阅读说明：本技术 通过电导率测量和过酸组合物监测过酸浓度的方法 (Method for monitoring peracid concentration by conductivity measurement and peracid composition ) 是由 李俊忠 C·鲍尔 A·普里多 R·斯托布 V·西瓦什瓦姆 J·P·克尔 于 2020-05-29 设计创作，主要内容包括：公开了包含相容的离子化合物的过氧羧酸组合物以递送电导率信号以在稀释使用时能够通过电导率监测过氧羧酸浓度。还公开了通过电导率测量过氧羧酸浓度的方法。有利地,电导率测量允许用户在无需繁琐的滴定步骤的情况下在使用点确定过氧羧酸的浓度来确定在使用应用中提供各种益处的浓度。(Peroxycarboxylic acid compositions comprising compatible ionic compounds are disclosed to deliver a conductivity signal to enable monitoring of peroxycarboxylic acid concentrations upon dilution for use by conductivity. Also disclosed is a method for measuring peroxycarboxylic acid concentration by conductivity. Advantageously, the conductivity measurement allows a user to determine the concentration of peroxycarboxylic acid at the point of use without the need for cumbersome titration steps to determine the concentration that provides various benefits in the use application.)

1. A method for monitoring the concentration of peroxycarboxylic acid,

the method comprises the following steps:

providing a peroxycarboxylic acid or a use solution of a peroxycarboxylic acid comprising at least about 5% by weight of a composition of an ionic compound;

contacting the conductivity probe or sensor to the use solution; and

detecting the conductivity signal to determine the concentration of peroxycarboxylic acid in the use solution.

2. The process of claim 1 wherein the peroxycarboxylic acid composition is formed from combining a C1-C22 carboxylic acid and hydrogen peroxide, and wherein the peroxycarboxylic acid is a C1-C22 peroxycarboxylic acid.

3. The method of any one of claims 1-2, wherein the carboxylate polymer is a peroxycarboxylic acid compatible magnesium, aluminum, or hydronium salt.

4. The method of claim 3, wherein the ionic compound is magnesium sulfate or sulfuric acid.

5. The method of any one of claims 1-4, wherein the ratio of the ionic compound to peroxycarboxylic acid is between about 5:1 to about 1:5 to ensure adequate conductivity readings.

6. The process of any one of claims 1-5, wherein the peroxycarboxylic acid composition comprises a stabilizer and wherein the ratio of the stabilizer to the ionic compound is between about 1:8 to about 1: 15.

7. The process of any one of claims 1-6 wherein the use solution pH of the peroxycarboxylic acid or peroxycarboxylic acid composition is from about 2 to about 9, or less than 5.

8. The process of any one of claims 1-7, wherein the peroxycarboxylic acid is peroxyacetic acid, or wherein the peroxycarboxylic acid composition comprises peroxyacetic acid, acetic acid, hydrogen peroxide, and water.

9. The method of any one of claims 1-8, wherein the detecting a conductance signal is before or after the use solution is applied to a surface in need of cleaning, sanitation, and/or disinfection.

10. A method of cleaning, sanitizing, and/or disinfecting, the method comprising:

providing a use solution of a peroxycarboxylic acid or a peroxycarboxylic acid composition comprising at least about 5% by weight of an ionic compound for conductivity monitoring to a surface in need of cleaning, sanitizing, and/or disinfecting;

contacting a conductivity probe or sensor with the use solution;

detecting a conductivity signal to determine a concentration of peroxycarboxylic acid in the use solution; and

removing dirt, scale and/or biofilm from a surface requiring surface cleaning or sanitation and/or disinfection.

11. The process of claim 10, wherein the peroxycarboxylic acid composition is formed by combining a C1-C22 carboxylic acid, hydrogen peroxide, and wherein the peroxycarboxylic acid is a C1-C22 peroxycarboxylic acid.

12. The method of any one of claims 10-11, wherein the ionic compound is a peroxycarboxylic acid compatible magnesium, aluminum or hydronium salt, preferably the ionic compound is magnesium sulfate or sulfuric acid.

13. The method of any one of claims 10-12, wherein the ratio of the ionic compound to the peroxycarboxylic acid is between about 5:1 to about 1:5 to ensure sufficient conductivity readings to ensure sufficient concentrations of peroxycarboxylic acid are dosed for cleaning, sanitizing, and/or disinfecting of a surface.

14. The process of any one of claims 10-13, wherein the peroxycarboxylic acid composition comprises a stabilizer and wherein the ratio of the stabilizer to the ionic compound is between about 1:8 to about 1:15, and/or wherein the pH of the peroxycarboxylic acid or peroxycarboxylic acid composition is from about 2 to about 9, or less than 5.

15. The process of any of claims 10-14 wherein the peroxycarboxylic acid composition is free of phosphorous.

16. A peroxycarboxylic acid forming composition having conductivity monitoring capabilities comprises:

C1-C22 carboxylic acid;

a source of hydrogen peroxide;

water;

an ionic compound comprising a peroxycarboxylic acid compatible magnesium salt, an aluminum salt or a hydronium salt; and

a stabilizing agent, a water-soluble stabilizer and a water-soluble stabilizer,

wherein a C1-C22 peroxycarboxylic acid is formed, and wherein the ratio of the ionic compound to the peroxycarboxylic acid is between about 5 to 1 and 1 to 5 to ensure a detectable conductivity signal.

17. The composition of claim 16, wherein the carboxylic acid is acetic acid, the stabilizers are dipicolinic acid and phosphonic acid, and the composition meets organic certification requirements.

18. The composition of any one of claims 16-17, wherein the non-ionic compound is magnesium sulfate or sulfuric acid.

19. The composition of any one of claims 16-18, wherein the C1-C22 carboxylic acid comprises about 10-50 wt.%, the hydrogen peroxide source comprises about 10-70 wt.%, the water comprises about 0.1-20 wt.%, the ionic compound comprises about 5-50 wt.%, and the stabilizing agent comprises about 0-5 wt.%.

20. A peroxycarboxylic acid composition having conductivity monitoring capabilities,

the peroxycarboxylic acid composition comprises:

about 5-20 wt% peroxyacetic acid;

about 15-40 wt% acetic acid;

about 5-50 wt% hydrogen peroxide;

water;

about 5-50% by weight of a peroxycarboxylic acid compatible ionic compound comprising a magnesium, aluminum or hydronium salt; and

about 0.001 to about 5 weight percent stabilizer.

Technical Field

The present invention relates to peroxycarboxylic acid ("peracid") compositions comprising compatible ionic compounds to deliver a conductivity signal to enable monitoring of peroxycarboxylic acid concentration by conductivity upon dilute use. Also provided are methods of measuring peroxycarboxylic acid concentration by conductivity. Advantageously, the conductivity measurement allows a user to determine the concentration of peroxycarboxylic acid at the point of use without the need for cumbersome titration steps to determine the concentration that provides various benefits in the use application.

Background

Peroxycarboxylic acid compositions can be prepared by acid-catalyzed equilibrium reactions, typically generated in chemical plants, and then shipped to a customer site for use. Due to the inherent manufacturing, storage, transportation and stability limitations of peroxycarboxylic acids, there is an increasing demand for on-site generation of peroxycarboxylic acids. Regardless of the source of peroxycarboxylic acid, stability challenges still exist, and challenges exist for accurate metering and application of peroxycarboxylic acid concentrations. Depending on the particular peroxycarboxylic acid, the half-life may vary from a few minutes to hours, to weeks to months.

Despite inherent stability limitations, peroxycarboxylic acids are very useful and effective in various technical fields of cleaning, disinfection, sterilization, and the like. Thus, there is a need for accurate dosing and delivery of peroxycarboxylic acids to ensure that the desired cleaning, disinfection, hygiene or sterilization is achieved.

A common method of ensuring accurate dosing and delivery of cleaning compositions (e.g., peroxycarboxylic acids) is titration, a well-known and practiced method of determining the concentration of a component of a solution. Various chemical titrations have been practiced, wherein a titrant is typically added to the solution in which it reacts with its selected component. Once all of the reaction components have reacted with the known titrant, a measurable or significant change occurs, indicating that the reaction is complete. In some cases, the apparent change comprises a color change. For example, the color change can vary greatly between various chemical titrations.

Titration can be a cumbersome process that requires the chemist or other skilled operator to perform carefully. In some cases, it may be impractical for a chemist or other technician to manually perform the titration, although it may be desirable to obtain data obtained by titration. An auto-titrator may be implemented that attempts to determine when a complete reaction has occurred and performs appropriate titration calculations to determine the amount of a component in solution. However, depending on the reaction, an automated process may have difficulty accurately determining the end point of the reaction. In addition, automated systems may require a significant amount of time to complete a process, which may be undesirable or unacceptable if the solution needs to be monitored at certain intervals. Although titration equipment has advanced, this process is not preferred by many of the dosed cleaning compositions in the field, such as peroxycarboxylic acids. Instead, it is common practice to simply over-dispense or deliver the cleaning composition for insurance to provide the minimum required threshold. However, this may result in delivery of an unnecessary excess of chemical and waste of chemical, resulting in increased costs.

Thus, there remains a need for methods of accurately determining the dosage and delivery concentration of peroxycarboxylic acids.

It is therefore an object of the present disclosure to provide compositions having an ionic compound compatible with peroxycarboxylic acids to allow conductivity measurements to be made to determine the concentration of peroxycarboxylic acids.

It is another object of the present disclosure to provide organic peroxycarboxylic acid compositions that can be measured by using the conductivity in solution.

It is another object of the present disclosure to formulate organic peroxycarboxylic acid compositions comprising an ionic compound compatible with peroxycarboxylic acids, i.e., peroxyacetic acid, and capable of being measured using conductivity in solution.

Other objects, aspects and advantages of the present invention will be apparent to those skilled in the art based on the following disclosure, drawings and appended claims.

Disclosure of Invention

One advantage of the present invention is the ability to monitor peroxycarboxylic acid concentration by conductivity during dilute use. Conductivity measurements advantageously allow a user to determine the concentration of peroxycarboxylic acid at the point of use without the need for cumbersome titration steps to determine the concentration that provides various benefits in the use application.

In one embodiment, a method of monitoring peroxycarboxylic acid concentration comprises: providing a use solution of a peroxycarboxylic acid composition comprising an ionic compound; contacting the conductivity probe or sensor with a use solution; and detecting the conductivity signal to determine the concentration of peroxycarboxylic acid in the use solution.

In other embodiments, peroxycarboxylic acid forming compositions having conductivity monitoring capabilities

The method comprises the following steps: C1-C22 carboxylic acid; a source of hydrogen peroxide; water; an ionic compound; and a stabilizer.

In other embodiments, a peroxycarboxylic acid composition having conductivity monitoring capabilities comprises: about 5-20 wt% peroxyacetic acid; about 15-40 wt% acetic acid; about 5-50 wt% hydrogen peroxide; water; about 5-50 wt% of an ionic compound; and about 0.001 to 5 weight percent of a stabilizer.

While multiple embodiments are disclosed, other embodiments will become apparent to those skilled in the art based on the following detailed description, which discloses and describes illustrative embodiments. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.

Drawings

Figure 1 shows a graph of measurements of peracetic acid concentration and conductivity measurements for formulation 1 using the evaluated peroxycarboxylic acid compositions disclosed in the examples.

Figure 2 shows a graph of measurements of peracetic acid concentration and conductivity measurements for formulation 2 using the evaluated peroxycarboxylic acid compositions disclosed in the examples.

Figure 3 shows a graph of measurements of the effect of ionic compounds in the peroxycarboxylic acid compositions evaluated as disclosed in the examples on antimicrobial efficacy against staphylococcus aureus and escherichia coli in use solutions.

Figure 4 shows a graph of measurements of the effect of ionic compounds in the assessed peroxycarboxylic acid compositions disclosed in the examples on the antimicrobial efficacy of pseudomonas aeruginosa in use solutions.

FIG. 5 shows a graph of the solubility of calcium phosphate in a peroxyacetic acid formulation; calcium was dissolved in a solution of Oxonia Active (0.20%, 0.24% and 0.28% v/v) and formulation 2 (0.11%, 0.15% and 0.20% v/v) by adding calcium phosphate (300RPM, 5 min, 25 ℃).

FIG. 6 shows a graph of the solubility of calcium carbonate in a peroxyacetic acid formulation; calcium was dissolved in a solution of Oxonia Active (0.20%, 0.24% and 0.28% v/v) and formulation 2 (0.11%, 0.15% and 0.20% v/v) by adding calcium carbonate (300RPM, 5 min, 25 ℃).

Figure 7 shows a graph of a SADT study of peroxycarboxylic acid compositions containing ionic compounds for conductivity monitoring.

Various embodiments of the present invention will be described in detail below with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the invention. The drawings presented herein are not limiting of various embodiments according to the invention and are intended to be illustrative of the invention.

Detailed Description

Embodiments are not limited to specific peroxycarboxylic acid compositions comprising ionic compounds and/or methods of measuring peroxycarboxylic acid composition concentrations using conductivity methods that can vary and are understood by the skilled artisan. It has been surprisingly found that peroxycarboxylic acid compositions can be accurately measured by conductivity, thereby enabling a user of the composition to quickly determine the dosing concentration of the composition, which provides various benefits and uses not previously available for peroxycarboxylic acid compositions.

It is also to be understood that all terms used herein are for the purpose of describing particular embodiments only, and are not intended to be limiting in any way or scope. For example, as used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the context clearly dictates otherwise. Further, all units, prefixes, and symbols may be denoted in their SI-accepted form. The numerical ranges set forth in the specification include numbers within the defined ranges. Throughout this disclosure, various aspects are presented in a range format. It should be understood that the description in range format is merely for convenience and clarity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

It is therefore to be more readily understood that the invention first defines certain terms. 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 the embodiments belong. Many methods and materials similar, modified, or equivalent to those described herein can be used in the practice of the embodiments without undue experimentation, but the preferred materials and methods are described herein. In describing and claiming the embodiments, the following terminology will be used in accordance with the definitions set out below.

The term "about" as used herein refers to variations in the amount that may occur, for example, through typical measurement and liquid handling steps used to make concentrates or use solutions in the real world; through inadvertent errors in these steps; by manufacturing, source, or difference in purity of the ingredients used to manufacture the compositions or perform the methods, and the like. The term "about" also includes amounts that differ due to different equilibrium conditions for the composition formed from a particular initial mixture. The claims include equivalents to these quantities whether or not modified by the term "about".

The terms "actives" or "percent by weight actives" or "active concentration" are used interchangeably herein and refer to the concentration of each ingredient involved in cleaning expressed as a percentage minus inert ingredients (e.g., water or salt).

The term "free" as used herein refers to a composition that is completely devoid of the component or has a small amount of the component such that the component does not affect the properties of the composition. This component may be present as an impurity or as an contaminant and should be less than 0.5 wt.%. In another embodiment, the amount of the component is less than 0.1 wt%, and in yet another embodiment, the amount of the component is less than 0.01 wt%.

As used herein, when the term "mixing" or "mixture" is used in reference to "peroxycarboxylic acid", "peroxycarboxylic acid composition", it refers to a composition or mixture comprising more than one peroxycarboxylic acid.

As used herein, the terms "weight percent," "wt%", "percent by weight," "percent by weight," and variations thereof, refer to the concentration of a substance as the substance divided by the total weight of the composition and multiplied by 100. It is understood that as used herein, "percent," "percent," and the like are intended to be synonymous with "weight percent," "wt%", and the like.

The methods and compositions can comprise, consist essentially of, or consist of these components and ingredients as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions may comprise additional steps, components, or ingredients, but that the additional steps, components, or ingredients alone do not materially alter the basic and novel characteristics of the claimed methods and compositions.

Peroxycarboxylic acid compositions

According to an embodiment, the peroxycarboxylic acid composition comprises a peroxycarboxylic acid, a carboxylic acid, an oxidizing agent, water, an ionic compound, and optionally additional ingredients, such as a stabilizer. These alkaline detergent compositions may contain additional functional ingredients and may be provided in the form of concentrates or use compositions. Exemplary peroxycarboxylic acid forming compositions are shown in tables 1A and 1B, and peroxyacetic acid forming compositions are shown in table 2 in weight percent.

TABLE 1A

TABLE 1B

TABLE 2

Exemplary peroxycarboxylic acid compositions are shown in tables 3A and 3B in weight percent and peroxyacetic acid compositions are shown in table 4 in weight percent. The peroxycarboxylic acid composition is an equilibrium composition.

TABLE 3A

TABLE 3B

TABLE 4

In various aspects of embodiments, including those described in tables 1-4, the peroxycarboxylic acid compositions meet the organic certification requirements of the national organic program. In some embodiments, the ionic compound and the oxidizing agent, along with the peroxycarboxylic acid composition, meet organic certification requirements.

Peroxycarboxylic acid compositions

Peroxycarboxylic acids (or percarboxylic acids) generally have the formula R (CO3H) n, wherein, for example, R is an alkyl, aralkyl, cycloalkyl, aromatic or heterocyclic group, n is 1,2 or 3, and the parent acid is designated by using the peroxygen prefix. The R groups may be saturated or unsaturated and substituted or unsubstituted. The composition may comprise a mixture or combination of several different peroxycarboxylic acids. Such compositions are commonly referred to as mixed peroxycarboxylic acids or mixed peroxycarboxylic acid compositions. For example, in some preferred embodiments, the composition comprises one or more C1 to C4 peroxycarboxylic acids and one or more C5 to C22 peroxycarboxylic acids.

As described herein, methods of use and compositions can include a peroxycarboxylic acid (or a peroxycarboxylic acid composition comprising a peroxycarboxylic acid, a carboxylic acid, hydrogen peroxide, water, and optionally additional components), or a mixed peroxycarboxylic acid (or a mixed peroxycarboxylic acid composition comprising more than one peroxycarboxylic acid, more than one carboxylic acid, hydrogen peroxide, water, and optionally additional components).

Peroxycarboxylic acid compositions can be formed by combining one or more carboxylic acids with an oxidizing agent (e.g., hydrogen peroxide). The peroxycarboxylic acid compositions, as monitored by conductivity, have a pH in the use solution of from about 2 to 9, or from about 2 to 5, or less than about 5, when diluted with various types of water. In a preferred embodiment, the peroxycarboxylic acid composition comprises peroxyacetic acid.

Carboxylic acids

The peroxycarboxylic acid compositions are formed by combining at least one carboxylic acid with an oxidizing agent. In some embodiments, at least two, at least three, or at least four or more carboxylic acids may be used. The carboxylic acids used in the compositions of the present invention are C1 to C22 carboxylic acids. In some embodiments, the carboxylic acid used in the compositions of the present invention is a C5 to C11 carboxylic acid. In some embodiments, the carboxylic acid is a C1 to C5 carboxylic acid. Examples of suitable carboxylic acids include, but are not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, dodecanoic acid, and branched chain isomers thereof, lactic acid, maleic acid, ascorbic acid, citric acid, glycolic acid, pivalic acid, neoheptanoic acid, neodecanoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and mixtures thereof.

Preferred carboxylic acids include organic compounds and/or those approved as organic certifications, such as acetic acid for the production of peroxyacetic acid.

In some embodiments, the carboxylic acid is included in the peroxycarboxylic acid forming composition in an amount of at least about 5% to about 50%, about 15% to about 40%, or about 15% to about 30% by weight. Further, without being limited by the invention, all ranges recited include the numbers defining the range and include each integer within the defined range.

Oxidizing agent

The peroxycarboxylic acid compositions are formed by combining at least one carboxylic acid with an oxidizing agent. Examples of inorganic oxidizing agents include the following types of compounds or sources of such compounds, or alkali metal salts comprising or forming adducts with such types of compounds: the following hydrogen peroxide or hydrogen peroxide donors: group 1 (IA) oxidizing agents, such as lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, such as magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizing agents, such as zinc peroxide; group 13(IIIA) oxidizing agents, e.g. boron compoundsSubstances, e.g. perborates, e.g. of the formula Na₂[BiO₂MOH)₄].6H₂Sodium perborate hexahydrate of O (also known as sodium perborate tetrahydrate); formula Na₂BiO2)₂[(OH)₄].4H₂Sodium perborate tetrahydrate of O (also known as sodium perborate trihydrate); formula Na₂[BiO2)iOH)₄]Sodium perborate (also known as sodium perborate monohydrate); group 14 (IVA) oxidants, such as persilicates and peroxycarbonates, also known as percarbonates, such as alkali metal persilicates or peroxycarbonates; group 15 (VA) oxidizing agents, such as peroxynitrous acid and its salts; peroxyphosphoric acid and its salts, such as perphosphate; group 16 (VIA) oxidizing agents, for example peroxysulfuric acid and salts thereof, such as peroxymonosulfuric acid and peroxydisulfuric acid, and salts thereof, such as persulfates, e.g., sodium persulfate; and group VIIa oxidants such as sodium periodate, potassium perchlorate. Other active inorganic oxygen compounds may include transition metal peroxides; and other such peroxy compounds, and mixtures thereof.

In some embodiments, the compositions and methods of the present invention employ one or more of the above-listed inorganic oxidizing agents. Suitable inorganic oxidizing agents include hydrogen peroxide 30 donors of ozone, hydrogen peroxide adducts, group IIIA or VIA oxidizing agents, group VA oxidizing agents, group VIIA oxidizing agents, or mixtures thereof. Suitable examples of such inorganic oxidizing agents include percarbonates, perborates, persulfates, perphosphates, persilicates, or mixtures thereof.

Hydrogen peroxide is one suitable example of an inorganic oxidizing agent. The hydrogen peroxide may be provided as a mixture of hydrogen peroxide and water, for example, as liquid hydrogen peroxide in an aqueous solution. Hydrogen peroxide is commercially available in water at concentrations of 35%, 40-70% and 90%. For safety reasons, 35-50% is usually used.

Preferred oxidizing agents include organic compounds and/or those approved for organic certification, such as hydrogen peroxide.

In some embodiments, the oxidizing agent is included in the peroxycarboxylic acid forming composition in an amount of at least about 10% to about 70%, about 15% to about 70%, about 20% to about 70%, or about 25% to about 65% by weight. Further, without being limited by the invention, all ranges recited include the numbers defining the range and include each integer within the defined range.

Water (W)

In some embodiments, the peroxycarboxylic acid forming composition can comprise water. The water may be added separately to the composition or may be provided in the composition as a result of being present in the aqueous material added to the composition. In some embodiments, the composition comprises from about 0% to about 30% by weight water, from about 0.1% to about 20% by weight water, or from about 0.5% to about 15% by weight water. It is to be understood that the invention encompasses all values and ranges between these values and ranges.

Ionic compounds

The peroxycarboxylic acid composition comprises at least one ionic compound to deliver a conductivity signal, thereby enabling the peroxycarboxylic acid concentration to be monitored by conductivity upon dilute use. The ionic compound must be compatible with the peroxycarboxylic acid without reducing stability and/or antimicrobial efficacy. Suitable ionic compounds include, but are not limited to, alkali metal salts, alkaline earth metal salts, such as magnesium salts, and hydronium salts.

Preferably, the ionic compound is a magnesium salt. Exemplary magnesium salts include, but are not limited to, magnesium acetate, magnesium benzoate, magnesium citrate, magnesium formate, magnesium hexafluorosilicate, magnesium hydroxide, magnesium lactate, magnesium molybdate, magnesium nitrate, magnesium perchlorate, magnesium phosphonate, magnesium salicylate, magnesium sulfate, magnesium sulfite, hydrates thereof, and mixtures thereof.

Preferred magnesium salts include magnesium sulfate, magnesium acetate and magnesium nitrate. More preferred magnesium salts include organic compounds and/or those approved as GRAS for direct food contact, such as magnesium sulfate.

Exemplary aluminum salts include, but are not limited to, aluminum acetate, aluminum benzoate, aluminum citrate, aluminum formate, aluminum hexafluorosilicate, aluminum lactate, aluminum molybdate, aluminum nitrate, aluminum perchlorate, aluminum phosphonate, aluminum salicylate, aluminum sulfate, hydrates thereof, and mixtures thereof.

The hydronium salt is of the formula H₃O⁺Salts of acids of A-. Exemplary hydronium salts include, but are not limited to, hydronium sulfate, bisulfate, nitrate, phosphate, phosphonate, sulfonate, acetate, formate, citrate, lactate, and gluconate. Preferably, ammonium bisulfate, i.e., sulfuric acid, H, is used in the peroxycarboxylic acid composition₂SO₄To provide electrical conductivity because it is very effective in delivering electrical conductivity.

As an additional benefit, the use of a hydrated hydrogen salt, such as sulfuric acid, provides further benefits for scale removal and biofilm. Without being limited by a particular mechanism of action, sulfuric acid provides a low pH, can prevent and remove mineral scale, and beneficially provides effective biofilm kill and removal. In one embodiment, biofilm efficacy is obtained at a pH of about 3 or less, or preferably about 2.3 or less. Thus, in preferred embodiments, compositions comprising hydrated hydrogen salt ionic compound species (particularly sulfuric acid in some embodiments) at a level of at least about 5% by weight provide effective performance against biofilms, providing stable peroxycarboxylic acid compositions that can be traced by conductivity.

In some embodiments, the ionic compound is included in the peroxycarboxylic acid composition in an amount of at least about 5% to about 50% by weight, about 10% to about 40% by weight, or about 15% to about 40% by weight. Further, without being limited by the invention, all ranges recited include the numbers defining the range and include each integer within the defined range.

In one embodiment, the ratio of ionic compound to peroxycarboxylic acid in the composition is between about 5 to 1 and 1 to 5 to ensure that a conductivity signal can be detected. In other embodiments, an increased ratio of ionic compound to peroxycarboxylic acid will further provide the benefit of a conductivity signal. In some embodiments, the ratio of ionic compound to peroxycarboxylic acid in the composition is greater than 5 to 1, e.g., 6 to 1, 7 to 1, 8 to 1, 9 to 1, 10 to 1, or greater. Without being limited by a particular mechanism of action, a concentration of at least about 5 wt.% of the ionic compound provides a sufficient concentration to ensure that a conductivity signal can be detected. This is different from the use of hydrated hydrogen salts (e.g., sulfuric acid) or mineral acid catalysts in peroxycarboxylic acid compositions to catalyze or accelerate the reaction to form an equilibrium peroxycarboxylic acid composition, because such concentrations are low, e.g., less than about 1 wt.%, or less than about 2 wt.%. However, such conventional use of inorganic acid catalysts does not provide water conductivity to the composition.

Additional functional ingredients

The components of the peroxycarboxylic acid compositions can be combined with various functional components suitable for the uses disclosed herein. In some embodiments, the peroxycarboxylic acid composition comprising peroxycarboxylic acid, carboxylic acid, hydrogen peroxide, ionic compound, and water comprises a substantial amount, or even substantially all, of the total weight of the composition. For example, in some embodiments, fewer or no additional functional ingredients are disposed therein.

In other embodiments, additional functional ingredients may be included in the composition. The functional ingredients provide the desired properties and functions to the composition. For the purposes of this application, the term "functional ingredient" includes materials that provide advantageous properties in a particular application when dispersed or dissolved in a use solution and/or a concentrate solution (e.g., an aqueous solution). Some specific examples of functional materials are discussed in more detail below, although the specific discussion of materials is given by way of example only, and a wide variety of other functional ingredients may be used. For example, many of the functional materials described below are related to materials used in cleaning. However, other embodiments may include functional ingredients for other uses.

In some embodiments, the peroxycarboxylic acid compositions can comprise a stabilizer. In some embodiments, the peroxycarboxylic acid compositions may include optical brighteners, defoamers, anti-redeposition agents, bleaches, solubility modifiers, dispersants, metal protection agents, soil anti-redeposition agents, stabilizers, corrosion inhibitors, builders/chelating agents (chelating agents), enzymes, aesthetic enhancers (including perfumes and/or dyes), additional rheology and/or solubility modifiers or thickeners, hydrotropes or couplants, buffers, solvents, additional cleaning agents, and the like. These additional ingredients may be pre-formulated with the composition or added to the use solution before, after, or substantially simultaneously with the addition of the composition.

According to various embodiments of the present invention, various additional functional ingredients may be provided in the composition in an amount of from about 0 wt% to about 50 wt%, from about 0.01 wt% to about 50 wt%, from about 0.1 wt% to about 50 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 25 wt%, or from about 1 wt% to about 20 wt%. Additionally, all ranges stated include the range number and include each integer within the range number, without limitation to the invention.

Stabilizer

The peroxycarboxylic acid composition can include a stabilizer. The stabilizer prevents or slows the decomposition of the peracid in the balanced peroxycarboxylic acid composition. According to embodiments, various stabilizers may be provided in the composition in an amount of from about 0% to about 20%, from about 0.1% to about 20%, from about 1% to about 10%, or from about 1% to about 5% by weight. According to preferred embodiments, various stabilizers may be provided in the composition in an amount of about 0% and about 5%, about 0.001% and about 5%, about 0.01% to about 1%, or about 0.05% to about 0.5% by weight. Additionally, all ranges stated include the range number and include each integer within the range number, without limitation to the invention.

Suitable stabilizers for peroxycarboxylic acid compositions include, for example, pyridine carboxylic acid compounds. The pyridine carboxylic acid comprises a pyridine dicarboxylic acid, comprising, for example, 2, 6-pyridinedicarboxylic acid (DPA). In a further aspect, the stabilizer is picolinic acid or a salt thereof. In one aspect of the invention, the stabilizer is picolinic acid or a compound having the following formula (IA):

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; r²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from zero to 3; or a salt thereof.

In a further aspect of the invention, the peracid stabilizer is a compound having the following formula (IB):

wherein R is¹Is OH or-NR^1aR^1bWherein R is^1aAnd R^1bIndependently is hydrogen or (C)₁-C₆) An alkyl group; r²Is OH or-NR^2aR^2bWherein R is^2aAnd R^2bIndependently is hydrogen or (C)₁-C₆) An alkyl group; each R³Independently is (C)₁-C₆) Alkyl, (C)₂-C₆) Alkenyl or (C)₂-C₆) An alkynyl group; and n is a number from zero to 3; or a salt thereof. Preferred stabilizers include organic compounds such as dipicolinic acid.

Other stabilizers suitable for use in peroxycarboxylic acid compositions include, for example, phosphonic acids or phosphonates and aminocarboxylic acids (aminocarboxylic acid type chelating agents). Suitable phosphonic acids and phosphonates include 1-hydroxyethylidene-l, l-diphosphonic acid (CH3C (PO3H2)2OH) (HEDP); ethylenediaminetetramethylenephosphonic acid (EDTMP); cyclohexane-1, 2-tetramethylenephosphonic acid (DTPMP); amino [ tris (methylenephosphonic acid) ]; (ethylenediamine [ tetramethylene-phosphonic acid) ]; 2-phosphonobutane-1, 2, 4-tricarboxylic acid; or a salt thereof, such as an alkali metal salt, an ammonium salt, or an alkanoylamine salt, such as a monoethanolamine, diethanolamine, or tetraethanolamine salt; or mixtures thereof. In some embodiments, the chelating agent comprises 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP). Preferred stabilizers include organic compounds such as HEDP.

Suitable aminocarboxylic acid type masking agents include acids or alkali metal salts thereof, such as aminoacetate and salts thereof. Suitable aminocarboxylates include, for example, N-hydroxyethylaminodiacetic acid; methylglycine diacetic acid (MGDA); hydroxy ethylene diamine tetraacetic acid; nitrilotriacetic acid (NTA); ethylenediaminetetraacetic acid (EDTA); n-hydroxyethyl-ethylenediamine triacetic acid (HEDTA); glutamic acid N, N-diacetic acid (GLDA), diethylenetriaminepentaacetic acid (DTPA); iminodisuccinic acid (IDS); ethylenediamine disuccinic acid (EDDS); 3-hydroxy-2, 2-iminodisuccinic acid (HIDS); hydroxyethyliminodiacetic acid (HEIDA); and alanine-N, N-diacetic acid; and the like; and mixtures thereof.

In a preferred embodiment, at least two stabilizers, such as dipicolinic acid and HEDP, are included in the composition.

In some embodiments, the stabilizer is free of phosphorous, and the peroxycarboxylic acid composition is further free of phosphorous.

In some embodiments, the weight ratio of ionic compound to stabilizer in the composition is between about 8:1 to about 15:1, or between about 8:1 to about 13: 1. Significantly higher concentrations of ionic compounds are required to deliver a conductivity signal compared to conventional use of some ionic compounds (e.g., metal salts) that stabilize peroxycarboxylic acid compositions with a molar ratio of metal salt to chelating agent or stabilizing agent of about 5:1 to about 1: 14.

Application method

Peroxycarboxylic acid compositions have many uses. They are suitable for use in cleaning and disinfecting compositions, for example compositions suitable for cleaning hard surfaces and objects and removing dirt, scale and/or biofilm from such surfaces and objects, including clean-out-of-place (COP) applications. They are also suitable for disinfecting water sources, treatment membranes, laundry applications, instrument and/or equipment disinfection, and the like. For various uses of peroxycarboxylic acids, a user needs to readily determine the dosage and/or dispense concentration of peroxycarboxylic acid for a particular use. This ensures that a sufficient concentration of the intended cleaning (including removal of dirt, scale and/or biofilm), hygiene and/or disinfection is provided, as well as reducing any overuse or consumption of the peroxycarboxylic acid composition. In a preferred aspect, the peroxycarboxylic acid composition is a single use composition.

In addition to the benefits described herein, conductivity measurements allow a user to determine the concentration of peroxycarboxylic acid at the point of use without the need for cumbersome titration steps to determine the concentrations that provide various benefits in the use application.

Advantageously, according to some embodiments, the use solution comprising peroxycarboxylic acid is provided as a stable composition free of phosphorus. In yet another embodiment, the use solution containing peroxycarboxylic acid is an organic peroxycarboxylic acid composition. In other embodiments, the use solution is a stabilized organic peroxycarboxylic acid composition further free of phosphorous.

In some embodiments, compositions comprising hydrated hydrogen salt ionic compound species (e.g., sulfuric acid) at levels of at least about 5 wt.% provide effective performance against biofilms, providing stable peroxycarboxylic acid compositions that can be tracked by conductivity. Embodiments using a hydrated hydrogen salt (e.g., sulfuric acid) provide benefits for scale removal and/or biofilm removal at acidic pH in the use solution, i.e., a pH below about 3, or below about 2.3. Without being limited by a particular mechanism of action, sulfuric acid provides a low pH, can prevent and remove mineral scale, and beneficially provides effective biofilm kill and removal. In still other embodiments where the composition comprises a hydrated hydrogen ion compound species (e.g., sulfuric acid), there is a efficacy benefit against non-biofilm bacteria, such as listeria, including listeria monocytogenes, in addition to biofilm.

The methods disclosed herein are suitable for monitoring and/or detecting the concentration of a peroxycarboxylic acid composition circulating within a system and/or within a cleaning application (e.g., before and/or during use of the application). In yet another aspect, the method is suitable for monitoring and/or detecting the concentration of a peroxycarboxylic acid composition stored and/or contained prior to use.

The disclosed method is suitable for testing use solutions that are particularly useful to users of the composition at the point of use because the use solution (as opposed to the concentrate) is applied to the surface. The use solution may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides the use solution with the desired disinfecting and/or other antimicrobial properties. The water used to dilute the concentrate to form the use composition may be referred to as dilution water or diluent, and may vary between different locations. Typical dilution factors are between about 1 and about 10,000, but will depend on factors including water hardness, the amount of soil, dirt and/or biofilm to be removed, and the like. In one embodiment, the concentrate is diluted at a concentrate to water ratio of between about 1:10 and about 1:10,000. Specifically, the concentrate is diluted at a ratio of concentrate to water of between about 1:100 and about 1:5,000. More specifically, the concentrate is diluted at a ratio of concentrate to water of between about 1:250 and about 1:2,000.

The frequency of monitoring the peroxycarboxylic acid concentration of the use solution (e.g., the monitoring frequency) will vary depending on the desired use application. For example, the monitoring device can be programmed to monitor the concentration of peroxycarboxylic acid in the initial use composition prior to the delivery time point. Alternatively, the concentration may be monitored every 15 minutes, every 30 minutes, every hour, every two hours, every day, or other suitable time. The monitoring frequency/interval can vary depending on the particular application for which the composition is used and the corresponding threshold concentration of peroxycarboxylic acid, among other things.

The detection sensitivity using ionic compounds can range from a few ppm to greater than 10,000 ppm. Advantageously, this allows for the detection of peroxycarboxylic acid concentrations for delivery to various applications requiring use of 1ppm and higher.

The detection method may be performed at any suitable temperature. In some embodiments, the process of the invention is carried out at a temperature in the range of from about 0 ℃ to about 70 ℃, e.g., from about 0 ℃ to about 4 ℃ or 5 ℃, from about 5 ℃ to about 10 ℃, from about 11 ℃ to about 20 ℃, from about 21 ℃ to about 30 ℃, from about 31 ℃ to about 40 ℃, including at a temperature of from about 37 ℃, from about 41 ℃ to about 50 ℃, from about 51 ℃ to about 60 ℃, or from about 61 ℃ to about 70 ℃.

Methods of measuring peroxycarboxylic acid concentration using conductivity include contacting a peroxycarboxylic acid composition with a conductivity sensor or probe. The methods described herein are not limited, as long as the sensor, probe and/or cell is compatible with the acidic peroxycarboxylic acid composition, depending on the particular sensor, probe and/or cell used to measure the conductivity of the peroxycarboxylic acid composition. The conductivity is measured in mS/cm (corresponding to the conductivity measurement expressed as. mu.S/cm).

The use of a conductivity probe provides an electroanalytical method of measuring a parameter of a product. An exemplary conductivity sensor includes two electrodes and operates by applying a voltage between the two electrodes and measuring the resulting current. The relationship between current magnitude and voltage allows the resistance and conductivity of the product to be determined.

The use of sensors (which may also be referred to as optical units and/or optical detectors) also provides an electrical analysis method of measuring product parameters. Exemplary sensors are disclosed in, for example, U.S. patent publication No. 2012/0014912, and U.S. patent nos. 8,835,874, 8,229,204, 8,143,070, 8,119,412, 8,187,540, 8,084,756, 8,076,155, 8,076,154, 7,572,687, and 7,169,236, which are incorporated by reference.

In one embodiment, the method comprises providing a sensor, probe and/or battery at a location that contacts the peroxycarboxylic acid composition to measure a sample of the use solution. Without being limited to the particular sequence of events used in the methods described herein, conductivity can be measured at various points in the sequence of events generally described herein. In one embodiment, the conductivity is measured in a flow or volume of the peroxycarboxylic acid composition prior to dosing. In another embodiment, the conductivity is preferably measured at the outlet and/or reservoir of the generator of the peroxycarboxylic acid composition. For example, in various applications, an existing generator of peroxycarboxylic acid compositions can be used, and the concentration of peroxycarboxylic acid composition can be measured in an inlet, a conduit, an outlet, and/or a reservoir (e.g., a reservoir) for the peroxycarboxylic acid composition produced. In another embodiment, the conductivity is measured in a stream or vessel that delivers the peroxycarboxylic acid composition in use application.

In one embodiment, the concentration of the peroxycarboxylic acid composition can be measured by first measuring the conductivity of the water as a baseline or control, and the difference between the conductivity readings of the peroxycarboxylic acid use solution and the water control is used to measure the peracid.

In one aspect, the measurement of the conductivity of the peroxycarboxylic acid composition is used to determine whether the concentration of peroxycarboxylic acid is at least a minimum threshold concentration for a desired use application (e.g., fouling, scaling, and/or biofilm removal, or other application). For example, applying a particular concentration may include: sterile vial rinses typically require about 1000-; or central disinfection typically requires about 100 and 1000ppm peracid.

In one aspect, suitable carriers or solvents for forming the use solutions of the peroxycarboxylic acid compositions include various types of water. In one aspect, deionized water, soft water, and/or hard water (e.g., 5 or more grids) can be used to measure conductivity. It is beneficial to implement conductivity measurements without being limited to a particular type of water.

The method of thereafter measuring peroxycarboxylic acid concentration using electrical conductivity can include applying or contacting the composition to a device, surface, substrate, or the like in need of cleaning, disinfecting, sanitizing, or the like.

The conductivity measurement can be combined with various other measurement and measurement devices that may be required for the peroxycarboxylic acid composition, i.e., the peroxycarboxylic acid composition generated in situ. One or more measuring devices may be combined with the device to measure conductivity. Exemplary measuring devices are devices suitable for measuring one or more of the reaction kinetics or system operation for producing the peroxycarboxylic acid composition, including, for example, devices that measure weight, flow rate (e.g., a flow meter or switch), pH, pressure, temperature, and combinations thereof. Examples of other suitable measuring devices include, for example, thermometers, end of product alarms, peroxide monitors, IR/UV/VIS spectroscopy, NMR and pressure switches.

Conductivity measurements using conductivity sensors may be used in conjunction with various control systems. In some aspects, it may be desirable to associate conductivity measurement capabilities with an optional controller or software platform. The software platform can provide a user or system with a production profile for selecting a desired peroxycarboxylic acid formulation for on-site production based on conductivity measurements. For example, a controller or control software for system operation can allow a user or system to select additional peroxycarboxylic acid formulations as well as desired volumes and dosage concentrations of the on-site generated formulations based on conductivity measurements. In another aspect, the control software can determine the timing, sequence and/or selection of raw materials (e.g., reagents) to be fed into the system, mixing time, and total reaction time required to produce a user or system selected peroxycarboxylic acid formulation. Examples of suitable controllers are disclosed herein, as well as various embodiments of those disclosed in U.S. patent nos. 7,547,421 and 8,075,857, entitled apparatus and methods for producing peroxycarboxylic acids, the entire contents of which are incorporated herein by reference.

The conductivity measurement may be combined with or include a data output device. The data output device can be used to share information related to the peroxycarboxylic acid composition as measured by conductivity and/or peroxycarboxylic acid compositions produced in situ and also as measured by conductivity. For example, the information backbone can be used to collect and disseminate data from processes that produce peroxycarboxylic acid compositions, including, for example, composition consumption, distribution, or use, as well as additional formulation production-related data. Such data may be generated in real-time and/or provided in a historical log of operational data that may be detected or stored by a user or system. These and other embodiments of data output devices, information sharing, remote system operation, and the like, which may be suitable for use in the methods described herein, are further described, for example, in U.S. patent nos. 8,162,175, 7,292,917, 6,895,307, 6,697,706, and 6,377,868, and U.S. patent publication nos. 2005/0065644, 2004/0088076, and 2003/0195656, which are expressly incorporated herein by reference.

In embodiments employing a control system and/or data output device, a user or system can monitor usage and performance, including, for example, chemical dispensing, managing chemical dispensing to various point-of-use applications, communicating with a system operator to control and monitor chemical dispensing, and/or formulation, and the like. According to further embodiments, a user or system can remotely control the system, including the program system and managing data output.

Examples

Embodiments of the present invention are further defined in the following non-limiting examples. It should be understood that these examples, while disclosing certain embodiments of the invention, are given by way of illustration only. From the above discussion and these examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various usages and conditions. Accordingly, various modifications of the embodiments of the present invention in addition to those illustrated and described herein will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

The compositions of Table 5 were analyzed in the examples and iodine titrations were performed using the procedure specified in QATM 317 to determine the levels of peracetic acid and hydrogen peroxide. The method comprises two steps of determining the peracid and hydrogen peroxide content. The first step is iodine titration while suppressing the oxidation of hydrogen peroxide by dilution and low temperature (ice water; the presence of ice does not interfere with the titration chemistry in the reaction flask). The second step uses the same sample and measures the hydrogen peroxide content by adding sulfuric acid and a molybdenum catalyst, which reagents can rapidly accelerate the hydrogen peroxide oxidation of iodide. The hydrogen peroxide concentration is determined by taking the difference between the volume of titrant used for the peracid endpoint and the volume required to reach the hydrogen peroxide endpoint.

1. Titration of peracetic acid: the peracid samples were dispensed into 250mL erlenmeyer flasks. The flask was filled with about 200mL of ice water (0 ℃ C. -10 ℃ C.). The flask was charged with 2mL of 2% starch indicator and 5mL of 10% KI (potassium iodide). The flask was placed on a stir plate and immediately titrated with 0.1N sodium thiosulfate to a colorless endpoint for at least 20 seconds. The titrant volume was recorded (EP 1).

2. Hydrogen peroxide titration: the burette was not refilled from the peracetic acid titration. The flask was charged with 12mL of 9N sulfuric acid and 10-15 drops of 1N ammonium molybdate. The solution will turn blue-black. Titrate to a second colorless endpoint lasting at least 20 seconds. The titration volume was recorded (EP 2).

The peracetic acid and hydrogen peroxide contents were calculated as follows:

peracetic acid content:

wherein N is the prescribed concentration of thiosulfate titrant

Equivalent of 38 ═ peracetic acid

1000-conversion from milliequivalents to equivalents

Hydrogen peroxide content:

wherein N is the prescribed concentration of thiosulfate titrant

17 equivalent of hydrogen peroxide

1000-conversion from milliequivalents to equivalents

TABLE 5

Example 1

Comparative formulation 1 (Ionic Compound MgSO) at 120ppm Peroxyacetic acid concentration using various water sources₄) And formulation 2 (H)₂SO₄) The conductivity of the ionic compound to determine any effect on conductivity. The conductivity was measured by an LMIT09 conductivity measurement device (with temperature compensation capability) manufactured by Ecolab Engineering GmbH, West Gesdodv, Germany.

The results are shown in table 6 comparing the conductivity of peroxycarboxylic acid compositions using various water sources. Oxonia Active (5.25-6.4% POAA, 25.6-29.4% H)₂O₂) Used as a positive control for comparison.

TABLE 6

For 17Grain Plus water, 500ppm NaHCO₃Added to 17G water to provide an increased water hardness threshold for conductivity measurements. As shown, only the conductivity of the water was initially tested. The conductivity of the control, formulation 1 and formulation 2 was then tested and the data in parentheses shows the difference between the evaluated formulation and water.

The results show that the concentration of peracetic acid at active concentration was measured using DI (deionized) water control, formulation 1 and formulation 2. However, when only soft water and 5 grain water were used, formulations 1 and 2 containing the ionic compound were able to accurately measure concentration by conductivity, as evidenced by a difference of mS/cm of greater than 0.1. The results show that 17 grains + with very high hardness and alkalinity are able to achieve the conductivity of formulation 1.

Example 2

Further testing of formulations 1 and 2 was performed to assess the effect of peracetic acid concentration on conductivity measurements. Measurements were made in 5 grain water at increasing concentrations. The results are shown in fig. 1 and 2, where the relationship between peracetic acid concentration and conductivity readings is taken at 5 grain water dilution. As shown, a linear response between the peroxyacetic acid concentration and the conductivity reading was observed for both formulations 1 and 2, providing a basis for monitoring the peroxyacid concentration by using the conductivity in the solution.

Example 3

After demonstrating the compatibility of the ionic compounds in examples 1 and 2 in the conductivity measurements, further tests were performed to confirm that the ionic compounds did not negatively interfere with the antimicrobial efficacy of the peroxycarboxylic acids.

Oxonia Active(5.25-6.4％POAA，25.6-29.4％H₂O₂) Used as a positive control for comparison, and H was added to the test formulation alone₂SO₄And MgSO₄Oxonia Active of (1). Oxonia Active and H₂SO₄And MgSO₄Test concentrations of the compositionsDegrees (POAA) are equal. Formulations 1 and 2 were also analyzed. 30 seconds exposure of each formulation to staphylococcus aureus and escherichia coli was performed. Log reductions were then measured for staphylococcus aureus and escherichia coli. The ATCC numbers tested were 7 to 8 logs.

The results are shown in fig. 3, where substantially similar performance was obtained in all formulations evaluated, as measured by less than a 1log difference in antimicrobial efficacy compared to the control. All formulations provided greater than 5log reduction in both S.aureus and E.coli in a 105ppm peracetic acid use solution.

Example 4

Additional tests were conducted to show the compatibility of the ionic compounds of examples 1 and 2 over various ranges of use concentrations. Formulations 1 and 2 were again compared to an Oxonia Active control at a concentration of 120 ppm. The test formulations were evaluated at use concentrations of 110ppm, 120ppm and 130 ppm. A 30 second exposure of pseudomonas aeruginosa to each formulation was performed. The log reduction of pseudomonas aeruginosa was then measured. The results in fig. 4 show that both formulations 1 and 2 provide equivalent antimicrobial efficacy at both 120ppm and 130ppm use concentrations.

Example 5

The peroxycarboxylic acid compositions comprising compatible ionic compounds were further evaluated to deliver a conductivity signal to enable monitoring of peroxycarboxylic acid concentration by conductivity upon dilute use. These conductivity measurements advantageously allow a user to determine the concentration of peroxycarboxylic acid at the point of use without the need for cumbersome titration steps to determine the concentration that provides various benefits in the use application. As an additional benefit, the use of a hydrated hydrogen salt, such as sulfuric acid, provides a further benefit for scale removal. Without being limited by a particular mechanism of action, sulfuric acid provides a low pH that prevents and removes mineral scale. Dissolution experiments were performed to evaluate various calcium (Ca)²⁺) Mineral salts in Oxonia Active (5.25-6.4% POAA, 25.6-29.4% H)₂O₂) And formulation 2 (H)₂SO₄) Solubility in (c). The calcium mineral salt evaluated is calcium phosphate or hydroxyapatite [ Ca ]₅(PO₄)₃(OH)]And calcium carbonate (CaCO)₃)。

Experimental procedure:

1. preparation of test solutions: two of the 100mL Oxonia Active test solutions were used at the following concentrations: 0.20%, 0.24% and 0.28% v/v; 100mL of the test solution of formulation 2 was prepared in deionized water in separate 150mL beakers at the following two concentrations: 0.11%, 0.15% and 0.20% v/v. A 1 inch stir bar was placed in each beaker. Each beaker was placed on a stir plate and the solution was mixed at a speed of 300RPM for at least one minute to ensure a homogeneous solution was prepared. One set of solutions (Oxonia Active: 0.20%, 0.24%, and 0.28% v/v; formulation 2: 0.11%, 0.15%, and 0.20% v/v) was dispensed for use in combination with calcium phosphate salts, and another set of solutions (Oxonia Active: 0.20%, 0.24%, and 0.28% v/v; formulation 2: 0.11%, 0.15%, and 0.20% v/v) was dispensed for use in combination with calcium carbonate salts.

2. Addition of calcium mineral salts: 2-5 g of the desired calcium salt are added to the solution. The addition of calcium salt was continued until the solution failed to dissolve further (the solution became cloudy). The solution was stirred at 300RPM for 5 minutes. The solution was not heated.

3. Filtration of undissolved calcium salt: after 5 minutes, pass through a 30mL plastic syringe (Luer-Lok)^TMTip REF 305618) extracted about 20mL of solution. Filter 0.45 μm syringe: (Syringe Filter,25mm,0.45 μm Nylon Membrane) was attached to the tip of the Syringe and the filtered solution was collected in a small sample container.

4. Quantification of calcium in solution: the filtered solutions were analyzed by ICP-MS (inductively coupled plasma mass spectrometry) to quantify the dissolved calcium in each solution.

Results and discussion:

each solution of Oxonia Active and formulation 2 was analyzed via ICP-MS to quantify the amount of calcium dissolved by the addition of calcium phosphate or calcium carbonate. The concentrations selected for Oxonia Active and formulation 2 represent concentrations that achieve the efficacy of food contact sanitizing microorganisms while maintaining rinse-free concentrations of all ingredients in the formulation below EPA approved (40CFR § 180.940). It was observed that formulation 2 dissolved significantly more calcium salts (calcium phosphate and calcium carbonate) at lower concentrations than Oxonia Active. At an equivalent concentration of 0.20% v/v, the solution of formulation 2 contained 342mg/L calcium, as calcium phosphate was added, whereas the solution of Oxonia Active contained only 44mg/L calcium (FIG. 5). Similarly, at an equivalent concentration of 0.20% v/v, the solution of formulation 2 contained 428mg/L calcium because calcium carbonate was added, while the solution of Oxonia Active contained only 78mg/L calcium (FIG. 6).

The above results show that formulation 2 has significantly higher capacity to help remove mineral soils common in food and beverage manufacturing environments (hard water scale from calcium carbonate and milk stone from calcium phosphate) than standard peracetic acid sanitizing compositions such as Oxonia Active. The increased calcium solubilizing ability in formulation 2 reduced the frequency of acid wash removal of mineral scale.

Example 6

Evaluation was performed by the self-accelerated decomposition test (SADT). SADT refers to the lowest temperature at which the peroxycarboxylic acid composition is likely to undergo self-accelerating decomposition. In some embodiments, SADT refers to the lowest temperature at which self-accelerated decomposition can occur under commercial packaging, storage, shipping, and/or use conditions. SADT may be evaluated, calculated, predicted, and/or measured by any suitable method. The complete testing protocol used in this example may be found in "recommendations for dangerous cargo transport", test and standards manual, revision 5: (United nations): classification procedures, test methods and criteria relating to the self-reacting species of item 4.1 and the organic peroxide of item 5.2: test H.4 regenerative storage test (28.4.4).

Since peroxycarboxylic acids belong to the class of organic peroxides and are therefore self-reacting, self-heating products, tests were conducted to demonstrate whether a given peroxycarboxylic acid product package requires cooling. The test simulates a large volume package with a dewar. In this example, an oven temperature of 50 ℃ was used for a spherical dewar having 3 rods, a volume of 1.0L and a heat transfer coefficient of 40mW/Kg K (equivalent to a 300 gallon peracid suitcase). Each sample volume was 800mL (952 g). The dewar was filled with the product to 80% of the total volume, equipped with a special sealing lid and a recording thermometer, and placed in an oven set at 50 ℃. When the inner package temperature rose to 48 ℃, the timer was started. The SADT of the product is defined as <55 ℃ if the temperature does not exceed the oven temperature of 50 ℃ by 7 days 6 ℃.. if the temperature does not exceed the oven temperature of 6 ℃, the SADT is considered to be >55 ℃, which can be considered for transport and storage without refrigeration.

The results are shown in FIG. 7. The upper row is the oven temperature and the lower row is the sample composition temperature.

Example 7

Using peroxyacetic acid (POAA) compositions and hydrogen peroxide (H)₂O₂) Evaluation of peroxycarboxylic acid stability at 40 ℃ and 54 ℃ to confirm POAA and H₂O₂The concentration did not decrease over time, indicating that the presence of the ionic compound negatively affected the stability of the composition. To predict POAA and H in concentrated solution₂O₂Accelerated stability test according to EPA recommendations (guidelines 830.6317 and 830.6320). The EPA recommends incubating the solution at elevated temperatures for various periods of time to assess the long-term stability of the active antimicrobial ingredient (40 ℃ for four (4) weeks, or 54 ℃ for two (2) weeks). These conditions are considered as predictors of twelve month room temperature stability.

Samples of formulation 2 were prepared and stored at 40 ℃ for 4 weeks. POAA and H₂O₂The concentration was measured by iodometric titration at the beginning and end of the incubation period. POAA and H measured after 4 weeks of incubation at 40 ℃₂O₂The concentration losses were 1.74% and 2.69%, respectively.

Three samples of formulation 2 were prepared and stored at 54 ℃ for two weeks. POAA and H₂O₂The concentration was measured by iodometric titration at the beginning and end of the incubation period. After two weeks incubation at 54 ℃, POAA and H in all three samples₂O₂The maximum measured loss of concentration was 6.79% and 5.53%, respectively.

It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments, advantages, and modifications are within the scope of the following claims. Additionally, the entire contents of all of the previously discussed patent applications are incorporated herein by reference.

The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof.