WO2024031514A1

WO2024031514A1 - A multipurpose liquid rinse aid

Info

Publication number: WO2024031514A1
Application number: PCT/CN2022/111693
Authority: WO
Inventors: Yi Guo; Xin Lu; Nathan D. Peitersen
Original assignee: Ecolab Usa Inc.
Priority date: 2022-08-11
Filing date: 2022-08-11
Publication date: 2024-02-15

Abstract

Multipurpose rinse aid compositions and methods of using the compositions are disclosed. Compositions containing scale-inhibiting organic phosphonates, polycarboxylates or polycarboxylic acids or salts thereof formulated with hydrotropes and surfactants provide enhanced antiscaling performance compared to traditional chelants and threshold inhibitors used in rinse aid compositions.

Description

A MULTIPURPOSE LIQUID RINSE AID

TECHNICAL FIELD

The disclosure relates generally to multipurpose rinse aid compositions and methods of using the compositions. The compositions containing scale-inhibiting organic phosphonates, polycarboxylates or polycarboxylic acids or salts thereof formulated with hydrotropes and surfactants to provide enhanced antiscaling performance compared to traditional chelants and threshold inhibitors used in rinse aid compositions.

BACKGROUND

The development of more highly concentrated liquid rinse aid compositions that provide desirable drying and sheeting performance while also improving antiscaling performance remains as an unmet commercial need. Concentrated liquid compositions that provide better drying and sheeting performance by lower dosage is also desirable from consumer cost expectations. However, the improvement in antiscaling performance remains a critical need.

Scaling causes significant interruptions in cleaning. In particular in areas having high water hardness scaling issues can present extreme challenges. For example, descaling steps, such as treatment with acid washes, may be required on occasion. The reduction of descaling frequency will save labor time and costs, freight and energy.

It is therefore an object of this disclosure to provide rinse aid compositions that provide desirable drying and sheeting performance while also improving antiscaling performance.

It is a further object of the disclosure to provide rinse aid compositions that can result in scale accumulation occurring more slowly and therefore requiring less frequent (or eliminated the need) descaling intervention.

It is another object of this disclosure to formulate rinse aid compositions that provide improved customer acceptance through use.

Other objects, embodiments and advantages of this disclosure will be apparent to one skilled in the art in view of the following disclosure, the drawings, and the appended claims.

BRIEF SUMMARY

The following objects, features, advantages, aspects, and/or embodiments, are not exhaustive and do not limit the overall disclosure. No single embodiment need provide each and every object, feature, or advantage. Any of the objects, features, advantages, aspects, and/or embodiments disclosed herein can be integrated with one another, either in full or in part.

It is a primary object, feature, and/or advantage of the present disclosure to improve on or overcome the deficiencies in the art and commercial products, including by providing enhanced multipurpose rinse aid compositions having enhanced antiscaling performance compared to traditional chelants and threshold inhibitors used in rinse aid compositions.

According to some aspects of the present disclosure, multipurpose liquid rinse aid compositions comprise: a scale-inhibiting organic phosphonate having one of the following structures:

wherein:

Y is

or a salt thereof;

Y’ is absent,

or a salt thereof;

X is N, O, or OH;

R ₁ and R ₂ are independently a linear or branched C1-C10 alkyl group;

R ₃ is -N (Y) ₂; and

n is 1-20;

an optional additional scale inhibitor comprising a polycarboxylate, polycarboxylic acid or salt thereof; a nonionic surfactant; a hydrotrope; and water.

According to some additional aspects of the present disclosure, methods of using a rinse aid composition comprise: providing a liquid rinse aid composition as described herein, contacting the rinse aid composition with water to form a use solution, and contacting the use solution to a surface in need of rinsing and drying. The compositions provide antiscaling efficacy and drying and sheeting performance.

These and/or other objects, features, advantages, aspects, and/or embodiments will become apparent to those skilled in the art after reviewing the following brief and detailed descriptions of the drawings. Furthermore, the present disclosure encompasses aspects and/or embodiments not expressly disclosed but which can be understood from a reading of the present disclosure, including at least: (a) combinations of disclosed aspects and/or embodiments and/or (b) reasonable modifications not shown or described.

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

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows photographs of glasses treated with a rinse aid composition as described in Example 1.

Figure 2 shows a graph depicting %inhibition of scaling with the evaluated liquid rinse aid compositions as described herein and in Example 2.

Figure 3 shows an interval plot of drying time with the evaluated surfactant packages and formulations of the liquid rinse aid compositions as described herein and in Example 3.

Various embodiments of the present disclosure will be described in detail 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 disclosure. Figures represented herein are not limitations to the various embodiments according to the disclosure and are presented for exemplary illustration of the invention. An artisan of ordinary skill in the art need not view, within isolated figure (s) , the near infinite number of distinct permutations of features described in the following detailed description to facilitate an understanding of the present invention.

DETAILED DESCRIPTION

The present disclosure is not to be limited to that described herein, which can vary and are understood by skilled artisans. No features shown or described are essential to permit basic operation of the present disclosure unless otherwise indicated. It has been surprisingly found that the described multipurpose rinse aid compositions have enhanced antiscaling performance compared to traditional chelants and threshold inhibitors used in rinse aid compositions.

It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a, " "an" and "the" can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.

Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this disclosure are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges, fractions, and individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 1 ¹/ ₂, and 4 ³/ ₄. This applies regardless of the breadth of the range.

As used herein, the term “and/or” , e.g., “X and/or Y” shall be understood to mean either "X and Y" or "X or Y" and shall be taken to provide explicit support for both meanings or for either meaning, e.g. A and/or B includes the options i) A, ii) B or iii) A and B.

It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.

The methods and compositions of the present disclosure may comprise, consist essentially of, or consist of the components and ingredients of the present disclosure as well as other ingredients described herein. As used herein, “consisting essentially of” means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.

Unless defined otherwise, all technical and scientific terms used above have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present disclosure pertain.

The terms “invention” or “present invention” are not intended to refer to any single embodiment of the particular invention but encompass all possible embodiments as described in the specification and the claims.

The term “about, ” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, temperature, pH, and the like. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like. The term “about” also encompasses these variations. Whether or not modified by the term “about, ” the claims include equivalents to the quantities.

The term "actives" or "percent actives" or "percent by weight actives" or "actives concentration" are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts. It is also sometimes indicated by a percentage in parentheses, for example, “chemical (10%) . ”

As used herein, the term “alkyl” or “alkyl groups” refers to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. ) , cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. ) , branched-chain alkyl groups (e.g., isopropyl, tert- butyl, sec-butyl, isobutyl, etc. ) , and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups) .

Unless otherwise specified, the term “alkyl” includes both “unsubstituted alkyls” and “substituted alkyls. ” As used herein, the term “substituted alkyls” refers to alkyl groups having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino) , acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido) , imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclic group. As used herein, the term “heterocyclic group” includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes) , thiirane (episulfides) , dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

The term “configured” describes structure capable of performing a task or adopting a particular configuration. The term “configured” can be used interchangeably with other similar phrases, such as constructed, arranged, adapted, manufactured, and the like.

Terms characterizing sequential order, a position, and/or an orientation are not limiting and are only referenced according to the views presented.

As used herein, the term “exemplary” refers to an example, an instance, or an illustration, and does not indicate a most preferred embodiment unless otherwise stated.

As used herein, the phrase “food processing surface” refers to a surface of a tool, a machine, equipment, a structure, a building, or the like that is employed as part of a food processing, preparation, or storage activity. Examples of food processing surfaces include surfaces of food processing or preparation equipment (e.g., slicing, canning, or transport equipment, including flumes) , of food processing wares (e.g., utensils, dishware, wash ware, and bar glasses) , and of floors, walls, or fixtures of structures in which food processing occurs. Food processing surfaces are found and employed in food anti-spoilage air circulation systems, aseptic packaging sanitizing, food refrigeration and cooler cleaners and sanitizers, ware washing sanitizing, blancher cleaning and sanitizing, food packaging materials, cutting board additives, third-sink sanitizing, beverage chillers and warmers, meat chilling or scalding waters, autodish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial garment sprays, and non-to-low-aqueous food preparation lubricants, oils, and rinse additives.

As used herein, the term "free" refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and shall be less than about 0.1 wt-%and in yet another embodiment, the amount of component is less than about 0.01 wt-%, or 0 wt-%.

The term “generally” encompasses both “about” and “substantially. ”

The term “hard surface” refers to a solid, substantially non-flexible surface such as a counter top, tile, floor, wall, panel, window, plumbing fixture, kitchen and bathroom furniture, appliance, engine, circuit board, dish, mirror, window, monitor, touch screen, and thermostat. Hard surfaces are not limited by the material; for example, a hard surface can be glass, metal, tile, vinyl, linoleum, composite, wood, plastic, etc. Hard surfaces may include for example, health care surfaces and food processing surfaces.

As used herein, the term “instrument” refers to the various medical or dental instruments or devices that can benefit from cleaning with a composition as described herein. As used herein, the phrases “medical instrument, ” “dental instrument, ” “medical device, ” “dental device, ” “medical equipment, ” or “dental equipment” refer to instruments, devices, tools, appliances, apparatus, and equipment used in medicine or dentistry. Such instruments, devices, and equipment can be cold sterilized, soaked or washed and then heat sterilized, or otherwise benefit from cleaning in a composition of the present disclosure. These various instruments, devices and equipment include, but are not limited to: diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g. bone saws and their blades) , hemostats, knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, retractors, straightener, punches, extractors, scoops, keratomes, spatulas, expressers, trocars, dilators, cages, glassware, tubing, catheters, cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes) and related equipment, and the like, or combinations thereof.

As used herein the term "polymer" refers to a molecular complex comprised of a more than ten monomeric units and generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, and higher "x" mers, further including their analogs, derivatives, combinations, and blends thereof. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible isomeric configurations of the molecule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometrical configurations of the molecule.

As used herein, the term “soil” or “stain” refers to any soil, including, but not limited to, non-polar oily and/or hydrophobic substances which may or may not contain particulate matter such as industrial soils, mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust, and/or food based soils such as blood, proteinaceous soils, starchy soils, fatty soils, cellulosic soils, etc.

The “scope” of the present disclosure is defined by the appended claims, along with the full scope of equivalents to which such claims are entitled. The scope of the disclosure is further qualified as including any possible modification to any of the aspects and/or embodiments disclosed herein which would result in other embodiments, combinations, subcombinations, or the like that would be obvious to those skilled in the art.

The term “substantially” refers to a great or significant extent. “Substantially” can thus refer to a plurality, majority, and/or a supermajority of said quantifiable variable, given proper context.

As used herein, the term “substantially free” refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and shall be less than about 0.5 wt-%.

The term "surfactant" or "surface active agent" refers to an organic chemical that when added to a liquid changes the properties of that liquid at a surface.

As used herein, the term “ware” refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. As used herein, the term “warewashing” refers to washing, cleaning, or rinsing ware. Ware also refers to items made of plastic. Types of plastics that can be cleaned with the compositions include but are not limited to, those that include polypropylene polymers (PP) , polycarbonate polymers (PC) , melamine formaldehyde resins or melamine resin (melamine) , acrylonitrile-butadiene-styrene polymers (ABS) , and polysulfone polymers (PS) . Other exemplary plastics that can be cleaned using the compounds and compositions of the disclosure include polyethylene terephthalate (PET) polystyrene polyamide.

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

RINSE AID COMPOSITIONS

According to embodiments, the liquid multipurpose rinse aid compositions include an organic phosphonate and optionally a polycarboxylate, polycarboxylic acid or salt thereof, hydrotrope, surfactant (s) , and water. The liquid multipurpose rinse aid compositions can include additional functional ingredients and can be provided as concentrate or use compositions. Exemplary compositions are shown in Tables 1A-1B in weight percentage. While the components may have a percent actives of 100%, it is noted that Tables 1A and 1B do not recite the percent actives of the components, but rather, recites the total weight percentage of the raw materials (i.e. active concentration plus inert ingredients) .

TABLE 1A

TABLE 1B

Organic Phosphonate

The liquid rinse aid compositions comprise an organic phosphonate. Organic phosphonates are organic derivatives of phosphonic acid, HP (O) (OH) ₂. The organic phosphonates preferably contain a single C-N bond adjacent (vicinal) to the C-P bond, unlike conventional organic phosphonate scale inhibitors, such as 1-hydroxyethylidene-1, 1-diphosphonic acid (HEDP) or 2-Phosphonobutane-1, 2, 4-tricarboxylic acid (PBTC) .

Organic phosphonates have one of the following general structures:

wherein:

Y is

or a salt thereof;

Y’ is absent,

or a salt thereof;

X is N, O, or OH;

R ₁ and R ₂ are independently a linear or branched C1-C10 alkyl group;

R ₃ is -N (Y) ₂; and

n is 1-20.

In the structures I-V the salt form of Y or Y’ is preferably a suitable cation, such as sodium or potassium.

The described organic phosphonates are particularly suitable for use in antiscaling in ware washing applications, including rinse aid applications.

A preferred class of organic phosphonates include polyether phosphonic acids, including polyamino polyether methylene phosphonic acid and polyamino polyether methylene phosphonates such as the those having the following structure:

wherein Z is independently H or CH ₃, and wherein n is 2-12. In a preferred embodiment the organic phosphonate is PAPEMP ( (HO) ₂P (O) CH ₂) ₂NCH (CH ₃) CH ₂ (OCH ₂CH (CH ₃) ₂N (CH ₂) ₆N (CH ₂P (O) (OH) ₂) ₂) having the structure:

Additional exemplary organic phosphonates include the structures:

Still further exemplary organic phosphonates include HMDTMP ( (HO) ₂P (O) CH ₂) ₂N (CH ₂) ₆N (CH ₂2P (O) (OH) ₂) ₂) having the structure:

and the like.

Still further exemplary organic phosphonates include DTMPA ( (HO) ₂P (O) CH ₂N [CH ₂CH ₂N (CH ₂P (O) (OH) ₂) ₂] ₂) having the structure:

A further preferred class of organic phosphonates include alkylene oxide phosphonates. Any combination of the foregoing scale inhibitors may be used and salts of any of these compounds can be used as well, such as ammonium salts. In some embodiments, the foregoing scale inhibitors can further be combined with conventional phosphonates. Examples of phosphonates include, but are not limited to: phosphinosuccinic acid oligomer (PSO) described in U.S. Patent No. 8,871,699, 2-phosphonobutane-l, 2, 4-tricarboxylic acid (PBTC) , 1-hydroxyethane-l, 1-diphosphonic acid, HEDP, aminotri (methylenephosphonic acid) ; 2-hydroxyethyliminobis (methylenephosphonic acid) , diethylenetriaminepenta (methylenephosphonic acid) , diethylenetriaminepenta (methylenephosphonate) , sodium salt (DTPMP) , hexamethylenediamine (tetramethylenephosphonate) , potassium salt bis (hexamethylene) triamine (pentamethylenephosphonic acid) ; and phosphorus acid.

In some embodiments, the organic phosphonate is included in the rinse aid composition at an amount of at least about 1 wt-%to about 30 wt-%, about 1 wt-%to about 25 wt-%, about 1 wt-%to about 20 wt-%, about 1 wt-%to about 15 wt-%, about 2 wt-%to about 15 wt-%, or about 2 wt-%to about 10 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

As described herein the organic phosphonate according to the formulae and various structures disclosed herein is a phosphonate or a salt thereof, including a cation. In preferred embodiments the organic phosphonate does not include any betaine or polybetaine structures, such that there is a charge separated, neutral molecule.

In some embodiments the organic phosphonate does not include ATMP (aminotris (methylenephosphonic acid) with chemical formula N (CH ₂PO ₃H ₂) ₃) . In still further embodiments, the organic phosphonate does not include PBTC (2-Phosphonobutane-1, 2, 4-tricarboxylic acid) .

Additional Scale Inhibitor

The liquid rinse aid composition comprises an optional additional scale inhibitor comprising a polycarboxylate, polycarboxylic acid or salt thereof. Beneficially the combination of the organic phosphonate and the polycarboxylate, polycarboxylic acid or salt thereof provides an improved performance for antiscaling over conventional threshold inhibitors used for antiscaling and hard water treatment.

Exemplary polycarboxylates that can be used as scale inhibitors include, but are not limited to: those having pendant carboxylate (--CO ₂-) groups such as polyacrylic acid, maleic acid, maleic/olefin copolymer, sulfonated copolymer or terpolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, and hydrolyzed acrylonitrile-methacrylonitrile copolymers.

Examples of suitable additional polymers include polyacrylic acid, polymethacrylic acid, polymaleic acid homopolymers, copolymers of acrylic methacrylic or maleic acids (and combinations thereof) .

A preferred group of polycarboxylates include polycarboxylic acid polymers (e.g. Acusol polymers) , including polyacrylic acid homopolymers and polymaleic acid homopolymers, and polymers modified by a fatty acid end group. Exemplary polyacrylic acid homopolymers include those with a molecular weight between about 500-100,000 g/mol, or between about 1,000-50,000 g/mol, or between about 1,000-25,000 g/mol.

A variety of such polycarboxylate homopolymers, copolymers and terpolymers are known and described in patent and other literature, and are available commercially. Exemplary polycarboxylates that may be utilized include for example: homopolymers, copolymers and terpolymers of polyacrylates; polymethacrylates; polymaleates. Examples of suitable polymers include acrylic acid homopolymers, maleic acid homopolymers, methacrylic acid homopolymers, acrylic/maleic copolymers, maelic acid copolymers, acrylic/methacrylic copolymers, maleic acid terpolymers, hydrophobically modified acrylic acid copolymers and terpolymers, hydrophobically modified maleic acid copolymers and terpolymers, hydrophobically modified methacrylic acid copolymers and terpolymers. Suitable polymers preferably have a molecular weight between about 500 to about 50,000 g/mol, more preferably between about 500 and about 25,000 g/mol and particularly between about 500 and about 10,000 g/mol.

Further suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two carboxyl groups which are in each case separated from one another by, preferably, no more than two carbon atoms. Polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid. Polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, for example, citric acid. Another suitable polycarboxylic acid is the homopolymer of acrylic acid. Polycarboxylates can further be end capped with sulfonates.

In some embodiments, the polycarboxylate, polycarboxylic acid or salt thereof is included in the rinse aid composition at an amount of at least about 1 wt-%to about 20 wt-%, about 1 wt-%to about 15 wt-%, about 1 wt-%to about 10 wt-%, about 1 wt-%to about 8 wt-%, or about 1 wt-%to about 5 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Hydrotrope

The liquid rinse aid composition comprises a hydrotrope, preferably an anionic hydrotrope. The compositions include at least one anionic hydrotrope, preferably a low foaming anionic hydrotrope that does not increase foaming of the nonionic surfactant (s) included in the liquid rinse aid compositions. The hydrotrope may be used to aid in maintaining the solubility of sheeting or wetting agents, and also to modify the aqueous solution creating increased solubility for organic material. In some embodiments, hydrotropes are low molecular weight aromatic sulfonate materials such as xylene sulfonates, dialkyldiphenyl oxide sulfonate materials, and cumene sulfonates.

Further exemplary anionic hydrotropes include short chain alkyl benzenes, alkyl naphthalenes and alkyl naphthalene sulfonates. In an aspect, the class of short chain alkyl benzene or alkyl naphthalene hydrotropes includes alkyl benzene sulfonates based on toluene, xylene, and cumene, and alkyl naphthalene sulfonates. These can include sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and sodium butylnaphthalene sulfonate. Sodium xylene sulfonate is a preferred anionic hydrotrope.

In an aspect, the composition includes from about 1 wt-%to about 40 wt-%, from about 5 wt-%to about 40 wt-%, from about 5 wt-%to about 30 wt-%, from about 5 wt-%to about 20 wt-%, or about 10 wt-%to about 20 wt-%of the anionic hydrotrope.

Surfactants

The liquid rinse aid composition comprises at least one nonionic surfactant.

In some embodiments, the least one nonionic surfactant is included in the liquid rinse aid composition at an amount of at least about 5 wt-%to about 50 wt-%, about 5 wt-%to about 40 wt-%, about 5 wt-%to about 35 wt-%, about 5 wt-%to about 30 wt-%, about 10 wt-%to about 30 wt-%, or about 10 wt-%to about 25 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Exemplary nonionic surfactants (A-E) and polymer surfactants (F-J) are shown in Table 2.

TABLE 2

The at least one nonionic surfactant can include compounds of the general formula (I) , R ₁- (A) _x- (B) _y1- (A) _z- (B) _y2-R ₂ (I) , wherein R ₁ and R ₂ independently denote H or linear or branched, substituted or unsubstituted C1-C22 alkyl,

A denotes CH ₂-CH ₂-O,

B denotes CH ₂-CHR ₃-O, wherein R ₃ denotes H or linear or branched, unsubstituted C1-C10 alkyl,

x is an integer in the range from 0 to 35,

y ₁ is an integer in the range from 0 to 60,

y ₂ is an integer in the range from 0 to 35,

z is an integer in the range from 0 to 35, and

wherein the sum of x+y ₁+z+y ₂ is at least 1.

Preferably the sum of x+y ₁+z+y ₂ is in the range of 1 to100, more preferably the sum of x+y ₁+z+y ₂ is in the range of 1 to 75 even more preferably the sum of x+y ₁+z+y ₂ is in the range of 2 to 75 and most preferably the sum of x+y ₁+z+y ₂ is in the range of 2 to 70. In preferred embodiments of the surfactant structures, the term “alkyl” refers to acyclic saturated aliphatic residues, including linear or branched alkyl residues. Furthermore, the alkyl residue is preferably unsubstituted and includes as in the case of C ₁-C ₂₂ alkyl 1 to 22 carbon atoms. As used herein, “branched” denotes a chain of atoms with one or more side chains attached to it. Branching occurs by the replacement of a substituent, e.g., a hydrogen atom, with a covalently bonded aliphatic moiety.

Representative examples of linear and branched, unsubstituted C ₁-C ₂₂ alkyl include, but are not limited to methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta-decyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, isopropyl, isobutyl, iso-pentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoe-icosyl, isoheneicosyl, isodocosyl, 2-propyl heptyl, 2-ethyl hexyl and t-butyl.

The at least one nonionic surfactant of general formula (I) according to embodiments B, G and L are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating ethylene oxide (EO) units and a block of repeating propylene oxide (PO) unit interposed between first and second block of repeating ethylene units represented by formula (V) ,

HO- (CH ₂CH ₂O) _x (CH (CH ₃) CH ₂O) _y1 (CH ₂CH ₂O) _z-H (V) .

In some embodiments, the nonionic surfactant of general formula (I) according to embodiments B, G and L have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.

In some embodiments, the nonionic surfactant of general formula (I) according to embodiments C, H and M are the block copolymers of ethylene oxide and higher alkylene oxide functionalized/capped with fatty alcohols. Preferred higher alkylene oxides are propylene oxide, butylene oxide and pentylene oxide. The preferred ratio of ethylene oxide to the higher alkylene oxide units is 1: 2 to 5: 2.

In some embodiments, the nonionic surfactant of general formula (I) according to embodiments E, J and O are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating propylene oxide (PO) units and a block of repeating ethylene oxide (EO) unit interposed between first and second block of repeating propylene units as represented by formula (VI) ,

HO- (CH (CH ₃) CH ₂O) _y1- (CH ₂CH ₂O) _z- (CH (CH ₃) CH ₂O) _y2-H (VI) .

In some embodiments, the nonionic surfactant of general formula (I) according to embodiments E, J and O have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.

In an embodiment, the at least one nonionic surfactant of the general formula (I) has a hydrophilic-lipophilic balance (HLB) value in the range of 2 to 17. In further embodiments, the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 11 when R ₂ is H. In further embodiments, the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 17 when R ₂ is linear or branched, substituted or unsubstituted C ₁-C ₂₂ alkyl.

The HLB value represents the hydrophilic-lipophilic balance of the molecule. The lower the HLB value the more hydrophobic the material is, and vice versa. The HLB values can be calculated according to the method given in Griffin, J. Soc. Cosmetic Chemists, 5 (1954) 249-256. Griffith’s method for nonionic surfactants as described in 1954 is as follows: HLB = 20 X M _h/M, where M _h is the molecular mass of the hydrophilic portion of the molecule; and M is the molecular mass of the whole molecule. Only the EO part in the surfactants is regarded as hydrophilic, all other parts contribute only to the whole molecule.

Additional Surfactants

Still further additional useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Practically any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent. The length of the hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound (1) . Examples of polymeric compounds made from a sequential propoxylation and ethoxylation of initiator are commercially available from BASF Corp. One class of compounds is difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10%by weight to about 80%by weight of the final molecule. Another class of compounds are tetra-flinctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000; and, the hydrophile, ethylene oxide, is added to constitute from about 10%by weight to about 80%by weight of the molecule.

Condensation products of one mole of alkyl phenol wherein the alkyl chain, of straight chain or branched chain configuration, or of single or dual alkyl constituent, contains from about 8 to about 18 carbon atoms with from about 3 to about 50 moles of ethylene oxide (2) . The alkyl group can, for example, be represented by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can be polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. Examples of commercial compounds of this chemistry are available on the market under the trade names

manufactured by Rhone-Poulenc and

manufactured by Union Carbide.

Condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide (3) . The alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range. Condensation products of one mole of saturated or unsaturated, straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide (4) . The acid moiety can consist of mixtures of acids in the above defined carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range. In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this invention for specialized embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances. Care must be exercised when adding these fatty ester or acylated carbohydrates to compositions of the present invention containing amylase and/or lipase enzymes because of potential incompatibility.

Examples of nonionic low foaming surfactants include:

Compounds from (1) which are modified, essentially reversed, by adding ethylene oxide to ethylene glycol to provide a hydrophile of designated molecular weight; and, then adding propylene oxide to obtain hydrophobic blocks on the outside (ends) of the molecule. The hydrophobic portion of the molecule weighs from about 1,000 to about 3,100 with the central hydrophile including 10%by weight to about 80%by weight of the final molecule. The hydrophobic portion of the molecule weighs from about 2,100 to about 6,700 with the central hydrophile including 10%by weight to 80%by weight of the final molecule. Compounds from groups (1) , (2) , (3) and (4) which are modified by "capping" or "end blocking" the terminal hydroxy group or groups (of multi-functional moieties) to reduce foaming by reaction with a small hydrophobic molecule such as propylene oxide, butylene oxide, benzyl chloride; and, short chain fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms; and mixtures thereof. Also included are reactants such as thionyl chloride which convert terminal hydroxy groups to a chloride group. Such modifications to the terminal hydroxy group may lead to all-block, block-heteric, heteric-block or all-heteric nonionics.

Additional examples of effective low foaming nonionics include:

The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issued Sep. 8, 1959 to Brown et al. and represented by the formula

in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued Aug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains where the weight of the terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight of the linking hydrophilic units each represent about one-third of the condensate.

The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. having the general formula Z [ (OR) _nOH] _z wherein Z is alkoxylatable material, R is a radical derived from an alkylene oxide which can be ethylene and propylene and n is an integer from, for example, 10 to 2,000 or more and z is an integer determined by the number of reactive oxyalkylatable groups.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,677,700, issued May 4, 1954 to Jackson et al. corresponding to the formula Y (C ₃H ₆O) _n (C ₂H ₄O) _mH wherein Y is the residue of organic compound having from about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of at least about 6.4, as determined by hydroxyl number and m has a value such that the oxyethylene portion constitutes about 10%to about 90%by weight of the molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formula Y [ (C ₃H ₆O _n (C ₂H ₄O) _mH] _x wherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms in which x has a value of at least about 2, n has a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900 and m has value such that the oxyethylene content of the molecule is from about 10%to about 90%by weight. Compounds falling within the scope of the definition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and the like. The oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.

Additional conjugated polyoxyalkylene surface-active agents which are advantageously used in the compositions of this invention correspond to the formula: P [ (C ₃H ₆O) _n (C ₂H ₄O) _mH] _x wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10%to about 90%by weight. In either case the oxypropylene chains may contain optionally, but advantageously, small amounts of ethylene oxide and the oxyethylene chains may contain also optionally, but advantageously, small amounts of propylene oxide.

Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R ₂CON _R1Z in which: R1 is H, C ₁-C ₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R ₂ is a C ₅-C ₃₁ hydrocarbyl, which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from a reducing sugar in a reductive amination reaction; such as a glycityl moiety.

The alkyl ethoxylate condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

The ethoxylated C ₆-C ₁₈ fatty alcohols and C ₆-C ₁₈ mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are water soluble. Suitable ethoxylated fatty alcohols include the C ₆-C ₁₈ ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50.

Suitable nonionic alkylpolysaccharide surfactants, particularly for use in the present compositions include those disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside. ) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.

Fatty acid amide surfactants suitable for use the present compositions include those having the formula: R ₆CON (R ₇) ₂ in which R ₆ is an alkyl group containing from 7 to 21 carbon atoms and each R ₇ is independently hydrogen, C ₁-C ₄ alkyl, C ₁-C ₄ hydroxyalkyl, or -- (C ₂H ₄O) _XH, where x is in the range of from 1 to 3.

A useful class of non-ionic surfactants includes the class defined as alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants. These non-ionic surfactants may be at least in part represented by the general formulae: R ²⁰-- (PO) _SN-- (EO) _tH, R ²⁰-- (PO) _SN-- (EO) _tH (EO) _tH, and R ²⁰--N (EO) _tH; in which R ²⁰ is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations on the scope of these compounds may be represented by the alternative formula: R ²⁰-- (PO) _V--N [ (EO) _wH] [ (EO) _zH] in which R ²⁰ is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2) ) , and w and z are independently 1-10, preferably 2-5.

The treatise Nonionic Surfactants, edited by Schick, M.J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds generally employed in the practice of the present invention. A typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents and detergents" (Vol. I and II by Schwartz, Perry and Berch) .

Additional Functional Ingredients

The components of the rinse aid compositions can further be combined with various functional components suitable for uses disclosed herein, including additional multipurpose applications. In some embodiments, the rinse aid compositions including the scale-inhibiting organic phosphonate, nonionic surfactants, hydrotropes, and water make up a large amount, or even substantially all of the total weight of the compositions. In other embodiments, the rinse aid compositions including the scale-inhibiting organic phosphonate, additional scale inhibitor (s) comprising a polycarboxylate, polycarboxylic acid or salt thereof and/or additional organic phosphonates, nonionic surfactants, hydrotropes, and water make up a large amount, or even substantially all of the total weight of the compositions. For example, in some embodiments few or no additional functional ingredients are disposed therein.

In other embodiments, additional functional ingredients may be included in the rinse aid compositions. The functional ingredients provide desired properties and functionalities to the compositions. For the purpose of this application, the term "functional ingredient" includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only, and that a broad variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning. However, other embodiments may include functional ingredients for use in other applications.

In some embodiments, the liquid rinse aid compositions may include optical brighteners, defoaming agents, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, metal protecting agents, stabilizing agents, preservatives, corrosion inhibitors, builders/sequestrants/chelating agents, enzymes, aesthetic enhancing agents including fragrances and/or dyes, additional rheology and/or solubility modifiers or thickeners, hydrotropes or couplers, buffers, solvents, additional cleaning agents, acidulants, isothiazolinones, glutaraldehydes, and the like.

According to embodiments of the disclosure, the various additional functional ingredients may be provided in a composition in the amount from about 0 wt-%and about 30 wt-%, from about 0 wt-%and about 25 wt-%, from about 0 wt-%and about 20 wt-%, from about 0.01 wt-%and about 30 wt-%, from about 0.1 wt-%and about 30 wt-%, from about 1 wt-%and about 30 wt-%, from about 1 wt-%and about 25 wt-%, from about 1 wt-%and about 20 wt-%, or from about 1 wt-%and about 15 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Chelants

The rinse aid compositions can further be combined with chelants, including for example an aminocarboxylic acid or an aminocarboxylate. Preferably, aminocarboxylic acid chelants include materials containing little or no NTA. Exemplary aminocarboxylates include, for example, N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) , methylglycinediacetic acid (MGDA) , hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic 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 other similar acids having an amino group with a carboxylic acid substituent. In an embodiment, the aminocarboxylate is ethylenediaminetetraacetic acid (EDTA) .

According to embodiments, the chelants may be provided in a composition in the amount from about 0 wt-%and about 30 wt-%, from about 0 wt-%and about 25 wt-%, from about 0 wt-%and about 20 wt-%, from about 0.01 wt-%and about 30 wt-%, from about 0.1 wt-%and about 30 wt-%, from about 1 wt-%and about 30 wt-%, from about 1 wt-%and about 25 wt-%, from about 1 wt-%and about 20 wt-%, or from about 1 wt-%and about 15 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

METHODS OF USE

Methods of use employing the multipurpose liquid rinse aid compositions are particularly suitable for consumer or institutional ware washing as a rinse aid. The methods can include first contacting the liquid rinse aid composition with water to form a use solution as the liquid composition is a concentrate composition. Beneficially the concentrate or a use solution of the composition provide antiscaling efficacy and drying and sheeting performance to various surfaces in need of rinsing and drying. These methods overcome limitations of rinse aids that do not protect against scaling that is common in various applications where hard water sources are used in the cleaning and/or rinsing process.

The multipurpose liquid rinse aid compositions are particularly suitable for treating ware surfaces, such as utensils, instruments, and the like, as well as various appliance surfaces such as kitchen or food processing surfaces. Each of these ware and appliance surfaces can be made of various materials. Beneficially the methods provide effective rinsing and fast drying without the need for supplemental descaling steps as the compositions provide effective antiscaling. As a result, the methods of use reduce the need for acid rinse steps and/or deliming steps (i.e. separate cleaning cycle using strong acids to clean a machine) to remove the films or residues on treated surfaces that accumulate over time. These benefits are achieved while providing at least substantially similar or improved rinsing and drying performance as conventional rinse aids without effective antiscaling.

In an embodiment, the methods of using the multipurpose liquid rinse aid compositions significantly reduce the need to use a descaling step in the dish machine. In embodiments, use of the multipurpose liquid rinse aid compositions provide rinsing efficacy that further prevents the need for machine descaling for at least about 1,000 hours of machine operation, at least about 1, 100 hours of machine operation, at least about 1, 200 hours of machine operation, at least about 1, 300 hours of machine operation, or at least about 1, 400 hours of machine operation.

In further embodiments, the methods of using the multipurpose liquid rinse aid compositions significantly reduce the need to use a descaling step in the rinsing cylcinder. In embodiments, use of the multipurpose liquid rinse aid compositions provide rinsing efficacy that further prevents the need for descaling the rinsing cylinder for at least about 4 months, at least about 5 months, or at least about 6 months.

Without being limited to a particular mechanism of action, the organic phosphonates that are alkylene oxide phosphonates add hydrophilicity with the ethylene oxide groups and have high solubility and calcium tolerance, providing benefits in hard water conditions where scaling is deleterious to various surfaces and appliances. Moreover, a synergistic combination of antiscaling is achieved by combining the organic phosphonate with the polycarboxylate polymers that provide further physical separation or dispersion effects.

Exemplary disclosure of warewashing applications is set forth in U.S. Patent Nos. 8,758,520, 9,139,800, and 10,905,305. The method may be carried out in any consumer or institutional dish machine, including for example those described in U.S. Patent No. 8,092,613, which is incorporated herein by reference in its entirety, including all figures and drawings. Some non-limiting examples of dish machines include door machines or hood machines, conveyor machines, undercounter machines, glasswashers, flight machines, pot and pan machines, utensil washers, and consumer dish machines. The dish machines may be either single tank or multi-tank machines.

A door dish machine, also called a hood dish machine, refers to a commercial dish machine wherein the soiled dishes are placed on a rack and the rack is then moved into the dish machine. Door dish machines clean one or two racks at a time. In such machines, the rack is stationary and the wash and rinse arms move. A door machine includes two sets arms, a set of wash arms and a rinse arm, or a set of rinse arms. Door machines may be a high temperature or low temperature machine. In a high temperature machine the dishes are sanitized by hot water. In a low temperature machine the dishes are sanitized by the chemical sanitizer. The door machine may either be a recirculation machine or a dump and fill machine. In a recirculation machine, the detergent solution is reused, or "recirculated" between wash cycles. The concentration of the detergent solution is adjusted between wash cycles so that an adequate concentration is maintained. In a dump and fill machine, the wash solution is not reused between wash cycles. New detergent solution is added before the next wash cycle.

In addition to the rinsing of ware the multipurpose liquid rinse aid compositions are suitable for rinsing various additional surfaces to provide descaling and efficient rinsing and drying. The ability to treat other surfaces, such as appliances and surfaces, that in contact with hard water and therefore prone to scaling provides a benefit to the multipurpose liquid rinse aid compositions.

In embodiments of using the rinse aid compositions, the composition is contacted with an aqueous source, preferably water, or may be mixed with an aqueous source, preferably water, prior to or at the point of use. This step provides a use solution from the liquid concentrate multipurpose liquid rinse aid compositions.

In some embodiments for use of the compositions in a ware washing process, the composition can be housed within a dispenser to provide the use dilution into a warewashing machine (or other point of use) . In an embodiment, a dispenser may be employed to spray water (e.g. in a spray pattern from a nozzle) to form a use solution. For example, water may be sprayed toward an apparatus or other holding reservoir with the liquid composition, wherein the water reacts to form the diluted use solution. In an aspect, the use solution may be dispensed into a wash solution of a ware wash machine.

The compositions or use solutions thereof can contact the surface or article by numerous methods for applying a composition, such as spraying the composition, immersing the object in the composition, or a combination thereof. A concentrate or use concentration of a composition can be applied to or brought into contact with an article by any conventional method or apparatus for applying a cleaning composition to an object. For example, the object can be wiped with, sprayed with, and/or immersed in the composition, or a use solution made from the composition. The composition can be sprayed, or wiped onto a surface; the composition can be caused to flow over the surface, or the surface can be dipped into the composition. Contacting can be manual or by machine. Preferred embodiments contact a use solution of the solid composition in a warewash machine.

In embodiments, a use solution of the liquid rinse aid compositions has a pH from about 1-9, from about 1-8, from about 1-7, from about 1-6, from about 1-5, from about 1-4, or from about 1-3.

In embodiments, a use solution of the liquid rinse aid compositions applied to surfaces in need of treatment can include at least about 10 ppm to about 200 ppm of total concentration, or at least about 20 ppm to about 200 ppm of total concentration, or at least about 30 ppm to about 200 ppm of total concentration, or at least about 40 ppm to about 200 ppm of total concentration, or preferably at least about 40 ppm to about 150 ppm of total concentration to provide antiscaling and drying.

In embodiments, the use solution of the liquid rinse aid compositions applied to surfaces in need of treatment can include at least about 1 ppm to about 100 ppm of antiscaling components, at least about 1 ppm to about 50 ppm of antiscaling components, or at least about 10 ppm to about 40 ppm of antiscaling components.

Exemplary articles for treatment with the compositions disclosed herein are in the warewashing industry, including ware, such as metal ware, plastics, dishware, cups, glasses, flatware, and cookware. For the purposes of this invention, the terms "dish" and "ware" are used in the broadest sense to refer to various types of articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room. In general, these types of articles can be referred to as food or beverage contacting articles because they have surfaces which are provided for contacting food and/or beverage. When used in these warewashing applications, the compositions provide effective sheeting action, low foaming properties and fast drying along with the antiscaling. In some aspects, the compositions aid in drying the article or surface (e.g. ware) within about 30 seconds to a few minutes, or within about 30 to about 90 seconds after the aqueous use solution is applied.

EXAMPLES

Embodiments of the present disclosure are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the disclosure, 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 disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the disclosure to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the disclosure, in addition to those shown 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 liquid rinse aid compositions shown in Table 3 were evaluated in the Examples:

EXAMPLE 1

Antiscaling efficacy of liquid rinse aid compositions were evaluated using glasses in a commercial dish machine. The efficiency of scale removal was evaluated according to %inhibition using a consistent surfactant package while comparing the scale inhibitor packages comparing a single scale inhibitor (phosphonate /chelant /polycarboxylate) compared to combinations thereof.

Before experimentation the dish machine was prepared as follows: Turn on the dish machine, fill water, after the water temperature as desired, add delimer (Strip Away or Lime A Way 0.5-1L, wash 3 cycles) . Then turn off the dish machine, drain all the water in the washing tank, and check whether the scale is completely removed. Rinse the dish machine with tap water (rinse out residual acid and foam) . Prepare compositions (detergent and rinse aid) to be used in experiment.

Turn on the dish machine, fill water, and keep the overflow pipe open for about 2 min (drain the water in the rinsing cylinder) . After 2 min, plug the overflow pipe tightly, adjust the chemical concentration, and start to fill water. After the dish machine is settled, wash 2-3 cycles, test water hardness, concentration and volume of chemicals.

For water hardness: take 5ml water from washing tank into 5ml tube, add moderate amounts of indicator (Eriochrome Black T) , the solution color changes to pink after the indicator dissolves completely, drop 0.02N EDTA until the solution color becomes blue, indicating that the titration end point is reached. The number of drops divided by 2 is the water hardness (gpg) . Check whether the water hardness is within the error range;

Detergent: take 5ml water from washing tank into 5ml tube, add 2D #014 (phenolphthalein) , and drop #002 (0.1N HCl) until the solution color becomes clear and colorless, indicating that the titration end point is reached. Check whether the number of drops is within the error range.

Rinse aid: use 5ml tube to receive the liquid at the outlet of disperser and read it.

Experiment Methodology: Ten iron sheets are weighted and tied around the rack. Seven glasses are placed in the rack, from corner to corner in the dish machine for 100 cycles. When 100 cycles are finish, remove the rack from dish machine, weight the iron sheets after they are completely dry and take pictures of glasses for evaluation.

Calculate added weight of iron sheet from the following equation:

Where: W _n = weight (g) of iron sheet after 100 cycles

W’ _n = weight (g) of iron sheet at beginning

S = area (m ²) of iron sheet

TABLE 4

The Formula tested is Formula 8 form Table 3. The results are shown in FIG. 1A-1C, where 1A is the baseline, 1B is control formulation (commercially-available competitive product with nonionic surfactant components) , and 1C is test Formula 8, where the pictures show a markedly improved performance in 1C as described according to the disclosure.

EXAMPLE 2

Calcium carbonate will precipitate from water containing calcium hardness and alkalinity when these ions exceed the normal solubility limit of the calcium carbonate. As the pH of the water increases, the driving force for calcium carbonate precipitation increases. A water that is stable at pH 8.0 can instantaneously precipitate calcium carbonate when the pH is increased to 9.0. Antiscaling efficacy of liquid rinse aid compositions shown in Table 3 were evaluated. The efficiency of scale removal was evaluated according to %inhibition using a consistent surfactant package while comparing the scale inhibitor packages comparing a single scale inhibitor (phosphonate /chelant /polycarboxylate) compared to combinations thereof.

After the equal volumes of the preheated (60℃) hardness and alkalinity solution are mixed, the test solution is stored for 48 hours at 60℃. At the end of the incubation time, soluble calcium is measured using the calcium titration and percent inhibition is calculated from the titration volumes as a measure of the effectiveness of an inhibitor.

Test Methodology:

All flasks were rinsed with dilute HCL (3: 1 distilled deionized water -concentrated HCl) and thoroughly rinsed with deionized water prior to use. Any flasks with remaining discoloration, excessive scratches or particle adherence not removed by the acid should be discarded.

Solutions to be Heated:

Alkalinity Solution: Add 96 grams, minus inhibitor volume, of distilled deionized water to a cleaned 250 mL Erlenmeyer flask. Add inhibitor volume (1 mL = 1 mg/L) , cap or stopper the flask and place in an oven or water bath controlled at 60℃.

Calcium Solution: Add 95 grams of distilled deionized water to a 250 mL Erlenmeyer flask followed by 5 mL of Calcium Stock solution. Cap or stopper the flask and place in an oven or water bath controlled at 60℃.

Allow all flasks to equilibrate to 60℃ (water bath -approximately 20 minutes; oven -approximately 1 hour, 15 minutes) .

Test Solution Preparation:

Alkalinity Addition: Add 4 mL of the Alkalinity Stock solution to the alkalinity flask after removing it from the constant temperature source.

Solution Mixing: Add the alkalinity and calcium solutions to a 500 mL Erlenmeyer flask by simultaneously pouring both solutions from a funnel. Record the pH and place the capped or stoppered flask back in the constant 60℃ temperature source for 5 hours.

After the 5 hour equilibration period, remove flasks from bath or oven. Immediately record final pH. Examine flask appearance and note what type of scale may have formed.

Typical observations would include:

-Adherent scale on sides of flasks.

-Scale particles settled to bottom of flask.

-Fluffy, non-adherent scale particles.

-Colloidal scale indicated by blue cast of solution.

Titration: Filter at least 10 g of the test solution through a 0.2 μm membrane filter. Dilute 10 g of the filtered sample to 50 mL total volume with distilled deionized water. Titrate the sample using Calgon Field Test No. 35-182-G for Determination of Calcium or Calgon Field Test No. 35-183-H for Total Hardness Determination. Prepare a calcium reference by diluting 10 mL of the Calcium Stock Solution to 500 mL with distilled deionized water. Analyze for calcium as described in prior steps.

Calculate %inhibition from the following equation:

Where: V _E = titrant volume (mL) required for treated test sample

V _o = titrant volume (mL) required for untreated (blank) test sample

V _T = titrant volume (mL) required for calcium reference sample

The results are shown in FIG. 1 and Table5.

TABLE 5

The results are shown in FIG. 2 and Table 5 show in FIG. 2 a %inhibition of scaling greater than 50%with the combination of chelant packages of Compositions 8-12. The combination of PAPEMP and PMA shows the best antiscaling performance.

EXAMPLE 3

Drying time of liquid rinse aid compositions were evaluated using ceramic and melamine plates in a commercial dish machine. The same preparation for the experimentation in Example 1 was utilized to prepare the dish machine.

Experiment Methodology: Five plates (numbered) were placed in the rack in a predetermined configuration from corner to corner in the dish machine. They are placed in the dish machine for a one cycle. When the one cycle is finish, wait for 3 seconds, then pull out the rack from dish machine and start recording time to assess drying time.

Pictures are taken immediately for each plate in sequence and the score recorded using the following grading: 1-Dewetting (spots) ; 2-Pinhole; 3 -partial sheeting (30%full sheeting) ; 4 -partial sheeting (50%full sheeting) ; and 5 -sheeting (80%full sheeting) .

The drying time is observed and recorded. To judge drying end point: when water drops on the plate are less than or equal to 3, or the drying time is longer than 90s, stop timekeeping as drying is complete.

The dishes are then washed with cold water to cool them down (to avoid influence of the residual temperature of the previous washing on the effect of drying) . For the same batch of plates, repeat prior steps 9 times (10 times in total, first 3 times are not included in the final results in order to ensure the stability of experimental conditions) under the same concentration and dosage of detergent and rinse aid, calculate the drying time and wetting score.

The surfactant package with hydrotrope was formulated (with remainder being water) alone and compared to the formulation of Composition 8 as shown in Table 3. The results are shown in FIG. 3. Drying performance was not negatively impacted by the scale-inhibitor package as shown in the interval plot that there is no statistically significant difference in the drying times. The results show that the scale inhibition packages as evaluated in Example 2 do not negatively impact the drying performance of the evaluated compositions.

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.

Any reference to accompanying drawings which form a part hereof, are shown, by way of illustration only. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure. All publications discussed and/or referenced herein are incorporated herein in their entirety.

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 utilized for realizing the invention in diverse forms thereof.

Claims

A multipurpose liquid rinse aid composition comprising:

a scale-inhibiting organic phosphonate having one of the following structures:

wherein:

Y is
or a salt thereof;

Y’ is absent,
or a salt thereof;

X is N, O, or OH;

R ₁ and R ₂ are independently a linear or branched C1-C10 alkyl group;

R ₃ is -N (Y) ₂; and

n is 1-20;

an optional additional scale inhibitor comprising a polycarboxylate, polycarboxylic acid or salt thereof;

a nonionic surfactant;

a hydrotrope; and

water.
The composition of claim 1, wherein the scale-inhibiting organic phosphonate and additional scale inhibitor comprising a polycarboxylate, polycarboxylic acid or salt thereof comprises from about 1 wt-%to about 20 wt-%of the composition, the nonionic surfactant comprises from about 5 wt-%to about 50 wt-%of the composition, and the hydrotrope comprises from about 5 wt-%to about 40 wt-%of the composition.
The composition of claim 1, wherein the scale-inhibiting organic phosphonate and additional scale inhibitor comprising a polycarboxylate, polycarboxylic acid or salt thereof comprises from about 5 wt-%to about 15 wt-%of the composition, the nonionic surfactant comprises from about 10 wt-%to about 25 wt-%of the composition, and the hydrotrope comprises from about 10 wt-%to about 20 wt-%of the composition.
The composition of any one of claims 1-3, wherein the salt of Y or Y’ is a cation, preferably sodium or potassium.
The composition of any one of claims 1-4, wherein the organic phosphonate has the structure:

wherein Z is independently H or CH _3, and wherein n is 2-12.
The composition of claim 5, wherein the organic phosphonate has the structure:
The composition of any one of claims 1-4, wherein the organic phosphonate has one of the following structures:
The composition of any one of claims 1-4, wherein the organic phosphonate has one of the following structures:
The composition of any one of claims 1-8, wherein the organic phosphonate comprises from about 1 wt-%to about 20 wt-%of the composition and wherein the additional scale inhibitor comprises from about 1 wt-%to about 10 wt-%of the composition.
The composition of any one of claims 1-9, wherein the polycarboxylate, polycarboxylic acid or salt thereof comprise a homopolymer, copolymer or terpolymer of a polyacrylate, polymethacrylate, and/or polymaleate.
The composition of claim 10, wherein the polycarboxylate, polycarboxylic acid or salt thereof is a polyacrylic acid polymer and/or a polyacrylic/polymaleic acid polymer.
The composition of any one of claims 1-11, comprising at least two nonionic surfactants.
The composition of any one of claims 1-12, wherein the nonionic surfactant (s) is an alcohol alkoxylate.
The composition of claim 13, wherein the alcohol alkoxylate has one of the following formulae:

R ¹-O- (EO) _x3 (PO) _y3-H  (A)

wherein R ¹ is a straight-chain C ₁₀-C ₁₆ alkyl, wherein x ₃ is from 5 to 8, and wherein y ₃ is from 2 to 5;

R ¹-O- (EO) _x4 (PO) _y4-H  (A2)

wherein R ¹ is a straight-chain C ₁₀-C ₁₆ alkyl, wherein x ₄ is from 4 to 6, and wherein y ₄ is from 3 to 5;

R ²-O- (EO) _x1-H  (B)

wherein R ² is C ₁₀-C ₁₄ alkyl with an average of at least 2 branches per residue, and

wherein x ₁ is from 5 to 10;

R ²-O- (EO) _x2-H  (C)

wherein R ² is C ₁₀-C ₁₄ alkyl with an average of at least 2 branches per residue, and wherein

x ₂ is from 2 to 4; and/or

a surfactant polymer according to the following formulae:

R ⁷-O- (PO) y ₅ (EO) x ₅ (PO) y ₆-H  (D)

wherein R ⁷ is a branched C ₈-C ₁₆ Guerbet alcohol, x ₅ is from 5 to 30, y ₅ is from 1 to 4,

and y ₆ is from 10 to 20;

R ⁶-O- (PO) y ₄ (EO) x ₄-H  (E)

wherein R ⁶ is a C ₈-C ₁₆ Guerbet alcohol, wherein x ₄ is from 2 to 10, and wherein y ₄ is from 1 to 2;

wherein x is from 120-220, y is from 12 to 20, and z is from 12 to 20;

wherein x is from 88 to 108, y is from 57 to 77, and z is from 88 to 108;

wherein x is from 15 to 25, y is from 10 to 25, and z is from 15 to 25;

R ⁴-O- (EO) _x (XO) _y-H  (I)

wherein R4 is C ₁₃-C ₁₅ alkyl, x is from 8 to 10, y is from 1 to 3, and XO is butylene oxide;

and/or

R ⁵-O- (EO) _x (PO) _y-H  (J)

wherein R5 is C ₁₂-C ₁₅ alkyl, x is from 3 to 5, and y is from 5 to 7.
The composition of any one of claims 1-14, wherein the hydrotrope is a short chain alkyl benzene and/or alkyl naphthalene sulfonate.
The composition of claim 15, wherein the short chain alkyl benzene and/or alkyl naphthalene sulfonate is selected from the group consisting of sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and sodium butylnaphthalene sulfonate.
The composition of any one of claims 1-16, further comprises at least one additional functional ingredient.
A method of using a rinse aid composition comprising:

providing a liquid rinse aid composition according to any of claims 1-17;

contacting the rinse aid composition with water to form a use solution;

contacting the use solution to a surface in need of rinsing and drying,

wherein the composition provides antiscaling efficacy and drying and sheeting performance.
The method of claim 18, wherein the surface is a hard surface comprising metal, glass, plastic, ceramic or tile.
The method of any one of claims 18-19, wherein the use solution is dispensed into a wash solution of a ware wash machine.
The method of claim 20, wherein the ware wash machine is an institutional dish machine, a clean in place dish machine, or a consumer dish machine.
The method of any one of claims 18-21, wherein the surface is a ware.
The method of any one of claims 18-22, wherein the use solution has a pH from about 1-9, from about 1-8, or from about 1-7.
The method of any one of claims 18-23, wherein the use solution has a concentration from about 100 ppm to about 3000 ppm.