Aqueous composition, method of making an aqueous composition, and method for treating a fiber or article

Abstract

Disclosed herein are aqueous compositions, methods of making aqueous compositions, and methods for treating fibers or articles. Disclosed herein are aqueous compositions containing silver ions, at least one polymer having at least 10 wt% of vinyl imidazole polymerized units, and at least one surfactant of the formula R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, wherein R 1 , R 2 , x, and y are as described herein. These compositions have improved applications for treating fibers or articles, such as textiles.

Description

Technical Field

[0001] This disclosure relates to compositions comprising silver ions and polymeric materials having improved applications for treating fibers or articles, such as textiles. Background Technology

[0002] Silver ions are considered a safe and effective antimicrobial solution for textile applications. However, silver ions can undesirably react with ionic components in aqueous solutions, leading to the precipitation of silver compounds. Polymer delivery systems for silver ions, such as those disclosed in US 7390774B2 and US2018347107A1, help mitigate this concern, but undesirable precipitation remains a concern, particularly when the processed solution contains hard water. The invention disclosed herein addresses this need by finding that certain surfactants are compatible with the silver-polymer materials of this disclosure and reduce precipitation or floc formation, even in hard water environments. Furthermore, compositions of this disclosure containing the surfactants disclosed herein advantageously exhibit improved stability and foam dissipation over a wide range of pH values ​​and water hardness levels. These features improve the application of the silver-polymer materials of this disclosure, and compositions containing such materials, under extended processing conditions, environments, and durations. Summary of the Invention

[0003] This document discloses an aqueous composition comprising: (a) silver ions; (b) at least one polymer comprising at least 10 wt% of polymeric units of vinylimidazole; and (c) at least one surfactant represented by the following formula: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 R 2 x and y are as described herein.

[0004] A method for preparing compositions that can be used to treat fibers or articles (such as textiles) is also disclosed, comprising combining (a) a silver ion source, (b) at least one polymer comprising at least 10 wt% vinylimidazole polymeric units and (c) at least one surfactant represented by the following formula in an aqueous medium: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 R 2 x and y are as described herein.

[0005] In a further aspect, this document discloses methods for treating fibers or articles (such as textiles), including contacting the fibers or articles with the compositions disclosed herein.

[0006] It should be understood that the foregoing general description and the following detailed description are merely embodiments of the invention and are intended to provide an overview or framework for understanding the nature and characteristics of the claimed invention. Detailed Implementation

[0007] Unless otherwise specified, temperatures are in degrees Celsius (°C). All operations are performed at room temperature (20–25°C) unless otherwise specified. The amount of polymer is based on solids, i.e., excluding any water or solvents that may be present with the polymer. The amount of monomer is based on solid polymers. The term "vinylimidazole" (or VI) refers to N-vinylimidazole. The term "silver ion" refers to Ag(I) ions.

[0008] As used in this article, “fabric” refers to woven or nonwoven textiles, such as cotton, polyester, nylon, Lycra, polyolefins, and their blends.

[0009] As used herein and in the appended claims, the term "(methyl)" followed by another term (such as acrylic acid, acrylate, acrylamide, etc.) means, for example, both acrylic acid and (meth)acrylic acid; both acrylate and methacrylate; both acrylamide and methacrylamide; and so on. Furthermore, any acid mentioned herein also includes its salt form, and vice versa.

[0010] Unless otherwise stated, percentages mentioned are weight percentages or ppm w / w. All range endpoints are included and can be combined.

[0011] The aqueous compositions disclosed herein can be used to provide one or more properties or benefits (e.g., antimicrobial activity and / or odor control) to fibers or articles, particularly textiles (such as fabrics).

[0012] The aqueous composition comprises (a) silver ions, (b) at least one polymer comprising at least 10 wt% vinylimidazole polymeric units, and (c) at least one surfactant represented by the following formula: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 R 2 x and y are as described in this article.

[0013] At least one polymer may contain up to about 100 wt% vinylimidazolium polymeric units; preferably at least 15 wt%, more preferably at least 20 wt%, most preferably at least 25 wt%, at least 30 wt%, or at least 35 wt%; preferably no more than 95 wt%, more preferably no more than 90 wt%, and most preferably no more than 85 wt%. The polymer preferably further contains from 10 to 70 wt% of one or more polar monomers; preferably at least 15 wt%; more preferably at least 20 wt%; preferably no more than 60 wt%, more preferably no more than 55 wt%. The polar monomer is preferably a monomer having at least one carboxyl group, sulfonic acid group, phosphonic acid group, or a polymeric unit having ethylene oxide. Preferred polar monomers include, for example, acrylic acid (AA), methacrylic acid (MAA), itaconic acid, maleic acid, fumaric acid, salts of the aforementioned acids and alkyl or hydroxyalkyl (e.g., C1-C22) esters, 2-acrylamido-2-methylpropanesulfonic acid and its sodium salt, polymerized ethylene oxide units or mixed ethylene oxide / propylene oxide units of (meth)acrylate, provided that the ethylene oxide residues are at least 50 wt% (or alternatively at least 75%, or alternatively at least 90%) of the ethylene oxide / propylene oxide residues, and combinations thereof. Preferably, the ethylene oxide units or mixed ethylene oxide / propylene oxide units are monoalkylated (e.g., polyethylene glycol monomethyl ether) and have a Mn of at least 150, preferably at least 300; preferably not more than 1000, preferably not more than 700, and preferably not more than 600. The polymer can be an "acrylic polymer," that is, a polymer having polymeric units of acrylic monomers comprising at least 30 wt%, preferably at least 35 wt%, preferably at least 40 wt%, and preferably at least 50 wt%. Acrylic monomers include (meth)acrylic acid, its salts, and their C1-C22 alkyl or hydroxyalkyl esters, including combinations thereof; crotonic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, (meth)acrylamide, (meth)acrylonitrile, and alkyl or hydroxyalkyl esters of crotonic acid, itaconic acid, fumaric acid, or maleic acid.

[0014] In a preferred embodiment, at least one polymer contains polymeric units of other olefinic unsaturated monomers, such as (meth)acrylates, vinyl esters, and (meth)acrylamide, in addition to the polymeric units of vinylimidazolium (and in some embodiments, in addition to the polymeric units of (meth)acrylic acid). In a preferred embodiment, the polymer contains 0 to 70 wt% polymeric units of alkyl or hydroxyalkyl (meth)acrylates; preferably not more than 60 wt%, more preferably not more than 55 wt%; preferably at least 5 wt%, more preferably at least 10 wt%. Preferred alkyl groups include C1-C8 alkyl groups, more preferably C1-C6 alkyl groups, and most preferably C1-C4 alkyl groups. Preferred hydroxyalkyl groups include C2-C6 hydroxyalkyl groups, more preferably C2-C4 hydroxyalkyl groups.

[0015] In a preferred embodiment, the polymer comprises (x) 60-90 wt% vinylimidazolium polymeric units and (y) 10-40 wt% monomer Y polymeric units, wherein monomer Y is an olefinic unsaturated compound. Monomer Y may be selected from, for example, carboxylic acids, organic sulfuric acids, sulfonic acids, phosphonic acids, and esters (e.g., (meth)acrylates) of polymeric units of ethylene oxide or a mixture of ethylene oxide / propylene oxide units, provided that the ethylene oxide residues constitute at least 50 wt% (or alternatively at least 75%, or alternatively at least 90%) of the ethylene oxide / propylene oxide residues, or the esters of the mixture of ethylene oxide / propylene oxide residues do not exceed 20 wt% of the copolymer, or alternatively not more than 15%, or alternatively not more than 10%. Preferably, the esters of polymeric units of ethylene oxide or a mixture of ethylene oxide / propylene oxide units comprise at least two ethylene oxide units, or alternatively at least three, four, five, or six. The number of polymerized ethylene oxide units or mixed ethylene oxide / propylene oxide units is calculated by the Mn of the polymerized ethylene oxide chain or mixed ethylene oxide / propylene oxide chain. Preferably, the ester of the polymerized ethylene oxide or mixed ethylene oxide / propylene oxide unit is (meth)acryloyl ester. The polymerized ethylene oxide or mixed ethylene oxide / propylene oxide unit may be end-capped with a C1-C6 alkyl group. In some embodiments, the polymerized ethylene oxide or mixed ethylene oxide / propylene oxide unit has an Mn of 100 to 3000, for example, from 200 to 1000, from 250 to 600, or from 300 to 500. In some embodiments, the monomer Y is selected from acrylic acid (AA), methacrylic acid (MAA), itaconic acid, maleic acid, fumaric acid, 2-acrylamido-2-methylpropanesulfonic acid and its sodium salts, and combinations thereof. In some aspects of these embodiments, the polymer further comprises other olefinic unsaturated monomers, such as (meth)acrylates, vinyl esters, and (meth)acrylamide.

[0016] More than one polymer may be incorporated in the compositions disclosed herein, such as first and second polymers, each of which, for example, comprises a vinylimidazole polymer unit. In a preferred embodiment, the composition comprises a first polymer comprising (x) 60-90 wt% vinylimidazole polymer units and (y) 10-40 wt% monomer Y polymer units, wherein monomer Y is an olefinic unsaturated compound as described above, and the composition further comprises a second polymer comprising: (w) vinylimidazole polymer units and (z) monomer Z polymer units, wherein monomer Z is a non-heterocyclic saturated compound selected from acrylic acid, (meth)acrylic acid, ethyl acrylate, butyl acrylate, and combinations thereof (i.e., combinations of acrylic acid monomers). The second polymer may comprise vinylimidazole monomer and monomer Z in a weight ratio of 95:5 to 5:95, alternatively 80:20 to 20:80, or alternatively 60:40 to 40:60. The vinylimidazolium polymer unit may be present in the second polymer, for example, in an amount from about 10 wt% to about 90 wt%, alternatively in an amount from about 10 wt% to about 65 wt%, and further alternatively in an amount from about 20 wt% to about 50 wt%. The monomer Z polymer unit may be present in the second polymer, for example, in an amount from about 10 wt% to about 90 wt%, alternatively in an amount from about 35 wt% to about 90 wt%, and further alternatively in an amount from about 50 wt% to about 80 wt%. For example, butyl acrylate (BA) may be present in the second polymer in an amount from about 5 wt% to about 60 wt%, optionally in an amount from about 5 wt% to about 45 wt%, and further alternatively in an amount from about 5 wt% to about 25 wt%. Acrylic acid (AA) may further be present in the copolymer in an amount from about 5 wt% to about 30 wt%, alternatively in an amount from about 5 wt% to about 20 wt%, and further alternatively in an amount from about 5 wt% to about 10 wt%.

[0017] Preferably, the polymer has a number average molecular weight (Mn) of 1,000 to 300,000; preferably at least 5,000, more preferably at least 10,000; preferably not more than 200,000, more preferably not more than 100,000, more preferably not more than 50,000.

[0018] The methods used to prepare the polymer types described herein are known in the art.

[0019] Preferably, the molar ratio of vinylimidazole to silver ions in the composition of the present invention is at least 3.5:1, preferably at least 4:1, preferably at least 5:1, preferably at least 8:1; preferably at least 12:1, preferably not more than 150:1, preferably not more than 100:1, preferably not more than 50:1, preferably not more than 24:1. When vinylimidazole is present in multiple polymers in the composition, the total amount of vinylimidazole from all such sources is considered for the ratio of vinylimidazole to silver ions in the composition. Preferably, the source of silver ions is a water-soluble silver salt, such as silver nitrate, silver / amine complex, silver acetate, etc.

[0020] The surfactant disclosed herein is represented by the following formula: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 It is C 6-10 Branched or straight-chain alkyl groups, R 2 It is CH3 or CH2CH3, x is a real number from about 1 to about 11, preferably from about 3 to about 6, and y is a real number from about 1 to about 20, preferably from about 3 to about 14, from about 6 to about 14, or from about 6 to about 11.

[0021] It should be understood that "x" and "y" represent propoxylation and / or butoxylation, respectively (depending on R). 2 The properties of x and y are the average degree of alkoxylation. Therefore, x and y do not need to be integers; they are intended to be indicated by using "about". In summary, x and y determine the degree of alkoxylation in the oligomer distribution. It should be understood that the order of x and y is either block-based or random. Preferably, the PO or BO portion and the EO portion are the result of a block feed.

[0022] The preferred surfactants of the chemical formulas disclosed herein are those in which X is about 3, about 4, about 5 or about 6, more preferably about 5.

[0023] Preferably, y is about 6, about 9, about 11 or about 14, more preferably about 9.

[0024] R 1 Preferably, it is C 6-10 Branched alkyl groups, more preferably C1646-2 ... 8-9 Branched alkyl groups, such as 2-ethylhexyl or 2-propylhexyl, most preferably 2-ethylhexyl.

[0025] R 2 CH3 is preferred.

[0026] For example, preferred surfactants include those in which x is about 3, about 4, about 5, or about 6, more preferably about 5; y is about 3, about 6, about 9, about 11, or about 14, more preferably about 6 or about 9, and most preferably about 9; R 1 It is C 8-9 Branched alkyl groups, such as 2-ethylhexyl; and R 2 It is CH3. More preferably, x is about 5, y is about 9, and R is about 5. 1 It is 2-ethylhexyl and R 2 Those are CH3.

[0027] Preferably, the HLB value of the surfactant is calculated using the method described in "Calculation of Hydrophile-Lipophile balance for polyethoxylated surfactants by group contribution method," Xiaowen Guo; Zongming Rong; Xugen Ying; Journal of Colloid and Interface Science 298 (2006) 441-450, and is about 8 to 15, more preferably about 9 to 14 or about 10 to 14, such as about 12.5.

[0028] The surfactants disclosed herein are commercially available or can be prepared by methods known in the art.

[0029] The aqueous compositions disclosed herein may be in a concentrated form, such as those intended for dilution prior to processing fibers or articles. Alternatively, the aqueous compositions may be in the form of a treatment or working composition or solution, such as after dilution from a concentrated form, or otherwise prepared in a form ready for processing.

[0030] The compositions disclosed herein are described as “aqueous”, meaning that the listed components of the composition are contained in water or an aqueous medium, such as a mixture consisting essentially of water and a water-miscible solvent (including buffered aqueous solutions).

[0031] The concentrated form of the aqueous composition may have a silver concentration of, for example, from about 20 ppm to about 100,000 ppm, alternatively from about 20 ppm to about 50,000 ppm, from about 30 ppm to about 35,000 ppm, from about 50 ppm, or from about 100 ppm to about 25,000 ppm, or from about 100 ppm to about 15,000 ppm, from about 10,000 ppm, or from about 5,000 ppm. Preferably, the concentrated composition contains at least 50 ppm or at least 100 ppm of silver. The concentrated form may contain a vinylimidazole-containing polymer at a concentration of, for example, from about 0.1 wt% to about 15 wt%, alternatively from about 0.3 wt% to about 13 wt%, or from about 0.5 wt% to about 6 wt%. The concentrated form of the composition may comprise at least one surfactant of the present disclosure at a concentration of, for example, from about 0.2 wt% to about 5 wt%, or alternatively from about 0.4 wt% to about 3 wt%, from about 0.4 wt% to about 5 wt%, or from about 2.5 wt%, or from about 0.6 wt% to about 2 wt%. The concentrated form preferably has a pH of about 5 to about 11.5, for example, from about 8 to about 11. Preferably, in the concentrated form, the γ in the chemical formula of the surfactant disclosed herein is from about 4 to about 14, more preferably from about 6 to about 14, or from about 6 to about 11.

[0032] The aqueous composition may be in the form of a treatment, a working composition, or a solution (e.g., after dilution in a concentrated form) having a silver concentration of, for example, from about 0.5 to about 200 ppm or about 180 ppm, alternatively from about 5 ppm or about 10 ppm to about 180 ppm, from about 160 ppm or about 140 ppm, alternatively from about 10 ppm or about 20 ppm to about 120 ppm, or from about 10 ppm or about 20 ppm to about 80 ppm. Preferably, the treatment or working composition contains at least 2 ppm, alternatively at least 5 ppm or at least 10 ppm; preferably not more than 160 ppm, alternatively not more than 120 ppm or not more than 100 ppm. The treatment or working composition may contain a vinylimidazole-containing polymer at a concentration of, for example, from about 0.004 wt% to about 1.5 wt%, or alternatively from about 0.01 wt% to about 1 wt%, or about 0.5 wt%, or about 0.01 wt% to about 0.3 wt%. The treatment or working composition may contain at least one surfactant of the present disclosure at a concentration of, for example, from about 0.001 wt% to about 1 wt%, or alternatively from about 0.004 wt% to about 0.75 wt%, or about 0.5 wt%, or alternatively from about 0.01 wt% to about 0.5 wt%, or about 0.05 wt% to about 0.35 wt%. Preferably, the treatment or working composition has a pH in the range of about 4 to about 11, for example, from about 5.5 to about 10.5. In some embodiments, the treatment or working composition comprises water having a hardness value characterized as at least 100 μS / cm, or alternatively at least 150 μS / cm, at least 180 μS / cm, at least 200 μS / cm, at least 220 μS / cm, at least 250 μS / cm, at least 300 μS / cm, at least 350 μS / cm, at least 400 μS / cm, at least 440 μS / cm, at least 480 μS / cm, at least 520 μS / cm, at least 560 μS / cm, or at least 600 μS / cm. Conductivity measures the ability of water to conduct electricity, which depends on the total concentration of dissolved ions. Hard water contains high levels of ionic substances, which may include calcium and magnesium ions, as well as other ions such as bicarbonates, chlorides, and sulfates, which increase conductivity. Increased ion concentration is generally associated with higher conductivity. The treatment or working composition may contain water having a hardness characterized by a conductivity value in the range of, for example, up to 2500 μS / cm, or alternatively up to 2000 μS / cm, or alternatively up to 1800 μS / cm, or alternatively up to 1400 μS / cm, or alternatively up to 1250 μS / cm, or alternatively up to 1150 μS / cm.

[0033] In another aspect of this disclosure, a method for preparing a composition that can be used to treat fibers or articles (such as textiles) includes combining (a) a silver ion source, (b) at least one polymer comprising at least 10 wt% of a polymeric unit containing vinylimidazole, and (c) at least one surfactant represented by the following formula in an aqueous medium: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 R 2 x and y are as described herein. It should be understood that the foregoing descriptions relating to the above components (a), (b) and (c) also apply to the preparation methods described herein.

[0034] The compositions disclosed herein are not limited to any specific technique for combining the components. Methods for preparing aqueous compositions comprising silver ions and polymers of the present disclosure are known in the art. Surfactants of the present disclosure can be combined with such components, for example, when or near the time when polymeric materials combine with each other (if more than one polymer is used) and / or when or near the time when a silver ion source is combined with one or more polymers. Furthermore, surfactants of the present disclosure can be added to compositions already comprising a silver ion source and one or more polymers. Similarly, surfactants can be added to treatments or working compositions or solutions already containing a silver ion source and one or more polymers, for example, in textile treatment facilities. Preferably, the silver ion source is a water-soluble silver salt, such as silver nitrate, silver / amine complex, silver acetate, etc., typically in the form of a silver solution, such as silver nitrate in water, an aqueous buffer solution prepared with a water-miscible solvent, or an aqueous / organic solution.

[0035] In another aspect, methods for treating fibers or articles (such as textiles) include contacting the fibers or articles with the compositions of this disclosure. As used herein, "fiber" refers to a unit of material capable of being spun into yarn or made into fabric by bonding or by interlacing in various ways, including, for example, weaving, knitting, braiding, felting, twisting, or web weaving. Articles can be textiles, such as fabrics, such as cotton, polyester, nylon, and combinations thereof. Fibers or articles may be contacted with the compositions of this disclosure according to known techniques, including but not limited to padding, exhaustion, spraying, brushing, impregnation, or coating.

[0036] As used herein, the articles “a,” “an,” and “the” preceding the elements or components of the invention are intended to be non-limiting in relation to the number of embodiments of the elements or components (i.e., occurrences). Thus, “a,” “an,” and “the” should be interpreted as including one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates a singularity.

[0037] As used herein, the term "comprising" means the presence of the features, integrals, steps, or components mentioned in the claims, but it does not exclude the presence or addition of one or more other features, integrals, steps, components, or groups thereof. The term "comprising" is intended to include embodiments covered by the terms "substantially consisting of" and "consisting of". Similarly, the term "substantially consisting of" is intended to include embodiments covered by the term "consisting of".

[0038] As used herein and unless otherwise indicated, the term “about” modifying the amount of an ingredient or reactant used refers to, for example, variations in numerical quantity that can occur through typical measurement and liquid handling procedures used in the real world to produce concentrates or use solutions; through unintentional errors in these procedures; through differences in the manufacture, origin, or purity of the ingredients used to prepare the composition or to carry out the method; and so on.

[0039] When present, all ranges are included and can be combined. For example, when stating the range "1 to 5", the range should be interpreted as including the ranges "1 to 4", "1 to 3", "1-2", "1-2 and 4-5", "1-3 and 5", etc.

[0040] When parameters are given as a range, preferred range, or a list of preferred upper and lower limits, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred range value and any lower or preferred range value, regardless of whether the range is disclosed individually. In the case of numerical ranges described herein, unless otherwise stated, the range is intended to include its endpoints, as well as all integers and fractions within that range. The scope of the invention is not intended to be limited to the specific values ​​and embodiments described in this specification.

[0041] Example

[0042] Examples 1-4

[0043] The concentrated aqueous composition of the samples was blended, each composition comprising a first polymer (45VI / 40BA / 15AA w / w / w), a second polymer (75VI / 25PEGMA w / w), and silver ions derived from silver nitrate. The concentration of silver ions in each sample was approximately 1000 ppm, and the molar ratio of VI to silver ions was approximately 8:1 in samples 1 and 2 and approximately 12:1 in samples 3–5. Samples were prepared in deionized water with a small amount of ammonium hydroxide to maintain the pH at 10.5–11.5. The samples were prepared with or without surfactant A of the following formula, as shown in Table 1 below by weight percentage.

[0044] Surfactant A:R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, where R 1 2-Ethylhexyl, R 2 :CH3, x:5 and y:9; (HLB value: 12.5).

[0045] Table 1

[0046] Example 1

[0047] Individual working solutions were prepared using Samples 1 and 2 above by adding 6 grams of sample to 94 grams of tap water in each case. This tap water had a hardness level characterized by a conductivity value of 440 μS / cm, as measured using an Oakton PC 450. The pH of each working solution was approximately 10.3. Three copies of the working solutions were prepared (three working solutions prepared using Sample 1 and three working solutions prepared using Sample 2), and the results discussed below are reported as averages.

[0048] Flocculation was visually observed in each working solution by adding 50 ml of the working solution to a glass jar under continuous shaking at 35°C–37°C. Flocculation was observed at 5 and 20 minutes. The degree of flocculation is shown in Table 2 below, where the number of "+" signs represents a higher degree of flocculation. All working solutions containing surfactant A showed no flocculation or very little flocculation.

[0049] Table 2

[0050] Example 2

[0051] Foam formation and dissipation were also evaluated for each working solution from Example 1 (with a water hardness characterized by conductivity of 440 μS / cm) by adding 20 g of the working solution to a 40 ml vial and shaking vigorously for 30 seconds. Foam formation was measured based on the foam height (cm) in the vial, and then measured at 5 and 10 minutes to determine foam dissipation (% foam reduction). The results are shown in Table 3. Similar levels of foam were initially produced in the working solutions with and without surfactant A; however, the foam advantageously dissipated more rapidly in the working solution containing surfactant A.

[0052] Table 3

[0053] Example 3

[0054] Using samples 3-5 (containing surfactant A) and sample 1 (without surfactant A), separate working solutions were prepared in each case by adding 6 g of sample to 94 g of tap water and separately to 94 g of deionized (DI) water with pH adjusted dropwise using glacial acetic acid. The tap water had a hardness level characterized by a conductivity value of 600 μS / cm as measured using an Oakton PC 450. The pH values ​​of the hard and deionized water solutions were approximately 10.3 and 5.5, respectively. The working solutions were mixed, and precipitate formation was observed after two weeks for the hard water solution and after one week for the deionized water solution. The presence of surfactant A ensured the stability of the working solutions at high pH with hard water and at lower pH with deionized water. The results are summarized in Table 4.

[0055] Table 4

[0056] Example 4

[0057] Foam formation and dissipation were evaluated for each working solution from Example 3 (with a conductivity characterized by a water hardness of 600 μS / cm) by adding 20 g of the working solution to a 40 ml vial and shaking vigorously for 30 seconds. Foam formation was measured based on the foam height (cm) in the vial, and then measured at 10 minutes to determine foam dissipation (foam reduction %). The results are shown in Table 5. The working solution containing surfactant A rapidly dissipated foam with hard water at high pH and with deionized (DI) water at lower pH.

[0058] Table 5

[0059] Examples 5-6

[0060] The concentrated aqueous compositions of the samples (samples 6-11) were blended, each composition comprising a first polymer (45VI / 40BA / 15AA w / w / w), a second polymer (75VI / 25PEGMA w / w), and silver ions derived from silver nitrate. The concentration of silver ions in each sample was approximately 1000 ppm, and the molar ratio of VI to silver ions was approximately 8:1. Samples were prepared in deionized water with a small amount of ammonium hydroxide to control the pH at 10.5-11.5. Samples were prepared with and without the various surfactants given in the following weight percentages as provided in Table 6.

[0061] Surfactant A: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, where R 1 2-Ethylhexyl, R 2 CH3, x:5, y:9 (HLB value: 12.5).

[0062] Surfactant W: , Where x:5 (HLB value: 10.5).

[0063] Surfactant X: The molecular formula of surfactant W, where x: 7 (HLB value: 12.1).

[0064] Surfactant Y: The molecular formula of surfactant W, where x: 9 (HLB value: 13.3).

[0065] Surfactant Z: CH3(CH2) n -O-(CH2CH2O)7-H, where n:C 12 -C 15 Straight-chain alkyl (HLB value: 12.2).

[0066] Example 5

[0067] 20 g of each sample was added to a 40 ml vial and shaken to assess the resulting foam height. Furthermore, the physical state of each sample composition was visually assessed after overnight storage at 4°C. The results are shown in Table 6. Although the other surfactants had similar HLB values, the concentrated composition containing surfactant A (sample 7) remained clear and produced significantly less foam compared to the concentrated composition containing other surfactants. The composition containing surfactant W, while producing minimal foam, exhibited phase separation after overnight storage at 4°C.

[0068] Table 6

[0069] Example 6

[0070] Prior to storage, using samples 6-11 above, separate working solutions were prepared by adding 6 grams of sample to 94 grams of tap water at two different hardness levels (characterized by conductivity values ​​of 641 μS / cm and 1107 μS / cm, respectively, measured using a conductivity meter (Oakton PC 450)). The pH of each working solution was approximately 10.3. Flocculation formation of each working solution was visually observed by adding 50 ml of the working solution to a glass jar under continuous shaking at 35°C–37°C. Flocculation formation of the sample working solutions was observed after 20 minutes. The degree of flocculation formation is shown in Table 7 below, where the number of “+” signs represents a higher degree of flocculation formation. As shown in Table 7, although these surfactants have similar HLB values, surfactant A provides greater protection against flocculation formation compared to other surfactants, while also producing the least amount of foam.

[0071] Table 7

[0072] Example 6

[0073] The concentrated aqueous compositions of the samples (samples 12-15) were blended, each composition comprising a first polymer (45VI / 40BA / 15AA w / w / w), a second polymer (75VI / 25PEGMA w / w), and silver ions derived from silver nitrate. The concentration of silver ions in each sample was approximately 1000 ppm, and the molar ratio of VI to silver ions was approximately 8:1. The samples were prepared in deionized water with a small amount of ammonium hydroxide to maintain the pH at 10.5-11.5. Surfactants were prepared with and without the surfactants shown in Table 8 below at their respective weight percentages.

[0074] Surfactant A: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, where R 1 2-Ethylhexyl, R 2 CH3, x:5, y:9 (HLB value: 12.5).

[0075] Surfactant B: The chemical formula of surfactant A, where R 1 2-Ethylhexyl, R 2 :CH3, x:5 and y:6 (HLB value: 10.8).

[0076] Surfactant C: The chemical formula of surfactant A, where R 1 2-Ethylhexyl, R 2 :CH3, x:5 and y:3 (HLB value: 7.9).

[0077] After being stored at room temperature for 8 hours, the physical state of each sample composition was visually assessed. The results are shown in Table 8. The concentrated compositions containing surfactants A and B (samples 13 and 14, respectively) were transparent. The concentrated composition containing surfactant C showed phase separation, indicating that when using surfactants in the concentrated form of the aqueous compositions disclosed in this invention, the preferred value of y in the chemical formula of the surfactants disclosed in this invention is greater than 3.

[0078] Table 8

[0079] Example 7

[0080] Prior to storage, individual working solutions were prepared using samples 12-15 described above, in each case by adding 6 grams of sample to 94 grams of tap water with a hardness level characterized by a conductivity value of 440 μS / cm. The pH of each working solution was approximately 10.3. Flocculation formation in each working solution was visually observed by adding 50 ml of the working solution to a glass jar under continuous shaking at 35°C–37°C. Flocculation formation in the sample working solutions was observed after 20 minutes. The degree of flocculation formation is shown in Table 9 below, where the number of “+” signs represents a higher degree of flocculation formation. As shown in Table 9, surfactants A, B, and C provide significant protection against floc formation in the working solutions.

[0081] Table 9 .

Claims

1. An aqueous composition comprising: (a) silver ions; (b) at least one polymer comprising at least 10 wt% of a vinylimidazole polymeric unit; and (c) at least one surfactant represented by the following formula: R 1 -O-[CH2CH(R 2 )-O] x [CH2CH2O] y -H, Where R 1 It is C 6-10 Branched or straight-chain alkyl groups, R 2 It is CH3 or CH2CH3, x is a real number from about 1 to about 11, and y is a real number from about 1 to about 20.

2. The aqueous composition according to claim 1, wherein the at least one polymer comprises at least 20 wt% of vinylimidazole polymeric units.

3. The aqueous composition according to claim 1 or 2, wherein the aqueous composition has a molar ratio of at least 3.5:1 for vinylimidazole to silver ions.

4. The aqueous composition according to any one of the preceding claims, wherein the at least one polymer further comprises about 10 wt% to about 70 wt% of one or more polar monomers.

5. The aqueous composition according to any one of the preceding claims, wherein R 1 It is C 8-9 Branched alkyl groups, R 2 It is CH3, x is about 3 to about 6, and y is about 6 to about 14.

6. The aqueous composition according to claim 5, wherein R 1 It is 2-ethylhexyl, x is about 5 and y is about 9.

7. The aqueous composition according to any one of the preceding claims, wherein the aqueous composition is in a concentrated form having a silver concentration of about 50 ppm to about 25,000 ppm, and wherein y is about 6 to about 14.

8. The aqueous composition according to any one of the preceding claims, wherein the aqueous composition is in a concentrated form having a concentration of about 0.2 wt% to about 5 wt% of the at least one surfactant.

9. The aqueous composition according to claim 8, wherein the concentration of the at least one surfactant is from about 0.4 wt% to about 3 wt%.

10. The aqueous composition according to any one of claims 1-6, wherein the aqueous composition has a silver concentration of about 10 ppm to about 200 ppm.

11. The aqueous composition according to any one of claims 1-6 and 10, wherein the aqueous composition has a concentration of about 0.001 wt% to about 1 wt% of the at least one surfactant.

12. The aqueous composition according to claim 11, wherein the concentration of the at least one surfactant is from about 0.004 wt% to about 0.5 wt%.

13. The aqueous composition according to any one of claims 1-6 and 10-12, wherein the aqueous composition comprises water having a hardness characterized by a conductivity value of at least 100 μS / cm.

14. The aqueous composition of claim 13, wherein the aqueous composition comprises water having a hardness characterized by a conductivity value of at least 250 μS / cm.

15. The aqueous composition of claim 13, wherein the aqueous composition comprises water having a hardness characterized by a conductivity value of at least 400 μS / cm.

16. The aqueous composition of claim 13, wherein the aqueous composition comprises water having a hardness characterized by a conductivity value of at least 600 μS / cm.

17. A method for preparing an aqueous composition according to any one of the preceding claims, comprising combining (a) a silver ion source, (b) the at least one polymer and (c) the at least one surfactant in an aqueous medium.

18. A method for treating fibers or articles, comprising contacting the fibers or articles with the aqueous composition according to any one of claims 1-6 and 10-16.

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