicrobial ingredient can comprise a pyrithione. Pyrithiones can have properties similar to a chelator and can also have antimicrobial properties.

[0053] Pyrithione is known by several names, including 2 mercaptopyridine-N- oxide; 2-pyridinethiol-1 -oxide (CAS Registry No. 1 121-31 -9); 1-hydroxypyridine-2- thione and 1 hydroxy-2(1 H)-pyridinethione (CAS Registry No. 1 121-30-8); 2- pyridinol-1 -oxide (HPNO) and N-hydroxy-6-octyloxypyridine 2(1 H)-one and - hydroxy-6-octyloxypyridine 2(1 H)-one ethanolamine salt. Pyrithione salts are commercially available from Arxada AG, such as Sodium OMADINE® or Zinc OMADINE®.

[0054] The pyrithione present as the preservative agent can be present in a water insoluble form or in a water soluble form. The pyrithione may comprise sodium pyrithione, zinc pyrithione, barium pyrithione, strontium pyrithione, copper pyrithione, cadmium pyrithione, and / or zirconium pyrithione. Other pyrithiones that may be present in the composition include sodium pyrithione, bismuth pyrithione, potassium pyrithione, lithium pyrithione, ammonium pyrithione, calcium pyrithione, magnesium pyrithione, silver pyrithione, gold pyrithione, manganese pyrithione, and / or an organic amine pyrithione. A single pyrithione may be present as thepreservative agent or a combination of any of the above may be included as the preservative agent.

[0055] The pyrithione particles can have a particle size such that 100% of the particles have a particle size of less than about 10 microns and at least 70% of the particles have a particle size less than 5 microns, such as at least about 50% of the particles can have a particle size of 1 micron or less. Particle size can be measured using a laser scattering particle size analyzer, such as a HORIBA LA 910 particle size analyzer.

[0056] The pyrithione particles can be produced by reacting pyrithione or a water-soluble salt of pyrithione, and a water-soluble polyvalent metal salt in a pressurized, turbulent flow reactor that generates pulverizing forces. The pulverizing forces produced by the pressurized, turbulent flow reactor efficiently generate pyrithione salt particles of micron size. The micron-sized pyrithione salt particles made by the method have a narrow and uniform size distribution, and have excellent surface deposition properties due to the large surface area provided by the population of micron particles.

[0057] One or more pyrithione compounds can be present in the preservative composition and the end use formulation in an amount generally less than about 1 % by weight, such as in an amount less than about 0.8% by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.3% by weight, such as in an amount less than about 0.1 % by weight, such as in an amount less than about 0.05% by weight, such as in an amount less than about 0.01 % by weight. One or more pyrithione compounds can be present in the preservative composition or the end use formulation in an amount greater than about 10 ppm, such as greater than about 50 ppm, such as greater than about 75 ppm, such as greater than about 100 ppm.

[0058] In one aspect, one or more pyrithione compounds can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more pyrithione compounds is from about 1 : 100 to about 100: 1 , such as from about 1 : 10 to about 10:1 , such as from about 1 :5 to about 5: 1.

[0059] In still another embodiment, the antimicrobial ingredient can comprise a formaldehyde donor such as an aldehyde, particularly a hydantoin. Theformaldehyde donor can comprise dimethylol dimethyl hydantoin (DMDMH), oxazolidine, sodium N-(hydroxymethyl)glycinate, 2,2',2-(hexahydro-1 ,3-5-triazine- 1 ,3,5-triyl-)triethanol (HHT), (ethylenedioxy)dimethanol (EDDM), or salts thereof, or mixtures thereof. One or more formaldehyde donors can be present in the preservative composition and / or the end use formulation in an amount less than about 0.3% by weight, such as in an amount less than about 0.2% by weight, such as in an amount less than about 0.1 % by weight, such as in an amount less than about 0.05% by weight, such as in an amount less than about 0.01% by weight. One or more formaldehyde donors can be present in the preservative composition or the end use formulation in an amount greater than about 1 ppm, such as in an amount greater than about 10 ppm, such as in an amount greater than about 50 ppm.

[0060] In one aspect, one or more formaldehyde donors can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to the one or more formaldehyde donors is from about 1 : 100 to about 100: 1 , such as from about 1 : 50 to about 50: 1 , such as from about 1 : 10 to about 10:1.

[0061] In another aspect, the antimicrobial ingredient can comprise bronopol. Bronopol is also known as 2-bromo-2-nitro-1 ,3-propane diol. Bronopol is effective against a wide range of bacteria, fungi, and algae. Bronopol works by disrupting the microbial cell membrane and inhibiting enzymatic activity, leading to cell death. Bronopol can be present in the preservative composition or the end use formulation in an amount less than about 2% by weight, such as in an amount less than about 1 % by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.1 % by weight, and in an amount greater than about 0.0001 % by weight, such as in an amount greater than about 0.01 % by weight.

[0062] In one aspect, bronopol can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to bronopol is from about 5,000:1 to about 10:1 , such as from about 1 : 1 ,000 to about 2: 1 , such as from about 1 :500 to about 1 :1.

[0063] In still another aspect, the antimicrobial ingredient can comprise a carbamate. For instance, the antimicrobial ingredient can comprise iodopropynylbutylcarbamate (IPBC). IPBC has bactericidal properties and can be effective against bacteria, fungi, and yeast. IPBC works by releasing iodine when it comes into contact with water, which subsequently prevents microbial growth. When present in the preservative composition or in an end use product, the composition can include a carbamate in an amount less than about 1 % by weight, such as in an amount less than about 0.8% by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.1 % by weight, and in an amount greater than about 10 ppm, such as in an amount greater than about 100 ppm, such as in an amount greater than about 500 ppm, such as in an amount greater than about 1 ,000 ppm.

[0064] In one aspect, carbamate can be present in the preservative composition or the end use formulation such that the weight ratio between the mixture of isothiazolinones to carbamate is from about 1 :5,000 to about 50:1 , such as from about 1 :2,000 to about 10:1 , such as from about 1 : 1 ,000 to about 1 :1.

[0065] In still another aspect, the antimicrobial ingredient can comprise an enzyme. Enzymes that can be incorporated into the preservative composition of the present disclosure, for instance, include lysozyme, nisin, natamycin, glucose oxidase, lactoperoxidase, transglutaminase, a protease, or mixtures thereof.

[0066] One or more enzymes can be incorporated into the preservative composition or to an end use product in an amount generally less than about 2% by weight, such as in an amount less than about 1 .5% by weight, such as in an amount less than about 1 % by weight, such as in an amount less than about 0.5% by weight, such as in an amount less than about 0.1 % by weight. For instance, one or more enzymes can be incorporated into the preservative composition or into the end use product in an amount less than about 1 ,000 ppm, such as in an amount less than about 750 ppm, such as in an amount less than about 500 ppm, such as in an amount less than about 300 ppm, such as in an amount less than about 100 ppm. The one or more enzymes can be present in the preservative composition or into the end use product in an amount greater than about 1 ppm, such as in an amount greater than about 2.5 ppm, such as in an amount greater than about 5 ppm, such as in an amount greater than about 10 ppm.

[0067] In one aspect, one or more enzymes can be present in the preservative composition or the end use formulation such that the weight ratio between themixture of isothiazolinones to the one or more enzymes is from about 1 :2,000 to about 500:1 , such as from about 1 :1 ,000 to about 200:1 , such as from about 1 :250 to about 1 :2.

[0068] The preservative composition of the present disclosure is particularly effective against bacteria, fungi, algae, and yeast. Exemplary microorganisms that can be controlled using the preservative composition of the present disclosure include the following.

[0069] Bacteria: Alcaligenes such as Alcaligenes faecalis, Acinetobacter such as Acinetobacter calcoaceticus, Bacillus such as Bacillus subtilis, Citrobacter such as Citrobacter freundii, Corynebacterium such as Corynebacterium ammoniagenes, Enterobacter such as Enterobacter aerogenes or Enterobacter cloacae, Enterococcus such as Enterococcus hirae, Escherichia such as Escherichia coli, Proteus such as Proteus hauseri, Pseudomonas such as Pseudomonas aeruginosa, Pseudomonas fluorescens or Pseudomonas stutzeri, Salmonella such as Salmonella enterica, Staphylococcus such as Staphylococcus aureus,

[0070] Fungi: Acremonium such as Acremonium strictum, Alternaria such as Alternaria tenuis or Alternaria alternata, Aspergillus such as Aspergillus niger or Aspergillus brasiliensis, Candida such as Candida albicans, Chaetomium such as Chaetomium globosum, Fusarium such as Fusarium solani, Geotrichum such as Geotrichum candidum, Lentinus such as Lentinus tigrinus, Penicillium such as Penicillium glaucum, Penicillium funiculosum or Penicillium pinophilum, Rhodotorula such as Rhodotorula rubra or Rhodotorula mucilaginosa, Stachybotrys such as Stachybotrys chartarum, Trichoderma such as Trichoderma virens.

[0071] The preservative composition of the present disclosure has numerous applications and can be used in any suitable industry or field. The preservative composition may be used in the form of a solution, an emulsion, a suspension, a dust, a powder, a foam, a paste, a granulate material, a resin, or can be microencapsulated in polymeric material.

[0072] In general, the preservation composition of the present disclosure can be incorporated into many different end use formulations or products. As used herein, “end use formulations” or “end use products” includes without limitationhome care products, industrial products, coating products, and agricultural products including crop protection products.

[0073] Home care product formulations, for instance, generally comprise a base composition to which the preservation composition of the present disclosure is added. The base composition may contain numerous and different ingredients depending upon the end use application. The home care product formulation, for instance, may contain solvents, surfactants, emulsifiers, complexing agents, corrosion inhibitors, alkalinity builders, pH adjusting agents, auxiliaries, acids, foaming agents, colorants, UV blocking agents, waxes, natural extracts, oils, consistency factors, conditioners, emollients, skin caring ingredients, moisturizers, thickeners, humectants, fillers, antioxidants, preservatives, fragrances and the like, as well as mixtures thereof.

[0074] Suitable surfactants for the base composition comprise: alkyl sulfates e.g. sodium lauryl sulfate, ammonium lauryl sulfate; sodium cetearyl sulfate; alkyl sulfoacetates e.g. sodium lauryl sulfoacetate; alkyl ether sulfates e.g. sodium laureth sulfate; sodium trideceth sulfate; sodium oleth sulfate; ammonium laureth sulfate; alkyl ether sulfosuccinates e.g. disodium laureth sulfosuccinate; alkyl glycosides e.g. decyl glucoside; lauryl glucoside; alkyl isethionates amphoterics e.g. cocam idopropyl betaine; sodium cocoamphoacetate; sodium lauroamphoacetate; disodium lauroamphodiacetate; disodium cocoamphodiacetate; sodium lauroamphopripionate; disodium lauroamphodipropionate; potassium or ammonium salts of the aforementioned amphoterics; capryl / capram idopropyl betaine; undecylenam idopropyl betaine; laurom idopropyl betaine; and fatty alcohol polyglycol ethers.

[0075] Suitable emulsifiers for the base composition are e.g. anionics as salts of fatty acids e.g. sodium stearate or sodium palmitate, organic soaps e.g. mono- di- or triethanolaminoeate, sulfated or sulfonated compounds e.g. sodium lauryl sulfate or sodium cetyl sulfonate, saponines, lamepones; cationics as quaternary ammonium salts; nonionics as fatty alcohols, fatty acid ester with saturated or unsaturated fatty acids, polyoxyethylenesters or polyoxyethylenethers of fatty acids, polymers from ethylene oxide and propylene oxide or propylene glycol, amphotherics as phosphatides, proteins as gelatine, casein alkylamidobetaines, alkyl betaines and amphoglycinates, alkyl phosphates, alkylpolyoxyethylenephosphates or the corresponding acids, silicone derivatives, e.g. alkyl dimethiconecoplyol.

[0076] Suitable emollients for the base composition are e.g. cetearyl isononanoate, cetearyl octanoate, decyl oleate, isooctyl stearate, coco caprylate / caprate, ethylhexyl hydroxystearate, ethylhexyl isononanoate, isopropyl isostearate, isopropyl myristate, oleyl oleate, hexyl laurate, paraffinum liquidum, PEG-75 lanolin, PEG-7 glyceryl cocoate, petrolatum, ozokerite cyclomethicone, dimethicone, dimethicone copolyol, dicaprylyl ether, butyrospermum parkii, buxus chinensis, canola, carnauba cera, copernicia cerifera, oenothera biennis, elaeis guineensis, prunus dulcis, squalane, zea mays, glycine soja, helianthus annuus, lanolin, hydrogenated castor oil, hydrogenated coconut oil, hydrogenated polyisobutene, sucrose cocoate, stearoxy dimethicone, lanolin alcohol, isohexadecane.

[0077] Suitable thickeners for the base composition are e.g. acrylates / steareth- 20 methacrylate copolymer, carbomer, carboxymethyl starch, cera alba, dimethicone / vinyl dimethicone crosspolymer, propylene glycol alginate, hydroxyethylcellulose, hydroxypropyl methylcellulose, silica, silica dimethyl silylate, xanthan gum, hydrogenated butylenes / ethylene / styrene copolymer.

[0078] Suitable humectants for the base composition are e.g. adipic acid, fumaric acid and its salts, benzoic acid and its salts, glycerine triacetate, sodium or magnesium lauryl sulfate, magnesium stearate, solid polyethylenglycol, polyvinylpyrrolidone, boric acid, mono-laurate or mono-palmitate, myristyl alcohol, cetyl alcohol, cetylstearyl alcohol, talcum, calcium or magnesium salts of higher fatty acids, mono-, di- or triglycerides of higher fatty acids, polytetrafluorethylene.

[0079] Suitable antioxidants for the base composition are e.g. sulfites, e.g. sodium sulfite, tocopherol or derivates thereof, ascorbic acid or derivates thereof, citric acid, propyl gallate, chitosan glycolate, cysteine, N-acetyl cysteine plus zinc sulfate, thiosulfates, e.g. sodium thiosulfate, polyphenols and the like.

[0080] The base composition of the home care product to which the preservation composition of the present disclosure is added can be various types of products.

[0081] Home care products include fabric care products, hand dish wash liquids, machine dish soaps, hard surface cleaners, polishes such as a car polishor furniture polish, and toilet care products. The home care product formulation may comprise all purpose cleaners and other similar formulations that are used around the home.

[0082] Fabric care products include, but are not limited to, fabric conditioner, laundry detergent liquid, laundry detergent pods or capsules, ironing aids, wrinkle treatments, clothing fragrances, stain removal liquids, carpet cleaners, washing machine cleaning solution, and fabric brightening solutions.

[0083] In one aspect, the fabric care product is a laundry detergent. Although the ingredients in laundry detergents can vary depending on whether the product is a liquid, pod, or capsule, many of the ingredients remain consistent among all of the laundry detergent product formulations.

[0084] Therefore, in another embodiment, the laundry detergent can contain the preservation composition of the present disclosure, surfactants, enzymes, dyes, hueing dyes, chelants, stabilizers, radical scavengers, perfumes, fluorescent whitening agents, suds-supressors, soil-suspension polymers, soil release polymers, dye-transfer inhibitors, fabric softening additives, rheology modifiers, washing or cleaning adjuvants, and other polymers.

[0085] Particularly suitable surfactants used in laundry detergents include nonionic surfactants, such as alkoxylate fatty alcohol nonionic surfactants, amphoteric surfactants, such as beta-n-alkylaminopropionic acids, n-alkyl-beta- iminodipropionic acids, imidazoline carboxylates, amine oxides, sultaines, betaines, phosphocholines, proprionates, di-propionates, sodium cocamphoacetate, disodium cocoamphodiacetate, 3-[(3- Cholamidopropyl)dimethylammonio]-1 -propanesulfonate (CHAPS), dipalmitoylphosphatidylcholine (DPPtdCho), sodium lauroamphocetate, or any combination of the foregoing.

[0086] Particularly suitable hueing dyes used in laundry detergents include Basic Violet 3 (Cl 42555) and Basic Violet 4 (Cl 426000), both commercially available from Standard Dyes.

[0087] Particularly suitable radical scavengers used in laundry detergents include trimethoxybenzoic acid.

[0088] Particularly suitable fluorescent whitening agents used in laundry detergents include Tinopal CBS-X.

[0089] Particularly suitable suds suppressors used in laundry detergents include non-fatty acid suds suppressors, such as silica / silicone, silicone oil, alcohols such as branched alcohols, dimethicone, and mixtures thereof.

[0090] Particularly suitable soil suspension polymers used in laundry detergents include PEI ethoxylate, HDMA diquate ethoxylates, sulfonated derivates, and hydrophobically modified copolymers.

[0091] Particularly suitable soil release polymers used in laundry detergents include PET alkoxylate short block copolymer.

[0092] Particularly suitable dye transfer inhibitors and dye fixatives included in laundry detergents include polyvinylpyrrolidone, poly-4-vinylpyridine-N-oxide, copolymers of N-viny-2-pyrrolidone and N-vinylimidazole and mixtures thereof.

[0093] Particularly suitable fabric softening additives used in laundry detergents include alkyl quaternary ammonium compounds, ester quaternary ammonium compounds, bentonite, silicones, cationic silicones, and mixtures thereof.

[0094] Particularly suitable rheology modifiers used in laundry detergents include methylcellulose, hydroxypropylmethylcellulose, xanthan gum, gellan gum, guar gum and hydroxypropyl guar gum, succinoglycan, and trihydroxystearin.

[0095] Particularly suitable wash or cleaning adjuvants used in laundry detergents include ethanol amine citrate, ethanol amine laurate, ethanol amine palmitate, ethanol amine oleate, ethanol amine stearate, C16 to C18 fatty acids, C18 unsaturated fatty acids, pentasodium pentetate, sodium laurate, sodium lauryl sulfate, sodium myristate, sodium oleate, sodium palmitate, sodium polyacrylate, sodium stearate, and mixtures thereof.

[0096] Particularly suitable stabilizers and blending aids used in laundry detergents include calcium formate, diethylene glycol, dipropylene glycol, an alcohol, ethanol amine, glycerin, hydrogenated castor oil, monoethanol amine citrate, polyethylene glycol, sodium bisulfite, sodium carbonate, sodium citrate, sodium cumene sulfonate, sodium formate, sodim silicate, trimethylsiloxy silicate, or mixtures thereof.

[0097] Hard surface cleaners include, but are not limited to, general purpose cleaners, bathroom cleaners, kitchen cleaners, cleaning creams, floor cleaners, and furniture care products.

[0098] In one aspect, the hard surface cleaner is a general purpose cleaner. The general purpose cleaner may contain the preservation composition of the present disclosure, water, surfactants, solvents, emulsifiers, pH adjusters, and fragrance. Particularly suitable surfactants used in general purpose cleaners include sodium lauryl sulfate and decyl glucoside. Particularly suitable solvents used in general purpose cleaners include isopropyl alcohol and ethanol. Particularly suitable emulsifiers used in general purpose cleaners include polysorbate 20 and alcohol ethoxylates i.e. (C9-C11 ) Alkyl alcohol, ethoxylate. Particularly suitable pH adjusters used in general purpose cleaners include citric acid and sodium hydroxide.

[0099] In another aspect, the hard surface cleaner is a bathroom cleaner. The bathroom cleaner may contain the preservation composition of the present disclosure, acid compounds, surfactants, fragrance, and thickeners. Particularly suitable acid compounds used in bathroom cleaners include hydrochloric acid and citric acid.

[0100] In yet another aspect, the hard surface cleaner is a kitchen cleaner. The kitchen cleaner may contain the preservation composition of the present disclosure, surfactants, solvents, degreasers, fragrance, and antimicrobial agents. Particularly suitable degreasers used in kitchen cleaners include sodium carbonate and sodium bicarbonate.

[0101] In one aspect, the hard surface cleaner is a cleaning cream. The cleaning cream may contain the preservation composition of the present disclosure, an abrasive agent, surfactants, emollients, and fragrance. Particularly suitable abrasive agents used in cleaning creams include calcium carbonate and silica. Particularly suitable emollients used in cleaning creams include glycerin.

[0102] In another aspect, the hard surface cleaner is a floor cleaner. The floor cleaner may contain the preservation composition of the present disclosure, water, surfactants, solvents, fragrance, and pH adjusters.

[0103] Dishwashing liquids include, but are not limited to, hand wash liquid, machine dish wash liquid, dishwash capsules, rise aid, and dish washing cleaning solution.

[0104] In one aspect, the dishwashing liquid is a hand dish wash liquid. The hand dish wash liquid may contain the preservation composition of the presentdisclosure, water, surfactants, emollients, solvents, and fragrance. Particularly suitable surfactants used in hand dish wash liquid include sodium lauryl sulfate and cocam idopropyl betaine. Particularly suitable emollients used in hand dish wash liquids include glycerin. Particularly suitable solvents used in hand dish wash liquids include isopropyl alcohol.

[0105] In another aspect, the dishwashing liquid is a machine dish wash liquid. The machine dish wash liquid may contain the preservation composition of the present disclosure, surfactants, enzymes, builders, bleaching agents, antiredeposition agents, and rinse aids. Particularly suitable enzymes used in machine dish wash liquids include protease and amylase. Particularly suitable builders used in machine dish wash liquids include sodium carbonate and sodium citrate. Particularly suitable bleaching agents used in machine dish wash liquids include sodium percarbonate. Particularly suitable antiredeposition agents used in machine dish was liquids include polyacrylate.

[0106] In yet another aspect, the dishwashing liquid is a dishwash capsule or pod. The dishwashing capsule or pod may contain the preservation composition of the present disclosure, surfactants, enzymes, builders, bleaching agents, rinse aid, and solvents. Particularly suitable solvents used in dishwash capsules or pods include PEG-75 and PEG-150.

[0107] In one aspect, the dishwashing liquid is a rinse aid. The rinse aid may contain the preservation composition of the present disclosure, water, surfactants, acidifiers, chelating agents, and anti-foaming agents. Particularly suitable acidifiers used in the rinse aid include citric acid. Particularly suitable chelating agents used in the rinse aid include tetrasodium EDTA.

[0108] Toilet care products include, but are not limited to, toilet cleaners and toilet fresheners.

[0109] In one aspect, the toilet care product is a toilet cleaner. The toilet cleaner may contain the preservation composition of the present disclosure, hydrochloric acid or sulfuric acid, surfactants, thickeners, fragrance, colorants, corrosion inhibitors, bleaching agents, thickening agents, solvents, and antibacterial agents. Particularly suitable surfactants used in the toilet cleaners include sodium lauryl sulfate and alkyl dimethyl amine oxides. Particularly suitable thickeners used in the toilet cleaners include xanthan gum and sodium chloride. Particularly suitablethickening agents used in the toilet cleaners include sodium hydroxide and sodium polyacrylate. Particularly suitable solvents used in the toilet cleaners include isopropanol.

[0110] Within these various types of products, the preservation composition and the base composition can be formulated differently depending on the function of the end-use product. For instance, the preservation composition of the present disclosure can be used in emulsions (both oil-in-water and water-in-oil), in aqueous solutions, in PIT (phase inversion temperature) emulsions, in oily solutions, in foaming cosmetic formulations (foams), and in so-called multiple emulsions, e.g. in triple emulsions (such as water / oil / water emulsions).

[0111] One particular use of the present preservation composition is to be incorporated into wiping solutions for premoistened wipes. When the preservation composition is used to saturate premoistened wipes, the preservation composition serves to preserve the premoistened wipe formulation and the wipe prior to use. Once the premoistened wipe composition is formulated, the premoistened wipe composition is applied to a substrate.

[0112] For example, the pre-moistened wipe can be a single use wipe that is impregnated with the formulation or wiping solution and is stored in a container that will dispense the wipe to a user. The container with the wipes may contain a single wipe, or several wipes.

[0113] Suitable wipe substrates include woven and nonwoven materials. Essentially any nonwoven web material may be used. Exemplary nonwoven materials may include, but are not limited to meltblown, coform, spunbond, airlaid, airlaced, hydroentangled nonwovens, spunlace, bonded carded webs, and laminates thereof. The fibers used to prepare the wipe substrate may be cellulosic fiber, thermoplastic fibers and mixtures thereof. The fibers may also be continuous fibers, discontinuous fibers, staple fibers and mixtures thereof. Basis weights of the nonwoven web may vary from about 12 grams per square meter to 200 grams per square meter (gsm) or more.

[0114] Once incorporated into the substrate, the resulting wiping product can have a weight ratio of liquid to substrate of from about 8:1 to about 1 :1 , such as from about 5: 1 to about 2: 1.

[0115] The composition disclosed herein may be added to various types of industrial formulations or products. For instance, the industrial formulation or product may include, but are not limited to, paints, coatings, varnishes, sealing compositions, leather auxiliaries, paper coating agents, plasters, adhesives, sealants, caulks, mineral slurries, pigment dispersions, pigment slurries, concrete, polymer emulsions, polymer dispersions, inks, sizes, or the like.

[0116] In still another aspect, the preservative composition of the present disclosure can be incorporated into an agricultural product. The agricultural product, for instance, can be a pesticide, such as a biopesticide, a biostimulant, a fertilizer, a micro-nutrient, a mineral slurry, a seed coating, or the like.

[0117] Typically, the composition of the present disclosure may be added to an end-use formulation to be preserved in an amount from about 0.0001 % to about 15% by weight of the formulation, such as from about 0.005% to about 12% by weight of the formulation, such as from about 0.01 % to about 10% by weight of the formulation, such as from about 0.05% to about 5% by weight of the formulation, or any range therebetween. More particularly, the composition may be added to an end-use formulation or product in an amount from about 0.1 % to about 5.0% by weight of the formulation.

[0118] The preceding description is exemplary in nature and is not intended to limit the scope, applicability or configuration of the disclosure in any way. Various changes to the described embodiments may be made in the function and arrangement of the elements described herein without departing from the scope of the disclosure.

[0119] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention is related.

[0120] As used in this application and in the claims, the singular forms “a”, “an”, and “the” include the plural forms unless the context clearly dictates otherwise. Additionally, the term “includes” means “comprises”. The methods and compositions of the present disclosure, including components thereof, can comprise, consist of, or consist essentially of the essential elements and limitations of the embodiments described herein, as well as any additional or optionalingredients, components or limitations described herein or otherwise useful in biocidal compositions.

[0121] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, percentages, and so forth, as used in the specification or claims are to be understood as being modified by the term “about”. Accordingly, unless otherwise indicated, implicitly or explicitly, the numerical parameters set forth are approximations that may depend on the desired properties sought and / or limits of detection under standard test conditions / methods. When directly and explicitly distinguishing embodiments from discussed prior art, the embodiment numbers are not approximates unless the word “about” is recited.

[0122] The term “about” is intended to mean approximately, in the region of, roughly, or around. When the term “about” is used in conjunction with a numerical range, it modifies that range by extending the boundaries above and below the numerical values set forth. Unless otherwise indicated, it should be understood that the numerical parameters set forth in the following specification and attached claims are approximations. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, numerical parameters should be read in light of the number of reported significant digits and the application of ordinary rounding techniques.

[0123] The term “antimicrobial” or “biocide” as used herein refers to any chemical compound that prevents the growth of organisms on a coating surface and / or that prevents the growth of organisms “in-can” in a paint or coating prior to surface application or in HPC products or an industrial formulation.

[0124] This written description uses examples to disclose the present disclosure, including the best mode, and also to enable any person skilled in the art to practice the disclosure, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the disclosure is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

[0125] Furthermore, certain aspects of the present disclosure may be better understood according to the following examples, which are intended to be nonlimiting and exemplary in nature. Moreover, it will be understood that the compositions described in the examples may be substantially free of any substance not expressly described.Examples

[0126] A mixture of isothiazolinones were combined with various different antimicrobial ingredients and tested for minimum inhibitory concentration (MIC). MIC is the lowest concentration of each mixture or single compound which prevents an observable level of growth. In the examples, MIC was tested against Pseudomonas aeruginosa ATCC 9027 / DSM 1128, Candida albicans ATCC 10231 and Pluralibacter gergoviae ATCC 33028.

[0127] Serial dilutions of each mixture or single compound were prepared. Micro-organisms were inoculated into media: Nutrient Broth (bacteria) or Malt Extract Broth (yeast). The final concentrations of micro-organisms in media were approximately 105 CFU / ml. The inoculated media was introduced to each of the serial dilutions at a 1 : 1 ratio and incubated at 30±1 °C for 24-48 hours.

[0128] The MICs for each mixture were compared with the MIC of each single compound alone.

[0129] Synergy was determined using a synergy index (“SI”) value, calculated using a method based on the Kull equation (F.C. Kull et. al., “Mixtures of Quaternary Ammonium Compounds and Long-chain Fatty Acids as Antifungal Agents”, Appl Microbiol. 1961 Nov; 9(6): 538-541 ):SI = Qa / QA + Qb / QB + Qc / QC whereinQA= concentration of compound A in ppm, acting alone produced an end point; Qa = concentration of compound A in ppm, in the mixture, which produced an end point;QB = concentration of compound B in ppm, acting alone produced an end point; Qb = concentration of compound B in ppm, in the mixture, which produced an end point;QC = concentration of compound C in ppm, acting alone produced an end point; andQc = concentration of compound C in ppm, in the mixture, which produced an end point.

[0130] In this study the end point is measured by the MIC. Synergy is demonstrated by an SI value of less than 1 . An additive effect is demonstrated by an SI value of equal to 1 . Antagonism is demonstrated by an SI value of greater than 1 .

[0131] In the first set of experiments, the mixture of isothiazolinones were tested in conjunction with an aromatic alcohol, namely phenoxyethanol. The following results were obtained:

[0132] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with an organic acid, namely lactic acid.

[0133] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a chelator, namely EDTA.

[0134] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another aromatic alcohol, namely benzyl alcohol.

[0135] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another aromatic alcohol, namely phenylpropanol.

[0136] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another chelator, namely GLDA.

[0137] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another chelator, namely MGDA.

[0138] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another chelator, namely DTPMP.

[0139] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a pyrithione, namely sodium pyrithione.

[0140] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a formaldehyde donor, namely DMDMH.

[0141] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another organic acid, namely benzoic acid.

[0142] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another organic acid, namely citric acid.

[0143] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another organic acid, namely itaconic acid.

[0144] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another organic acid, namely salicylic acid.

[0145] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another organic acid, namely levulinic acid.

[0146] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a quarternary ammonium compound, namely didecyldimethylammonium chloride (DDAC).

[0147] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another quarternary ammonium compound, namely alkyldimethylbenzylammonium chloride (ADBAC).

[0148] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a salt of organic compounds, namely sodium benzoate.

[0149] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with another salt of organic compounds, namely potassium sorbate.

[0150] In the next set of experiments, the mixture of isothiazolinones was tested in conjunction with a bromine compound, namely 2-bromo-2-nitro-1 ,3- propanediol (Bronopol).assessed in a preservation efficacy test (PET) against Candida albicans ATCC 10231 and Aspergillus brasilensis ATCC 16404. PET was carried out in accordance to ISO 11930 requirements.* DI water is used to mass balance where preservative levels were below 5% inclusion level to ensure the formulation adds to 100%.

[0152] Samples were inoculated on Day 0. Preservation efficacy testing starts upon sample inoculation. Preservation efficacy testing was performed over a period of 14 days.

[0153] Test samples were inoculated with both yeast and mould. The microbial load in sample was between 1x105 - 1x106 colony forming units (cfu) / ml.

[0154] Upon reaching the specified contact time a 1ml aliquot of each test sample was added to 9ml neutralizing broth and the whole solution mixed. Subsequent dilutions were prepared by serial dilution to 10-3. For each dilutionprepare duplicate 1 ml pour plates using MEA and incubated at 27.5±2.5C for up to 3 days.

[0155] Log recovery was calculated by enumerating colonies recovered from pour plates and factoring in the sample volume and the dilution factor to determine the cfu / ml count.Synergistic Activity of BIT, CIT / MIT and lodopropynyl butylcarbamate against the Microorganism A. Brasiliensis determined using Modified Kulls equation.SI=( CmixtureXPA ) I CA + (CmixturexPB ) / CBSI is the Synergy Index according to KulllCA is the cell count for substance ACB is the cell count for substance BCmixture is the cell count for the mixture of substances A BPz\ is the proportion of the substance A in the mixturePB is the proportion of the substance B in the mixtureA synergistic effect is evident if the SI value determined is less than 1 . On the other hand, if the SI is calculated to be exactly 1 , there is a purely additive effect of two antimicrobial substances. If the SI value is greater than 1 , however, there is an (often undesirable) antagonistic effect.Active Cone (%) Dav 7 Dav 14

[0156] As shown above, each of the antimicrobial ingredients displays a synergistic effect when combined with a mixture of isothiazolinones.

[0157] These and other modifications and variations to the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention, which is more particularly set forth in the appended claims. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims

What Is Claimed:1 . A preservative composition comprising: i) A mixture of isothiazolinones comprising 1 ,2-benzisothiazolin-3-one (BIT), 2-methyl-2H-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-2H-isothiazolin- 3-one (CMIT); and ii) an antimicrobial ingredient; wherein the antimicrobial ingredient increases the efficacy of the preservative composition against at least one microorganism in comparison to a similar composition only containing the mixture of isothiazolinones and the increase in efficacy is greater than the additive effect of the biocidal activity of the antimicrobial ingredient and the mixture of isothiazolinones taken alone.

2. The preservative composition according to claim 1 , wherein the 1 ,2- benzisothiazolin-3-one (BIT) is present in the composition in an amount of from about 1 to about 40 ppm.

3. The preservative composition according to claims 1 or 2, wherein the total amount of 2-methyl-2H-isothiazolin-3-one (MIT) and 5-chloro-2-methyl-2H- isothiazolin-3-one (CMIT) present in the composition is less than about 2 ppm.

4. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises an aromatic alhohol, and wherein the aromatic alcohol comprises phenoxyethanol, benzyl alcohol, 3-phenyl-1- propanol, or mixtures thereof; and wherein the mixture of isothiazolinones and the aromatic alcohol are contained in the preservative composition at a weight ratio of from about 1 : 10 to about 1 :5,000, such as from about 1 : 15 to about 1 :3,000, such as from about 1 :20 to about 1 :2,000.

5. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises an organic acid, and wherein the organic acid comprises benzoic acid, sorbic acid, lactic acid, itaconic acid, citric acid, levulinic acid, salicylic acid, gluconic acid, formic acid, dehydroacetic acid, glycolic acid or salts thereof, or mixtures thereof; and wherein the mixture of isothiazolinones and the organic acid or salts thereof are contained in the preservative composition at a weight ratio of from about 1 :5 to about 1 :5,000, such as from about 1 :10 to about 1 :2,000, such as from about 1 :15 to about 1 :500.

6. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises a pyrithione, and wherein the pyrithione comprises sodium pyrithione, zinc pyrithione, or mixtures thereof; and wherein the weight ratio between the mixture of isothiazolinones to the one or more pyrithione compounds is from about 1 :100 to about 100:1 , such as from about 1 : 10 to about 10: 1 , such as from about 1 :5 to about 5: 1 .

7. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises a quaternary ammonium compound and wherein the quaternary ammonium compound comprises a compound of the following general formula:[R1R2R3R4N+]rYr- wherein R1is an optionally substituted benzyl group or an optionally substituted alkyl or aryl-substituted alkyl group;R2and R3are independently optionally substituted alkyl groups;R4is selected from the group consisting of an optionally substituted alkyl or aryl-substituted alkyl group, benzyl group, and -[(CH2)2-O]n-R5, wherein n is an integer from 1 to 20 and R5is selected from the group consisting of hydrogen, phenyl, and alkyl-substituted phenyl groups;Y- is a chlorine ion, bromine ion, phosphate, carbonate, bicarbonate, carboxylate, saccharinate, ethosulfate, sulfate, sulfonate, or nitrate; and r is 1 , 2 or 3; and wherein the weight ratio between the mixture of isothiazolinones to the one or more quaternary ammonium compounds is from about 1 :100 to about 100:1 , such as from about 1 :10 to about 10:1 , such as from about 1 :5 to about 5:1.

8. A composition as defined in claim 7, wherein the at least one quaternary ammonium compound comprises an alkyl dimethyl benzyl ammonium chloride.

9. A composition as defined in claim 7, wherein the at least one quaternary ammonium compound comprises at least one dialkyl dimethyl ammonium chloride.

10. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises a formaldehyde donor, wherein the formaldehyde donor comprises dimethylol dimethyl hydantoin (DMDMH), oxazolidine, sodium N-(hydroxymethyl)glycinate, 2,2',2-(hexahydro-1 ,3-5-triazine- 1 ,3,5-triyl-)triethanol (HHT), (ethylenedioxy)dimethanol (EDDM), or salts thereof, or mixtures thereof; and wherein the weight ratio between the mixture of isothiazolinones to the one or more hydantoins is from about 1 :100 to about 100:1 , such as from about 1 : 50 to about 50: 1 , such as from about 1 : 10 to about 10: 1 .11 . The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises a chelator, and wherein the chelator comprises ethylenediaminetetraacetic acid, glutamic acid N,N-diacetic acid, methylglycinediacetic acid, diethylenetriaminepenta (methylene phosphonic acid) (DTPMP), Etidronic acid (HEDP), Amino tris(methylene phosphonic acid (ATMP), ethylenediamine tetra(methylene phosphonic acid)(EDTMP), gluconic acid, gluconolactone, or salts thereof, or mixtures thereof; and wherein the weight ratio between the mixture of isothiazolinones to the one or more chelators is from about 2:1 to about 1 :10, such as from about 1 :1 to about 1 :8, such as from about 1 :1 to about 1 :5.

12. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises a carbamate, and wherein the carbamate comprises iodopropynyl butyl carbamate (IPBC); and wherein the weight ratio between the mixture of isothiazolinones to carbamate is from about1 :5,000 to about 50:1 , such as from about 1 :2,000 to about 10:1 , such as from about 1 : 1 ,000 to about 1 :1.

13. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises bronopol, and wherein the weight ratio between the mixture of isothiazolinones to bronopol is from about 5,000:1 to about 10:1 , such as from about 1 : 1 ,000 to about 2: 1 , such as from about 1 :500 to about 1 :1.

14. The preservative composition according to any of claims 1 through 3, wherein the antimicrobial ingredient comprises an enzyme and wherein the weight ratio between the mixture of isothiazolinones to one or more enzymes is fromabout 1 :2,000 to about 500:1 , such as from about 1 :1 ,000 to about 200:1 , such as from about 1 :250 to about 1 :

215. A composition as defined in any of the preceding claims, wherein the composition contains at least one of a solvent, a surfactant, a complexing agent, a corrosion inhibitor, an alkalinity builder, a pH adjusting agent, an auxiliary, an acid, a foaming agent, a perfume, an enzyme, a colorant, a humectant, an emulsifier, a thickener, an antioxidant, a UV blocking agent, a wax, a natural extract, or an oil.

16. A home care product, wherein the home care product comprises the composition as defined in any of claims 1 through 15.

17. The home care product according to claim 16, wherein the home care product comprises a hand-dish soap, a machine dish soap, a machine dish rinse-aid, a laundry detergent, a polish, a laundry fabric conditioner, a clothing fragrance, a wrinkle treatment, an ironing aid, or an all-purpose cleaner.

18. An industrial product, wherein the industrial product comprises the composition as defined in any of claims 1 through 15.

19. The industrial product according to claim 18, wherein the industrial product comprises a paint, a coating, a varnish, a sealing composition, a leather auxiliary, a paper coating agent, a plaster, an adhesive, a sealant, a caulk, a mineral slurry, a pigment dispersion, a pigment slurry, a concrete, a polymer emulsion, a polymer dispersion, an ink, a size, or an agricultural pesticide formulation.

20. An agricultural chemical product, wherein the agricultural chemical product comprises the composition as defined in any of claims 1 through 15.21 . The agricultural chemical product according to claim 20, wherein the agricultural chemical product comprises a pesticide, a biopesticide, a biostimulant, a fertilizer, a micro-nutrient, a mineral slurry, a colorant, a dye, an adjuvant, or a seed coating.

22. A method for protecting a product subject or susceptible to infestation with and / or destruction or deterioration by microorganisms, by incorporating into or onto the product in an amount which is effective to adversely affect the growth and / or survival of said microorganisms, the preservative composition according to any one of claims 1 through 15.

23. Use of the preservative composition according to any of claims 1 through 15 for preventing destruction or deterioration by microorganisms of a product.

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