NZ756199B2 - Alkaline cleaning compositions comprising a hydroxyphosphono carboxylic acid and methods of reducing metal corrosion - Google Patents

Abstract

The invention relates to compositions, methods of manufacture, and methods for reducing metal corrosion during alkaline cleaning. In particular, the method employs a hydroxyphosphono carboxylic acid in alkaline cleaning of hard surfaces.

Description

TITLE: ALKALINE CLEANING COMPOSITIONS COMPRISING A HYDROXYPHOSPHONO CARBOXYLIC ACID AND METHODS OF REDUCING METAL CORROSION CROSS-REFERENCE TO RELATED APPLICA TIONS This application is related to and claims priorit under 35 U.S.C. § 119 to U.S.

Provisional Application Ser. No. 62/464,938 fled on February 28, 2017 and entitled 1 O "ALKALINE CLEANING COMPOSITIONS COMPRISING A HYDROXYPHOSPHONO CARBOXYLIC ACID AND METHODS OF REDUCING METAL CORROSION." The entire contents of this patent application are hereby expressly incorporated herein by refrence including, without limitation, te specifcation, claims, and abstract, as well as any fgures, tables, or drawings thereof This application is related to U.S. patent application Ser. No. 62/464,864 and U.S.

Patent Application Ser. No. 15/904,880 (Attomey Docket Number Pl 1937US01) each entitled "ALKALINE CLEANING COMPOSITIONS COMPRISING AN ALKYLAMINO HYDROXY ACID AND/OR SECONDARY AMINE AND METHODS OF REDUCING METAL CORROSION." The entire contents ofthese patent applications are hereby expressly incorporated herein by refrence including, without limitation, the specifcation, claims, and abstract, as well as any fgures, tables, or drawings thereof FIELD OF THE INVENTION The invention relates to compositions and methods fr reducing metal corrosion during alkaine cleaning. In particular, the method employs a hydroxyphosphono carboxylic acid in alkaline cleaning of hard surfaces.

BACKGROUND OF THE INVENTION Many tpes of metals (e.g., aluminum and its alloys, nickel and its alloys, tin and its alloys, and some grades of stainless steel, e.g., 300 and 400 series and their alloys) corrode, discolor, and/or stain when subjected to high alkainity. Corrosion refers to destruction, degradation or deterioration ofthe metal due to reactions ofthe material and its environment. The rate of corrosion may vary, depending on the surrounding conditions and also the composition ofthe steel. Stainless steel, fr example, is more resistant to corrosion than plain carbon and other steels. This resistace is due to the addition of chromium to alloys of iron and carbon. Although stainless steel has appreciable resistance to corrosion, it will still corrode in certain circumstances and attempts have been made to prevent or reduce tis corrosion.

Corrosion, including, discoloration, staining, and pitting can be worsened when the high alkalinit is coupled with high temperatures. This ca be particularly problematic in contexts where a metal is subjected to an alkaline environment, particularly, when it is coupled with high temperatures. Thus, clean-in-place technologies, clean-out-of -place 1 O technologies, warewash, fod ad beverages surfces, and boilers can suffr fom this problem.

Some attempts to remedy this problem have been provided and exist. Examples include the use of corrosion inhibitors. Many metalic ion corrosion inhibitors have been used alone or in combination in various chemical treatment frmulations. Some inhibitors, however, have been fund to be toxic and/or detrimental to the environment. Inorganic phosphates such as orthophosphate and pyrophosphate have been widely used corrosion inhibitors. However, te inorganic phosphates have been fund to contribute to scale frmation ( e.g., calcium phosphate, iron phosphate and zinc phosphate salts ). Some organic phosphonates (e.g. 2-phosphono-butane-1,2,4-tricarboxylic acid (PBTC), 1- hydroxyethylidene-1,1-diphosphonic acid (HEDP), and aminotrimethylene-phosphonic acid (AMP)) have been used as corrosion inhibitors; however, the efectiveness has not been optimized. Some hydroxycarboxylic acids (e.g. gluconic acid) have also been used as corrosion inhibitors in aqueous applications such as cleaning cooling towers; however, there are microbiological growth control concems and perfrmance concems when used in certain conditions, such as high alkalinit, temperature andor oxidizing environments.

This is particularly problematic in the area of fod processing surfces, such as CIP and COP technologies or other fod processing surfces comprised offod grade stainless steel. For example, such surfaces are used in the manufcture of fods and beverages, where hard surfces commonly become contaminated with soils such as carbohydrate, proteinaceous, and hardness soils, fod oil soils and other soils. Food and beverage soils are particularly tenacious when they are heated during processing (e.g. in dairy plants, dairy products are heated on a pasteurizer such as a high temperature short time pasteurizer or ultra-high temperature pasteurizer). Also, many food and beverage products are concentrated or created as a result of evaporation. When that surface is a heat exchange surface, the soil becomes thermally degraded rendering it even more difficult to remove.

Surfaces cleaned in a CIP process are most often stainless steel surfaces. The cleaning requires a complete or partial shutdown of the equipment being cleaned, which results in lost production time. Many times, the equipment is not thoroughly cleaned, due to the large downtime needed. Therefore, what is needed is an improved method for cleaning this equipment, using the CIP process, which uses an alkaline cleaning composition that will prevent corrosion and damage to the stainless steel surfaces treated in order to thoroughly remove the soils. It is against this background that the present invention has been made.

Accordingly, it is an objective of the invention to develop compositions and methods for reducing metal corrosion, discoloration, and/or staining in an alkaline environment.

Another object of the invention is to develop compositions and methods for preventing metal corrosion, discoloration, and/or staining in an alkaline environment.

A further object of the invention is to reduce the metal corrosion, discoloration, and/or staining in alkaline and high temperature environments.

Still another object of the invention is to prevent the metal corrosion, discoloration, and/or staining in alkaline and high temperature environments.

Other objects, advantages and features of the present invention will become apparent from the following specification taken in conjunction with the accompanying drawings.

BRIEF SUMMARY OF THE INVENTION An advantage of the invention is that it can reduce corrosion, staining, and/or In a first aspect there is provided a method for cleaning a hard surface comprising: contacting a hard surface with a cleaning composition comprising an alkalinity source and a hydroxyphosphono carboxylic acid; wherein the alkalinity source comprises an alkali metal hydroxide; diluting the cleaning composition to form an aqueous cleaning solution; adding an oxidizer to the aqueous cleaning solution, wherein the aqueous cleaning solution has a pH of at least about 9; and rinsing the hard surface.

In a second aspect there is provided a hard surface cleaning composition comprising: between about 5 wt.% and about 99 wt.% (active) of an alkalinity source, wherein the alkalinity source comprises an alkali metal hydroxide; between about 0.01 wt.% to about 40 wt.% of a hydroxyphosphono carboxylic acid; and an oxidizer, wherein the oxidizer is in a separate part from the alkalinity source.

In a third aspect there is provided a method of making a hard surface cleaning composition comprising: combining a hydroxyphosphono carboxylic acid, an oxidizer, and an alkalinity source to form a cleaning composition; wherein the alkalinity source is between about 5 wt.% and about 99 wt.% (active) of the composition and comprises an alkali metal hydroxide; and wherein the hydroxyphosphono carboxylic acid is between about 0.01 wt.% to about 40 wt.% of the composition, and wherein the composition is prepared from a multi-part system and the oxidizer is in a separate part from the alkalinity source.

In an embodiment, the present invention comprises a method for cleaning a hard surface comprising contacting a hard surface with a cleaning composition comprising an alkalinity source and a hydroxyphosphono carboxylic acid; diluting the cleaning composition to frm an aqueous cleaning solution; and rinsing the hard surfce. The alkalinit source can comprise an alkali metal hydroxide ad the pH ofthe aqueous cleaning solution ca be at least about 9.

A further embodiment of the invention can be fund in a method fr cleaning a hard surface comprising contacting a hard surface with an aqueous cleaning solution comprising an alkalinit source and a hydroxyphosphono carboxylic acid, and rinsing the hard surface. The alkalinit source can be in an amount between about 0.001 % (active) and about 12% (active) and comprise an alkali metal hydroxide. The hydroxyphosphono carboxylic acid can be in an amount between about 0.001 % (active) and about 4% (active). 1 O The aqueous cleaning solution can have a pH of at least about 1 O.

Another embodiment of the invention can be found in a method fr cleaning a hard surface comprising contacting a hard surfce with a cleaning composition comprising an alkalinit source and a hydroxyphosphono carboxylic acid; diluting the cleaing composition to frm an aqueous cleaning solution; adding an oxidizer to the aqueous cleaning solution to the aqueous cleaning solution to achieve a concentration between about O ppm and about 5000 ppm; and rinsing the hard surfce. The alkalinity source can comprise an alkali metal hydroxide ad the pH ofthe aqueous cleaning solution can be at least about 9. The concentration ofthe alkalinit source in the aqueous cleaing solution can be between about 0.001 % (active) and about 12% (active). The concentration ofthe hydroxyphosphono carboxylic acid in the aqueous cleaing solution can be between about 0.001 % (active) ad about 4% (active).

While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art fom the fllowing detailed description, which shows and describes illustrative embodiments ofthe invention.

Accordingly, the fgures, detailed description, and examples are to be regarded as illustrative in nature and not restrictive.

BRIEF DESCRIPTION OF THE FIGURES shows the percent area of discoloration on stainless steel series 304 coupons afer being subjected to 4% (active) NaOH fr eight weeks and the efect of a hydroxyphosphono carboxylic acid in reducing the discoloration. Data series A is the 4% (active) NaOH and data series B is the 4% (active) NaOH with 1 % (active) Belcor 575. shows the percent area of discoloration on stainless steel series 316 coupons afer being subjected to 4% (active) NaOH fr eight weeks and the efect of a hydroxyphosphono carboxylic acid in reducing the discoloration. Data series A is the 4% (active) NaOH and data series B is the 4% (active) NaOH with 1 % (active) Belcor 575. shows the percent area of discoloration on stainless steel series 304 and 316 coupons ater being subjected to 4% (active) NaOH fr two weeks and the efect ofthe concentration of a hydroxyphosphono carboxylic acid in reducing the discoloration.

Belcor 575 was tested in active concentrations of 0.01 %, 0.1 %, 0.25%, 0.5%, and 1 %.

Data series A represents stainless steel series 304 ad data series B represents stainless steel series 316. shows the percent area of discoloration fr stainless steel series 304 and 316 coupons ater being subjected to 4% (active) NaOH along with 1000 ppm of an oxidizer composition fr twelve cycles and the efect ofthe concentration of a hydroxyphosphono carboxylic acid in reducing the discoloration. Belcor 575 was tested in active concentrations of 0.5% and 1 %. Data series A represents stainless steel series 304 and data series B represents stanless steel series 316. shows the percent area of discoloration on stainless steel series 304 and 316 coupons after being subjected to 4% (active) NaOH fr six weeks and comparing the efect of an exemplary hydroxyphosphono carboxylic acid (Belcor 575 at 1 % active) versus etylenediaminetetraacetic acid (at 1 % active) in reducing the discoloration. Data series A is represents stainless steel series 304 and data series B represents stainless steel series 316.

Various embodiments of the present invention will be described in detail with refrence to the drawings, wherein like refrence numerals represent like parts throughout the several views. Refrence to various embodiments does not limit the scope of the invention. Figures represented herein are not limitations to the various embodiments according to the invention and are presented fr exemplary illustration ofthe invention.

DETAILED DESCRIPTION The present invention relates to compositions and methods fr reducing and/or preventing the corrosion of metals in an alkaline environment. The compositions and methods of the invention have many advantages over existing compositions and methods of reducing and/or preventing corrosion of metals in an akaline environment. For example, the present invention provid es methods fr using high akalinit on stainless steel surfaces without discoloring, staining, and corroding the stainless steel to the extent that other methods do. This provides fr cleaner surfaces, the abilit to clean with high 1 O alkalinit, and generally more sanitary surfces.

All publications and patent applications in this specifcation are indicative ofthe level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by refrence to the same extent as if each individual publication or patent application was specifcally and individually indicated as incorporated by refrence.

Definitions The embodiments of this invention are not limited to use alongside particular detergents, cleaing agents, or end-use ofthe meta surface, which ca n vary and are understood by skilled artisans. It is further to be understood that all terminology used herein is fr the purpose of describing paicula embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specifcation and the appended claims, the singular frms "a," "an" and "the" can include plural refrents unless the content clearly indicates oterwise. Further, all units, prefxes, and symbols may be denoted in its SI accepted form.

Numeric ranges recited within the specifcation are inclusive ofthe numbers within the defned range. Throughout this disclosure, various aspects of this invention are presented in a range frmat. It should be understood that the description in range frmat is merely fr convenience and brevit and should not be constmed as an infexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifcaly disclosed all the possible sub-ranges as well as individual numerical values within that range, including, but not limited to subsumed integers, decimals, and factions (e.g. 1 to 5 includes 1, 1.5, 2, 2¾, 3, 3.80, 4, and 5).

So that the present invention may be more readily understood, certain terms are frst defned. Unless defned otherwise, ai technical and scientifc terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments ofthe invention pertain. Many methods and materiais similar, modified, or equivalent to those described herein can be used in the practice of the embodiments ofthe present invention without undue experimentation, the prefrred materiais and methods are described herein. In describing and claiming te embodiments of the present invention, the fllowing terminology will be used in accordance with the definitions set out below.

The term "about," as used herein, refrs to vaiation in the numerical quantit that 1 O can occur, fr example, through tpical measuring and liquid handling procedures used fr making concentrates or use solutions in the real world; through inadvertent error in these procedures; through diferences in the manufacture, source, or purit ofte ingredients used to make the compositions or carry out the methods; and the like. The term "about" also encompasses amounts that difer due to different equilibrium conditions fr a composition resulting fom a particular initial mixture. Whether or not modifed 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 ofthose ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts.

As used herein, the term "alkyl" or "alkyl groups" refrs to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butl, pentl, hexyl, heptl, octl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentl, cyclohexyl, cycloheptl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butl, sec-butl, isobutl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl­ substituted cycloalkyl groups and cycloalkyl-substituted akyl groups).

Unless otherwise specifed, the term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls." As used herein, the term "substituted alkyls" refrs to alkyl groups having substituents replacing one or more hydrogens on one or more carbons ofthe hydrocarbon backbone. Such substituents may include, fr example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, ary loxy carb ony loxy, carb oxy late, alky lcarbony 1, aryl carbony 1, alkoxy carbony 1, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkyltiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and akylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfydryl, alkylthio, arylthio, thiocarboxylate, sulftes, alkylsulfnyl, sulfnates, sulfaoyl, sulfnaido, nitro, trifuoromethyl, cyao, azido, heterocyclic, alkylaryl, or aomatic (including heteroaromatic) groups.

In some embodiments, substituted alkyls can include a heterocyclic group. As used 1 O herein, te term "heterocyclic group" includes closed ring structures aalogous to carbocyclic groups in which one or more ofthe carbon atoms in the ring is an element other than carbon, fr example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated. Exempla heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes), thiirane (episulfdes), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

An "antiredeposition agent" refrs to a compound that helps keep suspended in water instead ofredepositing onto the object being cleaned. Antiredeposition agents are usefl in the present invention to assist in reducing redepositing of the removed soil onto the surfce being cleaned.

As used herein, the term "cleaning" refrs to a method used to fcilitate or aid in soil removal, bleaching, microbial population reduction, ad ay combination thereof As used herein, the term "microorganism" refrs to any noncellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae. As used herein, the term "microbe" is synonymous with rmcroorga1sm.

As used herein, the phrase "fod processing surfce" refrs to a surfce of a tool, a machine, equipment, a structure, a building, or the like that is employed as part of a fod processing, preparation, or storage activit. Exaples of fod processing surfces include surfaces offod processing or preparation equipment (e.g., slicing, canning, or transport equipment, including fumes), offod processing wares (e.g., utensils, dishware, wash ware, and bar glasses ), and of foors, walls, or :xtures of structures in which food processing occurs. Food processing surfces are fund and employed in fod anti-spoilage air circulation systems, aseptic packaging sanitizing, fod refigeration and cooler cleaners and sanitizers, ware washing sanitizing, blancher cleaning and sanitizing, fod packaging materiais, cutting board additives, third-sink sanitizing, beverage chillers and warmers, meat chilling or scalding waters, autodish sanitizers, sanitizing gels, cooling towers, fod processing antimicrobial garment sprays, and non-to-low-aqueous fod preparation lubricants, oils, and rinse additives.

As used herein, the term "hard surface" can include, but is not limited to, a fod 1 O processing surfce, warewashing surfce, foor, shower, sink, and toilet.

As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as fr example, block, graf, random and altemating copolymers, terpolymers, ad higher "x"mers, further including their derivatives, combinations, and blends thereof Furthermore, unless oterwise specifcally limited, the term "polymer" shall include all possible isomeric con:gurations of the molecule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof Furthermore, unless otherwise speci:cally limited, the term "polymer" shall include all possible geometrica con:gurations ofthe molecule.

As used herein, the term "solid", refrs to a hardened composition that will not fow and will substantialy retain its shape under moderate stress or pressure or mere gravit. A solid may be in various frms such as a powder, a fake, a granule, a pellet, a tablet, a lozenge, a puck, a briquette, a brick, a solid block, a unit dose, or another solid frm known to those of skill in the art. The degree of hardness of the solid cast composition and/or a pressed solid composition may range fom that of a fsed solid product which is relatively dense and had, fr example, like concrete, to a consistency characterized as being a hadened paste. In addition, the term "solid" refrs to te state ofthe detergent composition under the expected conditions of storage and use of the solid detergent composition. In genera, it is expected that the detergent composition will reman in solid frm when exposed to temperatures of up to approximately 100 ºF and paticula ly up to approximately 120 ºF.

As used herein, the term "stainless steel," refrs to te classification of carbon steels containing at least about 5 weight percent, usually about 5 to about 40 weight percent, and normally about 1 O to about 25 weight percent chromium. They may also contain other alloying elements such as nickel, cerium, aluminum, titanium, copper, or other elements. Stainless steels are usually classifed in three diferent categories -­ austenitic, frritic, and matensitic steels -- which have in common the fct that they contain signifcant amounts of chromium and resist corrosion and oxidation to a greater extent than do ordinary carbon steels and most alloy steels. Additional description of the classifcations (including SAE steel grades used fr grading in the U.S. fr stainless steel) and compositions of stainless steel, including those stainless steel having higher corrosion­ resistant properties which are also suitable fr use with the present application, is disclosed fr example in U.S. Patent Publication No. 2013/0062568, the entire disclosure ofwhich is herein incorporated by reference.

As used herein, the term "substantially fee" refrs to compositions completely lacking the component or having such a small amount ofthe component that the component does not afect the perfrmance ofthe composition. The component may be present as an impurit or as a contaminant and shall be less than 0.5 wt-%. In another embodiment, the amount ofthe component is less than 0.1 wt-% and in yet another embodiment, the amount of component is less than O. 01 wt-%.

The term "substantially similar cleaning perfrmance" refers generally to achievement by a substitute cleaing product or substitute cleaning system of generally the same degree (or at least not a signifcantly lesser degree) of cleanliness or with generally the same expenditure (or at least not a significantly lesser expenditure) of efort, or both.

As used herein, the term "sulfperoxycarboxylic acid," "sulfnated peracid," or "sulfnated peroxycarboxylic acid" refrs to the peroxycarboxylic acid frm of a sulfnated carboxylic acid. In some embodiments, the sulfnated peracids ofthe present invention are mid-chan sulfnated peracids. As used herein, the term "mid-chain sulfnated peracid" refers to a peracid compound that includes a sulfnate group attached to a carbon tat is at least one carbon (e.g., the three position or frther) fom the carbon of the percarboxylic acid group in te carbon backbone of the percarboxylic acid chain, wherein the at least one carbon is not in the terminal position. As used herein, the term "terminal position," refrs to the carbon on the carbon backbone chain of a percarboxylic acid that is frthest fom the percarboxyl group.

The term "threshold agent" refrs to a compound that inhibits crystallization of water hardness ions fom solution, but that need not frm a specifc complex with the water hardness ion. Threshold agents include but are not limited to a polyacrylate, a polymetacrylate, an olefin/maleic copolymer, ad the like.

As used herein, the term "warewashing surfce" refrs to items such as eating and cooking utensils, dishes, warewash machines, tubs, sinks, and countertops. As used herein, the term "warewashing" refrs to washing, cleaning, or rinsing ware.

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

The methods, systems, apparatuses, and compositions of the present invention may comprise, consist essentially of, or consist ofthe components and ingredients of the present invention 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 ifte additional steps, components or ingredients do not materially alter te basic and novel characteristics ofthe claimed methods, systems, apparatuses, and compositions.

It should also be noted that, as used in this specifcation and the appended claims, the term "confgured" describes a system, apparatus, or other structure that is constructed or confgured to perform a particular task or adopt a particular confguration. The term "confgured" can be used interchangeably with other similar phrases such as arranged and confgured, constructed and arranged, adapted and confgured, adapted, constructed, manufactured and arranged, and the like.

Compositions The compositions ofthe invention can be concentrated or diluted use solution. The concentrated compositions can be in solid or liquid frm. The compositions of the invention generally include an alkalinit source, a hydroxyphosphono caboxylic acid, a surfactant, water, and optional functional ingredients. The hydroxyphosphono carboxylic acid can be included in a composition with the other ingredients fr an alkaline detergent composition or the hydroxyphosphono carboxylic acid ca be added separately to a use solution. Similarly, the additional functional ingredients can be included in the composition with the alkalinit source, hydroxyphosphono carboxylic acid, surfactant, and water, or the additional functional ingredients can be added separately to a use solution.

Prefrably, the compositions provide a pH ofbetween about 9.5 and about 14; more prefrably between about 11 and about 13.5; and most prefrably between about 12 and 13.5.

Alkalinit Source The compositions ofthe invention include an alkalinit source. The alkalinit source is an alkali metal hydroxide. Exemplary alkali metal hydroxides that can be used 1 O include, but are not limited to sodium, lithium, and potassium hydroxide.

In general, alkainit sources are commonly available in either aqueous, powdered, flake, or bead frm, either of which is useful in frmulating the present detergent compositions. The alkalinity may be added to the composition in any frm known in the art, including as solid beads, fakes, granulated or particulate frm, dissolved in an aqueous solution, or a combination thereof The concentrations of alkalinit sources here are described as active amounts of alkalinity as diferent types of alkalinity sources and diferent frms of alkalinit sources ofen have varying active amounts.

In general, it is expected that the compositions can contain the alkalinit source in an amount between about 5% and about 99% active alkalinit by weight, between about 10% and about 50% active alkalinit by weight, and between about 35% and about 50% active alkalinit by weight of the total weight ofte detergent composition. When diluted to a use solution, the compositions of the present invention can include between about 0.001 % to about 12% of active alkainit source, prefrably between about 0.01 % and about 10% active alkalinity, most prefrably between about 0.1 % and about 6% active alkalinit.

Hydroxyphosphono Carboxylic Acid The compositions of the invention include a hydroxyphosphono carboxylic acid.

Prefrably, hydroxyphosphono carboxylic acid has a carbon chain length between 1 and 8 carbons in the carboxylic acid group. More prefrably, the carbon chain length of the carboxylic acid group is between 1 and 6 carbons. Most prefrably, the carbon chain length ofthe carboxylic acid group is between 1 and 4 carbons. Ifthe carbon chain length is too long, the chain length can interfre with the water solubility and ofthe hydroxyphosphono carboxylic acid and reduce its dispersabilit.

The compositions of the invention can be difcult to frmulate in concentrated form due to instabilit ofthe hydroxyphosphono carboxylic acid in the highly alkaline composition. While not wishing to be bound by te theory, it is believed that the hydroxyphosphono carboyxylic acid may not be stable in a highly alkaline frmulation.

Thus, fr applications where the alkalinit desired is particularly high, i.e., greater than pH it may be prefrable to keep the hydroxyphosphono carboxylic acid in a separate composition fom the alkalinit source until preparation of a use solution. Such a 1 O composition is a multi-part system. In embodiments of the invention containing an oxidizer, the oxidizer is also kept in a separate part fom the alkalinit source. Thus, in some embodiments the composition can be a two-part system or a three-part system.

In concentrated compositions where the aqueous use solution is not greater than 10, the composition can be kept in a pre-mix composition, where all the components, except the water of dilution and optional oxidizer, are kept in a single composition. In such a composition, the oxidizer can be added immediately befre use or simultaneously to a hard surface at the time of use.

In general, it is expected that the concentrated compositions can contain the hydroxyphosphono carboxylic acid in an between about 0.01 wt.% and about 40 wt.%, prefrably between about 0.25 wt. % and about 20 wt. %, and more prefrably between about 0.5 wt.% and about 10 wt.% ofthe concentrated composition.

In use solution, the compositions of the present invention can include te hydroxyphosphono carboxylic acid in an between about 0.001 wt.% and about 4 wt.%, prefrably between about O.Olwt.% and about 2 wt.%, more prefrably between about 0.01 wt. % and about 1 wt. %.

Surfactants The compositions ofthe invention can include a surfactant. Surfactants suitable fr use with the compositions of the present invention include, but are not limited to, nonionic surfactants, cationic surfctants, anionics, and zwitterionic surfactants. In embodiments of the invention the compositions and methods can be substantially fee of anionic and other high foaming surfctants In other embodiments ofthe invention, anionic surfactants and other high faming surfctants can be included with a defamer.

The concentrated compositions of the present invention can contain between about O wt. % and about 50 wt. % of a surfactant, prefrably between about O wt. % and about 25 wt.%, and more prefrably between about O wt.% and about 10 wt.%. The use solution compositions, can contan between about O ppm to about 1000 ppm of a surfactat, prefrably between about O ppm and about 500 ppm of a surfctant, more prefrably between about O ppm of a surfctant and about 100 ppm of a surfctant.

Nonionic Surfactants Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by 1 O the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiet 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 a propylene oxide to frm a nonionic surface-acive agent. The length ofthe 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 surfctants include: 1. Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Examples of polymeric compounds made fom a sequential propoxylation and ethoxylation ofinitiator are commercialy available fom BASF Corp. One class of compounds are difunctional (two reactive hydrogens) compounds frmed by condensing ethylene oxide with a hydrophobic base frmed by the addition ofpropylene oxide to the two hydroxyl groups ofpropylene glycol. This hydrophobic portion ofthe 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 fom about 10% by weight to about 80% by weight of the fnal molecule. Another class of compounds are tetra-finctional block copolymers derived fom the sequential addition ofpropyl ene oxide and ethylene oxide to ethylenediamine. The molecular weight ofthe propylene oxide hydrotpe ranges fom about 500 to about 7,000; and, the hydrophile, ethylene oxide, is added to constitute fom about 10% by weight to about 80% by weight of the molecule. 2. 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 fom about 8 to about 18 carbon atoms with fom about 3 to about 50 moles of et ylene oxide. The alkyl group can, fr exaple, be represented by diisobutlene, di­ amyl, polymerized propylene, iso-octl, nonyl, and di-nonyl. These surfctants can be polyethylene, polypropylene, and polybutlene oxide condensates of alkyl phenols.

Exaples of commercial compounds oftis chemistry are available on the market under 1 O the trade names IGEPAL manufactured by Rhone-Poulenc and TRITON manufactured by Union Carbide. 3. Condensation products of one mole of a saturated or unsaturated, straight or branched chan alcohol having fom about 6 to about 24 carbon atoms with fom about 3 to about 50 moles of ethylene oxide. The alcohol moiet can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specifc number of carbon atoms wthin this range. Examples of like commercial surfactant are available under te trade names LUTENSOL , DEHYDOL manufctured by BASF, NEODOL manufctured by Shell Chemical Co. and ALFONIC manufactured by Vista Chemical Co. 4. Condensation products of one mole of saturated or unsaturated, straight or branched chain carboxylic acid having fom about 8 to about 18 carbon atoms with fom about 6 to about 50 moles of ethylene oxide. The acid moiet can consist of mixtures of acids in the above defned carbon atoms range or it can consist of an acid having a specifc number of carbon atoms within the range. Exaples of commercial compounds oftis chemistry are available on the market under the trade names DISPONIL or AGNIQUE manufactured by BASF and LIPOPEG manufctured by Lipo Chemicals, Inc.

In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters frmed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitasorbitol) alcohols have application in this invention fr specialized embodiments, particularly indirect fod additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo frther acylation or ethylene oxide (alkoxide) addition to control the hydrophilicit of these substances. Care must be exercised when adding these ftty ester or acylated carbohydrates to compositions ofthe present invention containing amylase and/or lipase enzymes because of potential incompatibilit.

Examples ofnonionic low foaming surfctants include: 5. Compounds fom (1) which are modifed, essentially reversed, by adding etylene 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 ofthe molecule weighs fom about 1,000 to about 3,100 with the central hydrophile including 10% by weight to about 80% by weight ofthe fna molecule. These reverse PLURONICS are manufactured by BASF Corporation under the trade name PLURONIC R surfctats. Likewise, the TETRONIC R surfactants are produced by BASF Corporation by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion ofthe molecule weighs fom about 2,100 to about 6,700 with the central hydrophile including 10% by weight to 80% by weight of the fnal molecule. 6. Compounds fom groups (1), (2), (3) and (4) which are modifed by "capping" or "end blocking" the terminal hydroxy group or groups (ofmulti-functional moieties) to reduce faing by reaction with a small hydrophobic molecule such as propylene oxide, butlene oxide, benzyl chloride; and, short chain ftt acids, alcohols or alkyl halides containing fom 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 modifcations to the terminal hydroxy group may lead to all-block, block-heteric, heteric-block or all-heteric nonionics.

Additional examples of efective low faming nonionics include: 7. The alkylphenoxypolyethoxyalkanols ofU.S. Pat. No. 2,903,486 issued Sep. 8, 1959 to Brown et al. and represented by the frmula in which Ris an alky 1 group of 8 to 9 carbon atoms, A is a alky len e chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 1 O The polyalkylene glycol condensates ofU.S. Pat. No. 3,048,548 issued Aug. 7, 1962 to Martin et al. having altemating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains where the weight ofthe terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight ofthe linking hydrophilic units each represent about one-third of the condensate.

The defaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. having the general frmula Z[(OR)nOH]z wherein Z is alkoxylatable material, Ris a radical derived fom an alkylene oxide which can be ethylene and propylene and n is an integer fom, fr example, 1 O to 2,000 or more and z is an integer determined by the number ofreactive 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 frmula Y(C3H60)n (C2H40)mH wherein Y is the residue of organic compound having fom 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 partian constitutes about % to about 90% by weight ofthe molecule.

The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the frmula Y[(C3H60n (Ci40)mH]x wherein Y is the residue of an organic compound having fom 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 ofthe molecule is fom about % to about 90% by weight. Compounds flling within the scope ofthe defnition fr Y include, fr example, propylene glycol, glycerine, pentaerythritol, trimethylolpropae, etylenediamine and the like. Te oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chans also optionally, but advantageously, contain small amounts of propylene oxide.

Additiona conjugated polyoxyalkylene surfce-active agents which are advantageously used in the compositions ofthis invention correspond to the frmula: P[(C3H6O)n (C2H4O)mH]x wherein P is the residue of an organic compound having fom 1 O 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 ofthe polyoxyethylene portion is at leat about 44 and m has a value such that the oxypropylene content of the molecule is fom about 10% to about 90% by weight. 1n either case the oxypropylene chains may contain optionally, but advantageously, small amounts of ethy Iene oxide and the oxyetylene chains may contain also optionally, but advatageously, small amounts of propylene oxide. 8. Polyhydroxy ftt acid amide surfactants suitable fr use in the present compositions include those having the structural frmula R2CONR1Z in which: Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R2 is a Cs-C31 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 (prefrably ethoxylated or propoxylated) thereof. Z can be derived fom a reducing sugar in a reductive anation reaction; such as a glycitl moiet. 9. The alkyl ethoxylate condensation products of aliphatic alcohols with fom about O to about 25 moles of ethylene oxide are suitable fr use in the present compositions. The alkyl chain ofthe aliphatic alcohol can either be straight or branched, primary or secondary, and generaly contains fom 6 to 22 carbon atoms.

. The ethoxylated C6-Cl8 ftt alcohols and C6-C1s mixed ethoxylated and propoxylated ftty alcohols are suitable surfactants fr use in the present compositions, particularly those that are water soluble. Suitable ethoxylated ftt alcohols include the C6- Cl8 ethoxylated ftt alcohols wit a degree of ethoxylation offom 3 to 50. 11. Suitable nonionic alkylpolysaccharide surfactants, particularly fr use in the present compositions include tose disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group contaning fom about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing fom about 1.3 to about 1 O saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties ca be substituted fr 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 ofthe additional saccharide units ad the 2-, 3-, 4-, ad/or 6-positions on the preceding saccharide units. 12. Fatt acid amide surfctats suitable fr use the present compositions include those having te frmula: R6CON(R1)2 in which R6 is a alkyl group containing fom 7 to 21 carbon atoms and each R1 is independently hydrogen, C1- C4 alkyl, C1- C4 hydroxyalkyl, or --( CzH4O)xH, where xis in the range of fom 1 to 3. 13. A useful class ofnon-ionic surfactants include the class defned as alkoxylated aines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants. These non-ionic surfctats may be at least in part represented by the general 2º 2º 2º frmulae: R --(PO)sN--(EO) tH, R --(PO)sN--(EO)tH(EO)tH, and R --N(EO)tH; in which R is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of fom 8 to , prefrably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, prefrably 2-5, tis 1-10, prefrably 2-5, and u is 1-10, prefrably 2-5. Other variations on the scope ofthese compounds ry be represented by the altemative frmula: R 0--(PO)v-­ N[(EO) wH][(EO) zH] in which R is as defned above, vis 1 to 20 (e.g., 1, 2, 3, or 4 (prefrably 2)), and w and z are independently 1-10, prefrably 2-5. These compounds are represented commercially by a line of products sold by Huntsman Chemicals as nonionic surfactants. A prefrred chemical ofthis class includes SURFONIC PEA 25 Amine Alkoxy late. Prefrred nonionic surfctants fr the compositions of the invention include alcohol alkoxylates, EO/PO block copolymers, alkylphenol akoxylates, and the like. 15. A polyakylene oxide-modifed polydimethylsiloxane, nonionic surfctant or a polybetaine-modifed polysiloxane amphoteric surfactant can be employed as a nonionic surfactant. Both, in some embodiments, ae linea polysiloxane copolymers to which polyethers or polybetaines have been grafted through a hydrosilation reaction. Some examples of specifc siloxane surfctants are known as SIL WET® surfctats available fom Union Carbide, ABIL® polyether or polybetaine polysiloxae copolymers available from Evonik Corporation, Tegopren® polyether polysiloxane copolymers available from Evonik Corporation and others described in U.S. PatNo. 4,654,161 which is incorporated herein by refrence.

The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the Surfctant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent refrence on the wide variet ofnonionic compounds generally employed in the practice ofthe present invention.

A tpical listing ofnonionic classes, and species ofthese surfctants, is given in U.S. Pat.

No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surfce Active Agents and detergents" (Vol. I ad II by Schwatz, Perry and Berch).

Semi-Polar Nonionic Surfactants The semi-polar type of nonionic surface active agents are another class of nonionic surfactant useful in compositions ofthe present invention. Generally, semi-polar nonionics are high famers and fam stabilizers, which can limit their application in CIP systems.

However, within compositional embodiments ofthis invention designed fr high fam cleaning methodology, semi-polar nonionics would have immediate utilit. The semi-polar nonionic surfctants include the aine oxides, phosphine oxides, sulfxides and their alkoxylated derivatives. 14. Amine oxides are tertiary amine oxides corresponding to the general frmula: T -/0R'-r�n wherein the arrow is a conventional representaton of a semi-polar bond; and, R , R , and R may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations thereof Generally, fr amine oxides of detergent interest, R is an alky 1 radical of fom about 8 to about 24 carbon atoms; R and R are alkyl or hydroxyalkyl of 1-3 carbon atoms or a mixture thereof; R and R can be attached to each other e g through an oxygen or nitrogen atom to frm a ring structure; R is an alkaline or a hydroxyalkylene group containing 2 to 3 carbon atoms; and n ranges fom O to about 20.

Useful water soluble amine oxide surfactants are selected fom the coconut or tallow alkyl di-(lower alkyl) amine oxides, specific examples ofwhich are dodecyldimethylamine oxide, tridecyldimethylamine oxide, etradecyldimethylamine oxide, pentadecyldimethylaine oxide, hexadecyldimethylamine oxide, heptadecyldimethylaine oxide, octadecyldimethylaine oxide, dodecyldipropylamine oxide, tetradecy ldipropy lamine oxide, hexadecy ldipropy lamine oxide, tetradecyldibutlamine oxide, octadecyldibutlamine oxide, bis(2- l O hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)dodecoxy-l­ hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9- trioctadecyldimethylamine oxide and 3-dodecoxyhydroxypropyldi-(2- hydroxyethyl)amine oxide.

Useful semi-polar nonionic surfactants also include the water soluble phosphine oxides having the fllowing structure: P -�J ""'► O wherein the arrow is a conventional representarian of a semi-polar bond; and, R is an alkyl, alkenyl or hydroxyalkyl moiet ranging fom 10 to about 24 carbon atoms in chain lengt; and, R and R are each alkyl moieties separately selected fom alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

Examples of usefl phosphine oxides include dimetyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphone oxide, dimethylhexadecylphosphine oxide, diethylhydroxyoctldecylphosphine oxide, bis(2- hy droxy ethy 1 )dodecy 1 phosphine oxide, and bis(hy droxymethy 1 )tetradecy lphosphine oxide.

Semi-polar nonionic surfctants useful herein also include the water soluble sulfxide compounds which have the structure: wherein the arow is a conventional representation of a semi-polar bond; and, R is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms, fom O to about 5 ether linkages and fom O to about 2 hydroxyl substituents; and R is an alkyl moiet consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

Useful examples ofthese sulfxides include dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfxide; 3-methoxy tridecyl methyl sulfxide; and 3-hydroxy dodecoxybutyl methyl sulfxide.

Semi-polar nonionic surfctants fr te compositions of the invention include dimethyl ane oxides, such as lauryl dimethyl amine oxide, myristyl dimethyl ane oxide, cetl dimethyl amine oxide, combinations thereof, and the like. Useful water soluble amine oxide surfactants are selected fom the octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl) amine oxides, specifc examples ofwhich are octldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylane oxide, hexadecyldimethylamine oxide, heptadecyldimethylane oxide, octadecyldimethylaine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutlamine oxide, octadecyldibutlamine oxide, bis(2- hy droxy ethy 1 )dodecy lamine oxide, bis(2-hy droxy ethy 1)dodecoxy-l - hy droxypropy lamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9- trioctadecyldimethylamine oxide and 3-dodecoxyhydroxypropyldi-(2- hydroxyethyl)amine oxide.

Suitable nonionic surfactants suitable fr use with the compositions ofthe present invention include alkoxylated surfctants. Suitable alkoxylated surfctants include EO/PO copolymers capped EO/PO copolymers alcohol alkoxylates capped alcohol alkoxylates mixtures thereof, or the like. Suitable alkoxylated surfactants fr use as solvents include EO/PO block copolymers, such as the Pluronic and reverse Pluronic surfctants; alcohol alkoxylates, such as Dehypon LS-54 (R-(EO)s(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6); and capped alcohol alkoxylates, such as Plurafac LF221 and Tegoten ECll; mixtures thereof, or the like.

Cationic Surfactants Surfce active substances are classifed as cationic if the charge on the hydrotrope portion of the molecule is positive. Surfctants in which the hydrotrope carries no charge unless the pH is lowered dose to neutrality or lower, but which are then cationic (e.g. alkyl amines), ae also included in this group. In theory, cationic surfctants may be synthesized fom any combination of elements containing an "onium" structure RnX+Y-- and could include compounds other than nitrogen (ammonium) such as phosphorus (phosphonium) and sulfur (sulfnium). In practice, the cationic surfactant feld is dominated by nitrogen containing compounds, probably because synthetic routes to nitrogenous cationics are simple and straightfrward and give high yields of product, which can mae them less expens1ve.

Cationic surfctants prefrably include, more prefrably refr to, compounds containing at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain group may be attached directly to te nitrogen atom by simple substitution; or more prefrably indirectly by a bridging functional group or groups in so-called interrupted alkylamines and amido amines. Such functional groups can make the molecule more hydrophilic and/or more water dispersible, more easily water solubilized by co-surfactant mixtures, and/or water soluble. For increased water solubilit, additional primary, secondary or tertiar amino groups ca be introduced or the amino nitrogen can be quatemized wit low molecular weight akyl groups. Further, the nitrogen can be a part of branched or straight chain moiet of varying degrees of unsaturation or of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants may contain complex linkages having more than one cationic nitrogen atom.

The surfactant compounds classifed as amine oxides, amphoterics and zwitterions are themselves tpically cationic in near neutral to acidic pH solutions and can overlap surfactant clasifcations. Polyoxyethylated cationic surfctants generally behave like nonionic surfctants in alkaline solution and like cationic surfctants in acidic solution.

The simplest cationic amines, amine salts and quatemary ammonium compounds can be schematically drawn thus: in which, R represents an alkyl chain, R', R", and R"' may be either alkyl chains or aryl groups or hydrogen and X represents an anion. The amine salts and quatemary ammonium compounds are prefrred fr practical use in this invention due to their high degree of water solubilit.

The majority oflarge volume commercial cationic surfctants can be subdivided into fur major classes and additional sub-groups known to those or skill in the at and described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Vol. 104 (2) 86-96 (1989). The frst class includes alkylamines and their salts. The second class includes alkyl imidazolines. The third class includes ethoxylated amines. The fourth class includes quatemaries, such as alkylbenzyldimethylammonium salts, alkyl benzene salts, heterocyclic ammonium salts, tetra alkylammonium salts, and the like. Cationic surfctants are known to have a variety of properties that can be benefcial in the present compositions. These desirable properties can include detergency in compositions of or below neutral pH, antimicrobial effcacy, thickening or gelling in cooperation with other agents, and the like.

Cationic surfctants useful in the compositions ofthe present invention include 1 2 1 those having the frmula R r xYLZ wherein each R is an orgaic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted by up to fur of the fllowing structures: or an isomer or mixture ofthese structures, and which contains from about 8 to 22 carbon atoms. The R groups can additionally contain up to 12 ethoxy groups. misa number fom 1 to 3. Prefrably, no more than one R group in a molecule has 16 or more carbon atoms when m is 2 or more than 12 cabon atoms when m is 3. Each R is an akyl or hydroxyalkyl group containing fom 1 to 4 carbon atoms or a benzyl group with no more than one R in a molecule being benzyl, and xis a number fom O to 11, prefrably fom O to 6. The remainder of any carbon atom positions on the Y group are flled by hydrogens.

Y is can be a group including, but not limited to: p "' about 1 to 12 p " abnut l tn 12 --P�- --s�- 1 1 o· 1 O or a mixture thereof Prefrably, L is 1 or 2, with the Y groups being separated by a moiety selected fom R and R analogs (preferably alkylene or alkenylene) having fom 1 to about 22 carbon atoms and two fee carbon single bonds when L is 2. Z is a water soluble anion, such as a halide, sulfte, methylsulfte, hydroxide, or nitrate anion, particularly prefrred being chloride, bromide, iodide, sulfate or methy 1 sulfte anions, in a number to give electrica neutralit ofthe cationic component.

Amphoteric Surfactants Amphoteric, or ampholytic, surfactants contain both a basic and an acidic hydrophilic group and an organic hydrophobic group. These ionic entities may be any of anionic or cationic groups described herein fr other tpes of surfctants. A basic nitrogen and an acidic carboxylate group are the tpical functional groups employed as the basic and acidic hydrophilic groups. In a fw surfctants, sulfnate, sulfte, phosphonate or phosphate provide the negative charge.

Amphoteric surfctants can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one ofthe aliphatic substituents contains from about 8 to 18 carbon atoms and one contains a anionic water solubilizing group, e.g., carboxy, sulf, sulfto, phosphato, or phosphono. Amphoteric surfctants are subdivided into two major classes known to those of skill in the art and described in "Surfctant Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989), which is herein incorporated by refrence in its entiret. The frst class includes acyl/dialkyl etylenediamine derivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) ad their salts. The second class includes N­ alkylamino acids ad their salts. Some amphoteric surfctants can be envisioned as ftting into both classes.

Amphoteric surfctants can be synthesized by methods known to those of skill in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring closure of a long chain carboxylic acid (or a derivative) with dialkyl ethylenediamine.

Commercial amphoteric surfctants are derivatized by subsequent hydrolysis and ring- opening ofthe imidazoline ring by alkylation -- fr exaple with chloroacetic acid or ethyl acetate. During alkylation, one or two carboxy-alkyl groups react to frm a tertiary amine and an ether linkage with differing alkylating agents yielding different tertiary amines.

Long chain imidaole derivatives having application in the present invention generally have the general frmula: (MONO)ACETATE (DI)PROPIONATE CH COO­ CH COO­ RCONHCH2CH2 +H RCONHCH,CH, CH,CH,C00H CH CH 0H CH CH 0H 2 2 2 2 Neutral pH Zwittemion AMPHOTERIC SULFONATE wherein Ris an acyclic hydrophobic group containing fom about 8 to 18 carbon atoms and Misa cation to neutralize the charge ofthe anion, generally sodium. Commercially 1 O prominent imidazoline-derived ampho terics that can be employed in te present compositions include fr example: Cocoamphopropionate, Cocoampho carboxy­ propionate, Cocoamphoglycinate, Cocoamphocarboxy-gly cinate, Cocoamphopropy 1- sulfnate, and Cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced fom ftt imidazolines in which the dicarboxylic acid functionalit of the amphod icarboxylic acid is diacetic acid and/or dipropionic acid.

The ca rboxymethylated compounds (glycinates) described herein above fequently are called betaines. Betaines are a special class of amphoteric discussed herein below in the section entitled, Zwitterion Surfctants.

Long chain N-alkylamino acids are readily prepared by reaction RH2, in which R=CB-C18 straight or branched chain alkyl, fatty amines with halogenated carboxylic acids.

Alkylation of the primary amino groups of an amino acid leads to secondar ad tertiary amines. Alkyl substituents may have additional amino groups that provide more than one reactive nitroge center. Most commercial N-akylamine acids are akyl derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examples of commercial N-alkylano acid ampholytes having app lication in this invention include alkyl beta-amino dipropionates, R(C2H4COOM)2 and RHC2H4COOM. In an embodiment, R can be an acyclic hydrophobic group containing fom about 8 to about 18 carbon atoms, and Misa cation to neutraize the charge ofthe anion.

Suitable amphoteric surfactants include those derived fom coconut products such as coconut oil or coconut ftt acid. Additional suitable coconut derived surfactants include as part oftheir structure a ethylenediamine moiet, an alkanolamide moiet, an amino acid moiet, e.g., glycine, or a combination thereof; and an aliphatic substituent of fom about 8 to 18 (e.g., 12) carbon atoms. Such a surfctant can also be considered an alkyl amphodicarboxylic acid. These amphoteric surfctants can include chemical (CH2-CH2-C02Na)2-C H2-CH2- structures represented as: C12-alkyl-C(O)-NH-CH2-CH2-N l O OH or C12-alkyl-C(O)-N(H)-CH2-CH2-N(CH2-C02Na)2-CH2-CH2-0H. Disodium cocoampho dipropionate is one suitable amphoteric surfctat and is commercially available under te trade name MIRANOL FBS fom Rhodia Inc., Cranbury, N.J.

Anoter suitable coconut derived amphoteric surfctant with the chemical name disodium cocoampho diacetate is sold under the trade name MIRAT AINE JCHA, also fom Rhodia Inc., Cranbury, N.J.

A typical listing of amphoteric classes, and species ofthese surfctants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surfce Active Agents and Detergents" (Vol. I and II by Schwartz, Pery and Berch). Each ofthese refrences are herein incorporated by refrence in their entiret.

Zwitterionic Surfactants Zwitterionic surfctants can be thought of as a subset of the amphoteric surfactants and can include an anionic charge. Zwitterionic surfctants can be broadly described as derivatives of secondar and tertiary amines, derivatives ofheterocyclic secondary and tertiary amines, or derivatives of quatemary ammonium, quatemar phosphonium or tertiary sulfnium compounds. Typically, a zwitterionic surfactant includes a positive charged quatemary ammonium or, in some cases, a sulfnium or phosphonium ion; a negative charged carboxyl group; and an alkyl group. Zwitterionics generally contain cationic and anionic groups which ionize to a nearly equa degree in the isoelectric region of the molecule and which ca develop strong" inner-salt" attraction between positive- negative charge centers. Examples of such zwitterionic synthetic surfctants include derivatives of aliphatic quatemary ammonium, phosphonium, and sulfnium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one ofthe aliphatic substituents contains fom 8 to 18 carbon atoms and one contans an aionic water solubilizing group, e.g., carboxy, sulfnate, sulfte, phosphate, or phosphonate.

Betaine and sultaine surfactants are exempla zwitterionic surfactants fr use herein. A general frmula fr these compounds is: (R ) 1 1 + 3 - R-Y-CH -R-Z wherein R contains an alkyl, alkenyl, or hydroxyakyl radical of fom 8 to 18 carbon atoms having fom O to 10 ethylene oxide moieties and fom O to 1 glyceryl moiety; Y is selected fom the group consisting ofnitrogen, phosphorus, and sulfur atoms; R is an alkyl 1 O or monohydroxy alkyl group containing 1 to 3 carbon atoms; xis 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R is an alkylene or hydroxy alkylene or hydroxy akylene of fom 1 to 4 carbon atoms and Z is a radica selected fom the group consisting of carboxylate, sulfnate, sulfte, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed above include: 4- [N ,N-di(2-hy droxy ethy 1)-N-octadecy lammonio ]-butanecarboxy late; 5-[ S hy droxypropy 1-S-hexadecy lsulfnio ]hydroxypentane-l-sulfte; 3-[P ,P-diethy l-P-3,6,9- trioxatetracosanephosphonio ]hydroxypropane-l-phosphate; 3-[N,N-dipropyl-N dodecoxyhy droxypropy 1-ammonio ]-propanephosphonate; 3-( ,N-dimethy 1-N­ hexadecy lammonio )-propanesulfonate; 3-(,N-dimethy 1-N-hexadecy lammonio ) hy droxy-propane sulfonate; 4-[N ,N-di(2(2-hy droxyethy 1 )-N (2- hy droxy dodecy l )ammoni o ]-butae-1 -carboxy late; 3-[S-ethy l-S-(3-dodecoxy hydroxypropy l)sulfnio ]-propanephosphate; 3-[P ,P-dimethyl-P-dodecy lphosphonio ]­ propane-1 -phosphonate; and S [N ,N-di(3-hy droxypropy 1 )-N-hexadecy lammonio ] hy droxy-pentane-l -sulfte. The alkyl groups contained in said detergent surfctants can be straight or branched and saturated or unsaturated.

The zwitterionic surfctant suitable fr use in the present compositions includes a betaine of the general structure: 11 11 1 1 + - 1 1 + - R-N -CH CO 2 R-S -CH CO R-P-CH2-C02 2 2 2 l 111 1111 These surfctant betaines typically do not exhibit strong cationic or anionic characters at pH extremes nor do they show reduced water solubilit in their isoelectric range. Unlike "extemal quatemary amonium salts, betaines are compatible with anionics. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; Cs-14 acylamidohexyldiethyl betaine; 4-C 14-1 6 acy lmethy lamidodiethy lammonio caboxy butane; C 16- 18 acy lamidodimety lbetane; C 12- 1 6 acylamidopentanediethylbetaine; and C12- 16 acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds having the 1 2 3 1 frmula (R(R )2 N RSO , in which Ris a C6 -Cl8 hydrocarbyl group, each R is tpically independently C1-C3 alkyl, e.g. methyl, and R is a C1 -C6 hydrocarbyl group, e.g. a C1-C 3 alkylene or hydroxyalkylene group.

A tpical listing of zwitterionic classes, and species ofthese surfctants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surfce Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). Each of these refrences are herein incorporated in their entiret.

Water The compositions include water. Water can be included in the solid compositions as water ofhydration fr a hydratable salt formulation. Those of skill in the art will be capable of selecting the grade of water desired with the desired levei of water hardness and grain. When water is included in the compositions of te present invention, it can comprise between about O wt.% and about 80 wt.%, prefrably between about 0.01 wt.% and about 75 wt.%, more prefrably between about 1 wt.% and about 50 wt.%,. In a use solution, the majorit ofthe solution will comprise water, preferably greater than 90 wt.%, more prefrably greater than 95 wt. %, and most prefrably 99 wt. % or greater.

Additional Functional Ingredients The components ofthe compositions can further be combined with various functional components. In some embodiments, the composition including the alkalinit source, hydroxyphosphono carboxylic acid, surfactant, and water make up a large amount, or even substantially all ofthe total weight ofthe composition. For example, in some embodiments fw or no additiona functional ingredients are disposed therein.

In other embodiments, additiona fnctional ingredients may be included in the 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 benefciai propert in a paticular use. Some particular examples offunctional materiais are discussed in more detail below, although the particular materiais discussed are given by way of example only, and that a broad 1 O variet of other functional ingredients may be used. For example, many ofthe functiona materiais discussed below relate to materiais used in cleaning, specifcally CIP and wae wash applications. However, other embodiments may include functional ingredients fr use in other applications.

In some embodiments, the compositions may include an aionic surfactant, a anti- redeposition agent, a bleaching agent, a carbonate, a chelant, a defaing agent, a dispersant, a dye, a fagrance, a hydrotrope, an oxidizer, and/or a stain inhibitor.

Anionic surfactants Also useful in the present invention are surface active substances Yhich are categorized a.s aníonics because the charge on the hydrophobe ís negative; or surfctants ín ,vhich the hydr ophobic section of the molecule canies no charge unless the pH is elevated io neutrality or above (e.g. caboxylic acids). Carboxy laie, sulfonate, sulfte and phosphate are the polar (hydrophilic) solubilizing groups found m anionic surfctats. Of the cations (counter ions) associated with these polar groups, sodium. lithium and potassium impart ,vater solubili ty; ammonium and substituted ammonium ions provide both water and oil solubilit; and, caci.um, barium. and magnesium promote oil solubility.

Generally, anionics have high fam profiles whích may limit appl ícations ofuse fr cleani ng systems such as ClP circuits that require stnct foam control. However, other applications of use, including high foaming applications are suitable for using anio nic surface active compouds to impaii special chemic:al or physical properties. TI1e majority of large volume commercial anionic surfactants can be subdivided into five major chemical classes ane additional suh-groups known to those of skill in the art and described in 'ºSurfctant Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 71-86 (1989). The first class includes acylamino acids (and salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates fo.g. N-acyl taurates and fatty acid amides ofmethyl tauride), and tbe like. The second class includes carboxyiic acids (and salts), such as alkanoic acids (ad alkanoates), ester carboxylic acids (e.g. alkyl succinates), ether carboxyiic acids, and the like. TI1e third clas includes sulfnic acids (and salts), such as 1sethionates (e.g. acyl isethionates), alkylaryl sulfnates, alkyl sulfnates, sulfsuccmates (e.g. monoesters and diesters of sulfsuccinate), and the like. The fth class includes sulfuric acid esters (and salts), such as alkyi ether sulfates, alkyl sulftes, ane the like.

Anionic sulfonate surfctants suitable fr use in the present compositions include alkyl sulfnates, the linear and branched primary ane secondary alkyi sulfnates, a.nd tbe aromatic sulfnates ,vith or without substituents. Anionic sulfate surf ctats suitable fr use in the present compositons include alkyl ether sulfates, alkyl sulfates, the linear and branched pnmary ad secondary alkyl sulfates, alkyl ethoxysulftes, ftty oleyl glycerol sulftes, alkyl phenol ethylene oxide ether sulftes, the Cs-Cl7 acl-N (C1-C4 alkyl) and ·---·-N---·-(C1-C:d1ydroxyaikyl) glucamine sulftes, and sulftes of aikylpoiysaccharides such as the sulfates of alkylpolyglucoside, and the like. Also included are the alkyl sulfates, alkyl poly(ethyleneoxy) ether sulf tes and aroratic poly(eihyleneoxy) sulfates such as the sulftes or condensation products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene groups per molecule). Particularly suitable anionic sulfnates include alkyldipheny loxide disulfonates, including for example C6 alkyiated diphenyi oxide disulfonic acid, commerciaily-available under the trade name DOWFAX®.

Anionic carboxylate surfctants suitable fr use in the present compositions include carhoxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates), ether carboxylic adds, and the like. Such carboxylates include alkyl etoxy carboxylates, alkyl aryl ethoxy carboxylates, all yl polyethoxy polycarboxylate surfctanis and soaps (e.g. alkyl carboxyls). Secondary carboxylates usefl in the present compositions indude those which contain a carboxyi uit connected to a secondary carhon.

The secondary carbon can be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-substituted cydohexyl carboxylates. The secondary carboxylate surfctants typically contain no ether linkages, no ester Iinkages and no hydroxyl groups. Further, they tpically lack nitrogen atoms in the head-group (amphiphilic portion). Suitable secondary soap surfctants tpically contain 11-13 total carbon atoms, although more carbons atoms (e.g., up to 16) can be present. Suitable carboxylates also include acylamino acids (ad salts), such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g.

N-acyi taurates and ftty acid amides of methyl tauride), and the like.

Suitable anionic carboxylate surfactants may further include polycarboxylates or related copolymers. A va riety of such polycarboxylate poly mers ad copolymers are known and descríbed in patent and other literature, ad are available commercially.

Exernplary polycarboxylates that may be uiilized according to ihe invention include for example: homopolymers and copolymers ofpolyacrylates; polymethacrylates; polymalates: materials such as acrylic, olefnic and/or maleic polymers and/or copolymers.

Various examples of commercially-available agents, namely acrylic-rnaleic acid copolymers include, for example: Acusol 445N and Acusol 448 (available from Dow ChemicaL Examples of suitable ac1ylic-maleic acid copolymers include, but are not limited to, acrylic-male1c acíd copolymers having a molecular weight of between about 1,000 to about 100,000 g/mol, particularly between about l,000 and about 75,000 g/mol and more particularly between about 1,000 and about 50,000 g/mol.

Suitable anionic surfctants include alkyl or alkylaJyl ethoxy carboxylates of the fliowing formula: ---- -- -O---C -(H2CR:O)n( CH2)m- CO2X in which R is a Cs to C22 alky l group or in which is a C4-C16 alkyl group; n 1s an integer of 1-20; misa integer of 1-3; and Xis a counier ion, such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine_ diethanolamine or triethanolamine. In some embodiments_ n is an integer of 4 to lO and m is 1. ln some embodiments, Ris a Cs-C16 alkyl group. ln some embodiments, R is a C 2-C 14 alky 1 group, n is 4, and m is 1.

In other embodiments, R is and R. is a C6-C1 alkyl group. ln still yet other embodiments, R is a C9 alkyl group, n is 1 O and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercialy available. These ethoxy carboxylates are typically available as the acid forms, vvhich can be readily converted to the anionic or sait frm. Commercially avaiiable carboxyiates include, Neodox 23-4, a C12.u alkyl polye thoxy (4) carboxylic ac1d (Shell Chemical), and Emcol CNP-l] O, a C9 akylaryl polyethoxy (10) carboxylic acid (Witco Cherical). Carboxylates are also available fom Clarant, e.g. the product SANDO PAN@ DTC, a Cn alkyl polyethoxy O) carboxylic acid.

Anti-Redeposition Agents The compositions can optionally include an anti-redeposition agent capable of 1 O fcilitating sustained suspension of soils in a cleaning solution and preventing te removed soils fom being redeposited onto the surface being cleaned. Examples of suitable anti­ redeposition agents include, but are not limited to: ftt acid amides, fuorocarbon surfctants, complex phosphate esters, polyacrylates, strene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose.

Bleaching Agents Suitable bleaches fr use in the compositions and metods ofthe invention can be halogen-based bleaches or oxygen-based bleaches.

A halogen-based bleach may be efectively used as ingredient of the frst component. In that case, sad bleach is desirably present at a concentration (as active halogen) in the range of fom O to 10%, prefrably fom 0.5 to 8%, more prefrably fom 1 to 6%, by weight. As halogen bleach, alkali metal hypochlorite may be used. Other suitable halogen bleaches are alkali metal salts of di- and tri-chloro and di-and tri-bromo canuric acids.

Suitable oxygen-based bleaches are the peroxygen bleaches, such as sodium perborate (tetra-or monohydrate), sodium percarbonate, hydrogen peroxide, and peracids.

These are prefrably used in conjunction with a bleach activator which alows the liberation of active oxygen species at a lower temperature. Numerous examples of activators of this tpe, ofen also refrred to a bleach precursors, are known in te art ad amply described in the literature such as U.S. Pat. No. 3,332,882 and U.S. Pat. No. 4,128,494 herein incorporated by reference. Prefrred bleach activators are tetraacetl ethylenediamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), glucose pentaacetate (GPA), tetraacetlmethylene diamine (TAMD), triacetl cyanurate, sodium sulphonyl ethyl carbonic acid ester, sodium acetloxybenzene and the mono long-chain acyl tetraacetl glucoses as disclosed in , but other activators, such as choline sulphophenyl carbonate (CSPC), as disclosed in U.S. Pat. No. 4,751,015 and U.S.

Pat. No. 4,818,426 can also be used. Prefrred peroxygen bleach precursors are sodium p­ benzoyloxy-benzene sulfnate, N,N,N,N-tetraacetl ethylenediamine (TEAD), sodium nonanoyloxybenzene sulfnate (SNOBS) and choline sulfphenyl carbonate (CSPC).

Peracids suitable fr the invention can be a single species or mixture. Suitable peracids can be selected based on the desired end use and based upon compatibility with 1 O other components in the compositions and methods. Prefrred peracids include those having a carbon chain length of C2 to C 12. Suitable peracids ca include those described in U.S. Patent No. 8,846,107, entitled, "In Situ Generation of Peroxycarboxylic Acids at Alkaline pH, and Methods of Use Thereof," which is expressly incorporated herein in its entiret by refrence, including without limitation all drawings and chemical structures contained therein. Suitable peracids can include akyl ester peroxycarboxylic acids, ester peroxycarboxylic acids, sulfperoxycarboxylic acids, and others. Suitable alkyl ester peroxycaboxylic acids and ester peroxycarboxylic acids can include those described in U.S. PatentNos. 7,816,555 and 7,622,606, both entitled "Peroxycarboxylic Acid Compositions with Reduced Odor," hereby expressly incorporated herein in its entiret by refrence, including without limitation all drawings and chemical structures contained therein. Suitable sulfpero xycaboxylic acids can include those described in U.S. Patent No. 8,809,392, entitled, "Sulfp eroxycab oxylic Acids, Their Preparation and Methods of Use as Bleaching and Antimicrobial Agents," which is expressly incorporated herein in its entiret by refrence, including without limitation all drawings and chemical structures contained therein.

Peroxybenzoic acid precursors are known in the art as described in GB-A-836,988, herein incorporated by refrence. Examples of suitable precursors are phenylbenzoate, phenyl p-nitrobenzoate, o-nitrophenyl benzoate, o-carboxyphenyl benzoate, pbromophenyl benzoate, sodium or potassium benzoyloxy benzene sulfnate and benzoic ahydride.

Halogen bleaching agents be present in the compositions and methods of the invention in an amount between about O ppm and about 1000 ppm. Peracid bleaching agents can be present in the compositions and methods ofthe invention in an amount between about O ppm and about 2500 ppm. Other peroxygen-based bleaching agents (e.g., peroxide, percarbonate, and perborate) can be present in the compositions and methods of the invention in an amount between about O ppm and about 15,000 ppm.

Carbonate The compositions and methods of the invention can optionally include a carbonate as a secondary alkalinit source ad/or hardening agent. Suitable carbonates include alkali metal carbonates, such as sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof When employed as a hardening agent, the carbonate can further comprise water ofhydration suffcient to solidif the carbonate. The optional carbonate can be present in the inventions in an amount between about 0.1 wt. % and about 50 wt. %.

Chelant The compositions can optionally include a chelant fr water conditioning/sequestering properties. Suitable chelants can include amino carboxylates, ano phosphonates, polyfunctionally-substituted aromatic chelating agents, hydroxycarboxylic acids and mixtures thereof Prefrred chelants fr use herein are ety lenediamine tetraacetic acid (EDT A), diethy lenetriamine pentaacetic acid (DTP A), gluconate,citrate, tartrate, and derivatives ad/or phosphonate-based chelants prefrably diethylenetriamine penta methylphosphonic acid.

Other chelants include amino carboxylates include ethylenediaminetetra-acetates, N-hydroxyethylethylenediaminetriacetates, nitrilo-triacetates, ethylenediamine tetrapro­ prionates, triethy lenetetraaminehexacetates, diethy 1 enetriaminepentaacetates, and ethanoldi-glycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. As well as MGDA (methyl-glycine-diacetic acid), and salts and derivatives thereof and GLDA (glutamic-N,N-diacetic acid) and salts and derivatives thereof GLDA (salts and derivatives thereof is especially preferred according to the invention, with the tetrasodium salt thereof being especially prefrred.

Other suitable chelants include amino acid based compound or a succinate based compound. The term "succinate based compound" and "succinic acid baed compound" are used interc hangeably herein. Other suitable chelants are descri bed in U.S Pat. No. 6,426,229. Particular suitable chelants include; fr example, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N,N-diacetic acid (ASDA), aspartic acid-N-monopropionic acid (ASMP), iminodisuccinic acid (IDS), Imino diacetic acid (IDA), N-(2- sulfmethyl)aspart ic acid (SMAS), N-(2-sulfethyl)aspartic acid (SEAS), N-(2- sulfomethyl)glutamic acid (SMGL), N-(2-sulfoethyl)glutamic acid (SEGL), N- methyliminodiacetic acid (MIDA), �-alanine-N,N-diacetic acid -ALDA), serine-N,N­ diacetic acid (SEDA), isoserine-N,N-diacetic acid (ISDA), phenylalanine-N,N-diacetic acid (PHDA), anthranilic acid-N,N-diacetic acid (ANDA), sulfanilic acid-N,N-diacetic acid (SLDA), taurine-N,N-diacetic acid (TUDA) and sulfmethyl-N,N-diacetic acid (SMDA) and alkali metal salts or ammonium salts thereof Also suitable is etylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.

Pat. No. 4,704,233. Furthermore, Hydroxyethyleneiminodiacetic acid, Hydroxyiminodisuccinic acid, Hydroxyethylene diaminetriacetic acid is also suitable.

Other chelants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. Prefrred salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts, and particularly prefrred sats are the sodium salts.

Suitable polycaboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two caboxyl groups which are in each case separated fom one another by, prefrably, no more than two carbon atoms.

Polycarboxylates which comprise two caboxyl groups include, fr 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, fr example, water-soluble citrate. Correspondingly, a suitable hydroxycarboxylic acid is, fr example, citric acid. Another suitable polycarboxylic acid is the homopolymer of acrlic acid. Prefrred are the polycarboxylates end capped with sulfnates.

Amino phosphonates ae also suitable fr use as chelating agents and include etylenediaminetet rakis(methylenephosphonates) as DEQUEST. Prefrred, these amino phosphonates that do not contain akyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefl in the compositions herein such as described in U. S. Pat. No. 3,812,044. Prefrred compounds of this tpe in acid frm are dihydroxydisulfbenzenes such as l,2-dihydroxy-3,5- disulfbenzene.

Further suitable polycarboxylates chelants fr use herein include citric acid, and succinic acid all preferably in the form of a water-soluble salt. Other suitable polycarboxylates are oxodisuccinates, carboxymethyloxysuccinate and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in U.S. Pat. No. 4,663,071.

Defoaming Agent The compositions and methods ofthe invention can optionally include a defaming agent. Defaming agents can be particularly suitable fr embodiments of the invention including foaming surfactants, such as anionic surfactants. Generally, defoamers which can be used in accordance with the invention include silica and silicones; aliphatic acids or esters; acohols; sulftes or sulfonates; amines or aides; halogenated compounds such as fuorochlorohydrocarbons; vegetable oils, waxes, minera oils as well as their sulfnated or sulfted derivatives; ftt acids and/or their soaps such as alkali, alkaline earth metal soaps; and phosphates and phosphate esters such as alkyl and alkaline diphosphates, and tributl phosphates aong others; and mixtures thereof In some embodiments, the compositions of the present invention can include antifaming agents or defamers which are of fod grade quality given the application of the method of the invention. To this end, one of the more efective antifoaming agents includes silicones. Silicones such as dimethyl silicone, glycol polysiloxane, methylphenol polysiloxane, trialkyl or tetralkyl silanes, hydrophobic silica defamers and mixtures thereof can all be used in defaming applications. Commercial defamers commonly fom Armour Industria Chemical available include silicones such as ARDEFOAM Company which is a silicone bound in an organic emulsion; FOAM KILL KRESSEO avalable from Krusable Chemical Company which are silicone and non­ silicone tpe defamers as well as silicone esters; and ANTI-FOAM A and DC-200 fom Dow Coming Corporation which are both fod grade tpe silicones among others.

In some embodiments, the compositions of the present invention can include antifaming agents or defaming agents which are based on alcohol alkoxylates that are stable in acid environments and are oxidatively stable. To this end one ofthe more efective antifaming agents are the alcohol alkoxylates having an alcohol chain length of about C8-12, and more specifcaly C9-l l, and having poly-propylene oxide alkoxylate in whole or part ofthe alkylene oxide portion. Commercial defamers commonly available of this tpe include alkoxylates such as the BASF DEGRESSAL products, especially DEGRESSAL SD20.

Dispersants The compositions can optionally include a dispersat. Examples of suitable dispersants that can be used in te solid detergent composition include, but are not limited to: maleic acid/olefn copolymers, polyacrylic acid, and mixtures thereof. 1 O Dyes and Fragrances The compositions can optionally include a dyes, fagrances including perfumes, and/or other aesthetic enhancing agent. Dyes may be included to alter the appearance of the composition, as fr example, any of a variet ofFD&C dyes, D&C dyes, and the like.

Additional suitable dyes include Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keystone Aniline and Chemical), Metanil Yellow (Keystone Aniline and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue/ Acid Blue 182 (Sandoz), Risol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), Pylakor Acid Bright Red (Pylam), and the like. Fragrances or perfumes that may be included in the compositions include, fr exaple, terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, ajasmine such as ClS-jasmine or jasmal, vanillin, and the like.

Functional Polydimethylsiloxnes The composition can also optionally include one or more functional polydimethylsiloxanes. For example, in some embodiments, a polyalkylene oxide-modifed polydimethylsiloxane, nonionic surfctant or a polybetane-modifed polysiloxane amphoteric surfctant can be employed as an additive. Both, in some embodiments, are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted through a hydrosilation reaction. Some examples of specifc siloxane surfctants are known as SIL WET surfactants available from Union Carbide or ABIL ™ polyether or polybetaine polysiloxane copolymers available from Goldschmidt Chemical Corp., and described in U.S. Pat. No. 4,654,161 which patent is incorporated herein by refrence. In some embodiments, the particular siloxanes used can be described as having, e.g., low surface tension, high wetting abilit and excellent lubricit. For example, these surfctants are said to be among te fw capable of wetting polytetrafuoroethylene surfaces. The siloxane surfctant employed as an additive ca be used alone or in combination with a fuorochemical surfctant. In some embodiments, the fuorochemical surfctant employed as an additive optionally in combination with a silane, can be, fr example, a nonionic fuorohydrocarbon, fr example, fuorinated alkyl polyoxyethylene ethanols, fuorinated alkyl alkoxylate and fuorinated alkyl esters. In some embodiments, the compositions do not include a fuorochemical surfctant. 1 O Further description of such functional polydimethy lsiloxones and/or fluorochemical surfactants are described in U.S. Pat. Nos. 5,880,088; 5,880,089; and 5,603,776, all of which patents ae incorporated herein by refrence. W e have fund, fr example, that the use of certain polysiloxane copolymers in a mixture with hydrocarbon surfctants provide excellent rinse aids on plasticware. We have also found that the combination of certain silicone polysiloxane copolymers and fuorocarbon surfactants with conventional hydrocarbon surfctants also provide excellent rinse aids on plasticware. This combination has been found to be better than the individual components except with certan polyalkylene oxide-modifed polydimethylsiloxanes and polybetaine polysiloxane copolymers, where the efectiveness is about equivalent. Therefre, some embodiments encompass the polysiloxane copolymers alone and the combination with the fuorocarbon surfactant can involve polyether polysiloxanes, te nonionic siloxane surfactants. The amphoteric siloxane surfctants, the polybetaine polysiloxane copolymers may be employed alone as the additive in the rinse aids to provide the same results.

Embodiments can optionally include a functional polydimethylsiloxanes in an amount in te range of up to about 10 wt-%. For example, some embodiments may include in the range of about 0.01 to 1 O wt-% of a polydimethylsiloxane.

Hydrotrope A hydrotrope component can be used to help stabilize the surfctant component. It should be understood that the hydrotrope component is optional and can be omitted if it is not needed fr stabilizing the surfactant component. In may cases, it is expected that the hydrotrope component will be present to help stabilize the surfctant component. Examples of the hydrotropes include the sodium, potassium, ammonium and alkanol ammonium salts of xy Iene sulfnate, tol uene sulfnate, ethy 1 benzoate sulfnate, isopropy 1 benzene, sulfnate naphthaene sulfnate, alkyl naphthalene sulfnates, phosphate esters of alkoxylated akyl phenols, phosphate esters of alkoxylated alcohols, short chan (C8 or less) alkyl polyglycoside, sodium, potassium and ammonium salts ofthe alkyl sarcosinates, salts of cumene sulfnates, amino propionates, diphenyl oxide sulfontes, and disulfnates.

The hydrotropes are useful in maintaining the organic materials including te surfactant readily dispersed in te aqueous cleaning solutian ad, in particular, in an aqueaus concentrate which is an especially prefrred frm of packaging the compasitions af the invention and allow the user ofthe compositians to accurately provide the desired amaunt 1 O of detergent composition.

Oxidizer An oxidizer can aptionally added ta the use salution ofthe invention. For stabilit purposes the oxidizer is tpically added separately during performance of the method or is part of a multi-part system. This is because the oxidizer is incampatible with the alkalinit saurce. Suitable axidizers, include peroxycarbaxylic acids, hydrogen peroxide, and combinations thereof Histarically it has been difcult to incarporate oxidizers into cleaning methods fr fod grade stainless steel ar other fad processing surfaces comprised of corradible metals as the oxidizer can dramaticaly increase corrosion ofthe surface. lt is an advantage af the present inventian that methods fr cleaning such surfces can be accomplished including the use of an oxidizer where the corrosion, discoloration, staining, ad/ar pitting of the surfce is reduced ar even prevented.

In a prefrred aspect, an oxidizer ar an oxidizer may be a peroxide or peroxyacid.

Peroxygen campaunds, which include peroxides and variaus percarbaxylic acids, including percarbonates, are suitable. In such an aspect, the catayst ofthe cleaning composition promotes the decomposition ofthe oxidizer providing enhanced soil remaval without having the expected staining and/or corrasion ofthe highly oxidizing canditions.

In an aspect, the oxidizers (e.g. oxygen compounds) react with the sail, especially when combined with a alkaline source fom the cleain g compasition and creates vigorous mechanical actian an ad within the sail, which enhances removal of the soil beyand that caused by the chemical and bleaching actian.

In the methods ofthe invention, the oxidizer can be added to provide a concentration in a use solution fom about 50 ppm to about 5000 ppm, fom about 100 to about 3000 ppm, or fom about 500 ppm to about 2500 ppm.

Peroxycarboxylic acids Peroxycarboxylic acid (i.e. peracid) are tpically included in cleaning applications fr antimicrobial and/or sanitizing effcacy. As used herein, the term "peracid" may also be refrred to as a "percarboxylic acid," "peroxycarboxylic acid" or "peroxyacid." Sulfperoxycarboxylic acids, sulfnated peracids and sulfnated peroxycarboxylic acids are also included within the terms "peroxycarboxylic acid" and "peracid" as used herein.

The terms "sulfperoxycarboxylic acid," "sulfnated peracid," or "sulfnated peroxycaboxylic acid" refrs to the peroxycarboxylic acid frm of a sulfnated carboxylic acid as disclosed in U.S. Patent No. 8,344,026, and U.S. Patent Publication Nos. 2010/0048730 and 2012/0052134, each of which are incorporated herein by refrence in their entiret. As one of skill in the art appreciates, a peracid refrs to an acid having the hydrogen ofte hydroxyl group in carboxylic acid replaced by a hydroxy group.

Oxidizing peracids may also be refrred to herein as peroxycarboxylic acids.

A peracid includes any compound ofthe frmula R--(COOOH)n in which R can be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl, heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named by prefxing the parent acid wit peroxy. Prefrably R includes hydrogen, alkyl, or alkenyl. The terms "alkyl," "alkenyl," "alkyne," "acylic," "alicyclic group," "aryl," "heteroaryl," and "heterocyclic group" are as defned herein.

As used herein, the term "akyl" or "alkyl groups" refrs to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, etyl, propyl, butyl, pentl, hexyl, heptl, octl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentl, cyclohexyl, cycloheptl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butl, sec-butyl, isobutl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl­ substituted cycloalkyl groups and cycloalkyl-substituted akyl groups). Prefrably, a straight or branched saturated aliphatic hydrocarbon chain having fom 1 to 22 carbon atoms, such as, fr example, methyl, etyl, propyl, isopropyl (1-methylethyl), butl, tert­ butl (1,1-dimethylethyl), and the like.

Unless otherwise specifed, the term "alkyl" includes both "unsubstituted alkyls" and "substituted alkyls." As used herein, the term "substituted alkyls" refrs to alkyl groups having substituents replacing one or more hydrogens on one or more carbons ofthe hydrocarbon backbone. Such substituents may include, fr example, akenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, ary loxy carbony loxy, carboxy late, alky lcarbony 1, ayl carbony 1, alkoxy carbony 1, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkyltiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl ano, dialkylano, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfydryl, alkylthio, arylthio, thiocarboxylate, sulftes, alkylsulfnyl, sulfnates, sulfaoyl, sulfnado, nitro, trifuoromethyl, cyano, azido, heterocyclic, alkylaryl, or aomatic (including heteroaromatic) groups.

The term "alkenyl" includes an unsaturated aliphatic hydrocarbon chain having fom 2 to 12 carbon atoms, such as, fr example, etheny 1, 1-propeny 1, 2-propeny 1, 1- buteny l, 2-methylpropenyl, and the like. The alkyl or alkenyl can be terminally substituted with a heteroatom, such as, fr example, a nitrogen, sulfur, or oxygen atom, frming an aminoalkyl, oxyalkyl, or thioalkyl, fr example, aminomethyl, thioethyl, oxypropyl, and the like. Similarly, the above alkyl or alkenyl can be interrupted in the chain by a heteroatom frming a alkylaminoalkyl, alkylthioalkyl, or alkoxyalkyl, fr example, methylaminoethyl, ethylthiopropyl, metoxymethyl, and the like.

Further, as used herein the term "alicyclic" includes any cyclic hydrocarbyl containing fom 3 to 8 carbon atoms. Examples of suitable alicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl, etc. 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 ofthe cabon atoms in the ring is an element other than cabon, fr 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 (episulfdes), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan Additional examples of suitable heterocyclic groups include groups derived fom tetrahydrofurans, furans, thiophenes, pyrrolidines, piperidines, pyridines, pyrrols, picoline, coumaline, etc.

According to the invention, alkyl, alkenyl, aicyclic groups, and heterocyclic groups can be unsubstituted or substituted by, for example, aryl, heteroarl, Ct-4 alkyl, Ct-4 alkenyl, Ct-4 alkoxy, amino, carboxy, halo, nitro, cyano, --SO3H, phosphono, or hydroxy.

When alkyl, alkenyl, alicyclic group, or heterocyclic group is substituted, prefrably the substitution is Ci-4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulpho, or phosphono. In one embodiment, R includes alkyl substituted with hydroxy. The term " l" includes aromatic hydrocarbyl, including fused aomatic rings, such as, fr example, phenyl and 1 O naphthyl. The term "heteroarl" includes heterocyclic aromatic derivatives having at least one heteroatom such as, fr example, nitrogen, oxygen, phosphorus, or sulfr, and includes, fr example, frl, pyrrolyl, thienyl, oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, etc. The term "heteroaryl" also includes fused rings in which at least one ring is aromatic, such as, fr example, indolyl, purinyl, benzofurl, etc.

According to the invention, aryl and heteroaryl groups can be unsubstituted or substituted on the ring by, fr example, l, heteroaryl, alkyl, alkenyl, akoxy, amino, carboxy, halo, nitro, cyano, --SO3H, phosphono, or hydroxy. When aryl, aralkyl, or hetero l is substituted, prefr ably the substitution is Ct-4 alkyl, halo, nitro, amido, hydroxy, carboxy, sulpho, or phosphono. In one embodiment, R includes aryl substituted with Ct- alkyl.

Typical peroxygen compounds suitable fr use as oxidizers include hydrogen peroxide (H2O2), peracetic acid, peroctanoic acid, a persulphate, a perborate, or a percarbonate. Some peroxycarboxylic acids include peroxypentanoic, peroxyhexanoic, peroxyheptaoic, peroxyoctanoic, peroxynonanoic, peroxyisononanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, peroxyascorbic, peroxyadipic, peroxycitric, peroxypimelic, or peroxysuberic acid, mixtures thereof, or the like. Some suitable branched chain peroxycarboxylic acid include peroxyisopentanoic, peroxyisononaoic, peroxyisohexanoic, peroxyisoheptanoic, peroxyisooctanoic, peroxyisonananoic, peroxyisodecanoic, peroxyisoundecanoic, peroxyisododecanoic, peroxyneopentanoic, peroxyneohexanoic, peroxyneoheptanoic, peroxyneooctanoic, peroxyneononaoic, peroxyneodecanoic, peroxyneoundecanoic, peroxyneododecanoic, mixtures thereof, or the like.

In another embodiment, a sulfperoxycarboxylic acid has the fllowing frmula: R -CH-R,-COOOH S03•X wherein R1 is hydrogen, or a substituted or unsubstituted alkyl group; R2 is a substituted or unsubstituted alkylene group; Xis hydrogen, a cationic group, or an ester frming moiet; or salts or esters thereof. In some embodiments, R1 is a substituted or unsubstituted Cr alkyl group; Xis hydrogen a cationic group, or an ester forming moiet; R2 is a substituted 1 to 10; and m+n is less than 18, or salts, or unsubstituted Cn alkyl group; m 1 to 1 O; n esters or mixtures thereof In some embodiments, R1 is hydrogen. In other embodiments, R1 is a substituted or 1 O unsubstituted alkyl group. In some embodiments, R1 is a substituted or unsubstituted alkyl group that does not include a cyclic alkyl group. In some embodiments, R1 is a substituted alkyl group. In some embodiments, R1 is an unsubstituted C1-C9 alkyl group. In some embodiments, R1 is an unsubstituted C1 or Cs alkyl. In other embodiments, R1 is a substituted Cs-C10 alkylene group. In some embodiments, R1 is a substituted Cs-C10 alkyl group is substituted with at least 1, or at least 2 hydroxyl groups. In still yet other embodiments, R1 is a substituted C1-C9 alkyl group. In some embodiments, R1 is a substituted C1-C9 substituted alkyl group is substituted with at least 1 S03H group. In other embodiments, R1 is a C9-C10 substituted alkyl group. In some embodiments, R1 is a substituted C9-C10 alkyl group wherein at least two of the carbons on the carbon backbone frm a heterocyclic group. In some embodiments, the heterocyclic group is an epoxide group.

In some embodiments, R2 is a substituted C1-C10 alkylene group. In some embodiments, R2 is a substituted Cs-C10 alkylene. In some embodiments, R2 is an unsubstituted C6-C9 alkylene. In other embodiments, R2 is a Cs-C10 alkylene group substituted with at least one hydroxyl group. In some embodiments, R2 is a Cio alkylene group substituted with at least two hydroxyl groups. In other embodiments, R2 is a Cs alkylene group substituted with at least one S03H group. In some embodiments, Rús a substituted C9 group, wherein at least two of the carbons on the carbon backbone frm a heterocyclic group. In some embodiments, the heterocyclic group is a epoxide group. In some embodiments, R1 is a C8-C9 substituted or unsubstituted alkyl, and R2 is a C7-C8 substituted or unsubstituted alkylene.

These and other suitable sulfperoxycarboxylic acid compounds fr use in the stabilized peroxycarboxylic acid compositions ofthe invention are further disclosed in U.S. Patent No. 8,344,026 and U.S. Patent Publication Nos. 2010/0048730 and 2012/0052134, which are incorporated herein by refrence in its entiret.

The peroxycarboxylic can be used at any suitable concentration in the oxidizer and/or methods ofte invention.

Hydrogen Peroxide 1 O In a prefrred aspect, an oxidizer or an oxidizer can comprise hydrogen peroxide.

Hydrogen peroxide, H2O2, provides the advantages ofhaving a high ratio of active oxygen because ofits low molecular weight (34.014 g/mole) and being compatible with numerous substances that ca be treated by methods of the invention because it is a weakly acidic, clear, and colorless liquid. Another advantage of hydrogen peroxide is that it decomposes into water and oxygen. It is advantageous to have these decomposition producs because they are generally compatible with substances being treated. For example, the decomposition products are generally compatible with metallic substance (e.g., substantially noncorrosive) and are generally innocuous to incidental contact and are environmentally fiendly.

The hydrogen peroxide ca be used at any suitable concentration in te oxidizer and/or methods of te invention.

Oxidizing Boosters Suitable oxidants can also be provided in the frm of a booster, which may include fr example oxidants such as chlorites, bromine, bromates, bromine monochloride, iodine, iodine monochloride, iodates, permangaates, nitrates, nitric acid, borates, perborates, and gaseous oxidants such as ozone, oxygen, chlorine dioxide, chlorine, sulfur dioxide and derivatives thereof In an aspect, such oxidants may be employed as a booster, alone or in combination with the oxidizer, such as a chlorine booster. Bene:cially, the alkaline cleaning compositions according to the invention do not interfre with the stabilit of chlorine and/or other boosters.

An oxidizer may include bleaching compounds capable ofliberating an active halogen species, such as Ch, Br2., -OCl and/or -OBr , under conditions tpically encountered during the cleansing process. Suitable bleaching agents for use in the present detergent compositions include, fr example, chlorine-containing compounds such as a chlorine, a hypochlorite (e.g. sodium hypochlorite), and/or chloramine. Prefrred halogen­ releasing compounds include te alkali metal dichloroisocyanurates, such as sodium dichloroisocyanurate, chlorinated trisodium phosphate, the alkali metal hypochlorites, monochlorarrine and dichloramine, and the like.

Stain Inhibitor The compositions can optionally include a stain inhibitor. Suitable stain inhibitors include a gluconic acid or other polyhydroxy carboxylic acid (or hydroxycarboxylic acid) or salts thereof A combination of gluconic acid and other polyhydroxy carboxylic acid (or hydroxycaboxylic acid) or salts tereof can be employed as a stain inhibitor. In a aspect, gluconic acid and glucaric acid are suitable for use as a stain inhibitor for the cleaning compositions and methods of the present invention. Prefra bly, the stain inhibitor is soluble in water. In embodiments of the invention, is is prefrred that the stain inhibitor is non- or low-foaming.

Polyhydroxy carboxylic acids or hydroxycarboxylic acids usefl as stain inhibitors prefrably include those having 10 or fwer carbon atoms, or fom 4 to 10 carbon atoms, with similar location ofthe carbon atoms and similar polyol grouping. These may include fr example, glycolic acid, citric acid, malic acid, tartaric acid, lactic acid, tartronic acid, glutaric acid, adipic acid and/or succinic acid.

In a prefrred aspect, gluconic acid or salts thereof are employed as the stain inhibitor. In an additional aspect, glucaric acid or salts thereof are employed as the stain inhibitor. In an aspect, gluconic acid and glucaric acid ae suitable fr use as a stain inhibitor package fr the compositions according to the invention. Gluconic acid / sodium gluconate is a mild organic acid frmed by the oxidation of glucose whereby the physiological d-frm is produced. lt is also called maltonic acid, and dextronic acid. lt has the molecular frmula C6H12O1 and condensed structural frmula HOCH2(CHOH)4COOH. lt is one ofthe 16 stereoisomers of 2,3,4,5,6-pentahydroxyhexanoic acid. In aqueous solution at neutral pH, gluconic acid frms the gluconate ion and exists in equilibrium with the cyclic ester glucono delta lactone. Gluconic acid, gluconate salts, ad gluconate esters occur widely in nature because such species arise fom the oxidation of glucose.

The stain inhibitor can be provided in amounts fom about 0.1-50 wt-% ofthe cleaning composition. In certain embodiments, the stain inhibitor can comprise fom about 0.1-25 wt-% ofthe cleaning composition, about 1-25 wt-% ofthe cleaning composition, or about 1-10 wt-% ofthe cleaning composition.

Embodiments Examples of suitable frmulations fr concentrated detergent compositions according to the inventon are shown below in Table 1. The concentrated compositons can be frmulated as liquids or solids.

Table 1 First Exemplary Second Exemplary Third Exemplary Ingredient Range (wt. % ) Range (wt.%) Range (wt.%) Alkalinit Source 5-99 % (active) 10-50 % (active) 35-50 % (active) Hydroxyphosphono 0.01-40 wt.% 0.25-20 wt.% 0.5-10 wt.% carboxylic acid Surfactant 0-50 wt.% 0.01-40 wt.% 0.1-30 wt.% The concentrated compositions can optionally include a hardenting or solidifcation 1 O agent in a solid embodiment. In a liquid embodiment the concentrated composition can include water or another suitable diluent suffcient to achieve the desired concentration and viscosit. In a liquid concentrated composition, the water can comprise between about 20 wt. % and about 90 wt. %, prefrably, between 50 wt. % and about 80 wt. %, more prefrably between about 50 wt.% and about 70 wt.%.

The compositions can be concentrate compositions or may be diluted to frm a use solution. In general, a concentrate refrs to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired cleaning, rinsing, or the like. The composition that contacts the surface(s) to be washed can be referred to as a concentrate or a use solution dependent upon the frmulation employed in methods according to the invention. It should be understood that the concentration of the alkalinit source, hydroxyphosphono carboxylic acid, surfctant, water, and other optional functional ingredients in the compositions will vary depending on whether the composition is provided as a concentate or as a use solution.

A use solution may be prepared fom the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having desired alkalinit fr te cleaning application, i.e., a specifcally desired pH range. The water that is used to dilute the concentrate to frm the use composition can be refrred to as water of dilution or a diluent, and can vary fom one location to another. The tpical dilution fctor is between approximately 1 and approximately 10,000 but will depend on fctors including water hardness, the amount of soil to be removed and the like. In an embodiment, the concentrate is diluted at a ratio of between about 1: 1 O and about 1: 1 O, 000 con cen trate to water.

Particularly, the concentrate is diluted at a ratio of between about 1: 100 and about 1:5,000 concentrate to water. More particularly, the concentrate is diluted at a ratio ofbetween about 1 :250 and about 1 :2,000 concentrate to water. Examples of suitable concentrations 1 O fr use solution compositions according to the invention are shown below in Table 2: Table 2 First Exemplary Second Exemplary Third Exemplary Ingredient Range Range Range Alkalinit Source 0.001-12% (active) 0.01-10% (active) 0.1-6% (active) Hydroxyphosphono 0.001-4 wt.% 0.01-2 wt.% 0.1-1 wt.% carboxylic acid Surfactant 0-1000 ppm 0-800 ppm 0-750 ppm Water/Additional q.s. q.s. q.s. functional ingredients 0-5000 ppm 0-3000 ppm 0-2500 ppm Optional Oxidizer t tThe oxidizer is not included in the compositions with the alkalinit source but can be used in the methods at the referenced concentrations or the use solution during the cleaning methods.

Methods of Preparing the Compositions Cleaning composition according to the present invention may be made using a mixing process. The alkainit source, hydroxyphosphono carboxylic acid, surfctant, water, and optional ingredients are mixed fr an amount oftime suffcient to frm a fnal, homogeneous composition. In an exemplary embodiment, the components ofthe cleaning composition are mixed fr approximately 10 minutes. The compositions ofthe invention can be prepared in a multi-part system (non-premix), e.g., two-pat system or three-part system. In such an embodiment, the parts can be in solid frm, liquid frm, or a combination thereof For example, in a two-part system one part can be a solid and the other part can be a liquid. A multi-part system is prefrred fr embodiments ofthe invention including an oxidizer as the oxidizer is incompatible with the alkalinity source.

In such an embodiment, the oxidizer can be applied befre or afer the step of applying the composition having an alkalinit source. Prefrably, the oxidizer is added in a step after.

A solid cleaning composition as used in the present disclosure encompasses a variet of frms including, fr example, solids, pellets, blocks, tablets, and powders. By way of example, pellets can have diameters of between about 1 mm and about 1 O mm, tablets can have diameters of between about 1 mm and about 1 O mm or between about 1 cm and about 1 O cm, and blocks can have diameters of at least about 1 O cm. It should be understood tat the term "solid" refrs to the state ofthe cleaning composition under the expected conditions of storage and use of the solid cleaning composition. In general, it is expected that the cleaning composition will remain a solid when provided at a temperature of up to about 100 ºF or lower than about 120 ºF.

In certain embodiments, the solid cleaing composition is provided in the frm of a unit dose. A unit dose refrs to a solid cleaning composition unit sized so that the entire unit is used during a single cycle, fr example, a single washing cycle of a warewash machine. When the solid cleaning composition is provided as a unit dose, it ca have a mass of about 1 g to about 50 g. In other embodiments, the composition can be a solid, a pellet, or a tablet having a size of about 50 g to 250 g, of about 100 g or greater, or about 40 g to about 11,000 g.

In other embodiments, the solid cleaning composition is provided in the frm of a multiple-use solid, such as, a block or a plurait of pellets, and can be repeatedly used to generate aqueous cleaning compositions fr multiple washing cycles. 1n certain embodiments, the solid cleaning composition is provided as a solid having a mass of about g to about 10 kg. In certain embodiments, a multiple-use frm ofthe solid cleaning composition has a mass of about 1 to about 10 kg. In further embodiments, a multiple-use frm of the solid cleaning composition has a mass of about 5 kg to about 8 kg. In other embodiments, a multiple-use frm of the solid cleaning composition has a mass of about 5 g to about 1 kg, or about 5 g and to about 500 g.

The components can be rxed and extruded or cast to frm a solid such as pellets, powders or blocks. Heat can be applied fom an extemal source to fcilitate processing of the rxture.

A mixing system provides fr continuous mixing ofthe ingredients at high shear to frm a substatially homogeneous liquid or semi-solid mixture in which the ingredients are distributed throughout its mass. Te mixing system includes means fr mixing the ingredients to provide shear efective for maintaning the mixture at a flowable consistency, with a viscosit during processing of about 1, 000-1, 000, 000 cP, prefrably about 50,000-200,000 cP. The mixing system can be a continuous fow mixer or a single or twin screw extruder apparatus.

The mixture can be processed at a temperature to maintain the physical and chemical stabilit ofthe ingredients, such as at ambient temperatures of about 20-80 C., 1 O and about 25-55 C. Although limited extemal heat may be applied to the mixture, the temperature achieved by the mixture may become elevated during processing due to fiction, variances in ambient conditions, and/or by an exothermic reaction between ingredients. Optionally, the temperature of the mixture may be increased, fr example, at the inlets or outlets of the mixing system.

An ingredient may be in the frm of a liquid or a solid such as a dry particulate, and may be added to the mixture separately or as part of a premix with another ingredient, as fr example, the scale control component may be separate fom the remander ofthe warewash detergent. One or more premixes may be added to the mixture.

The ingredients are mixed to frm a substantially homogeneous consistency wherein the ingredients are distributed substantially evenly throughout the mas. The mixture can be discharged fom the mixing system through a die or other shaping means.

The profled extrudate can be divided into useful sizes with a controlled mass. The extruded solid can be packaged in flm. The temperature ofthe mixture when discharged fom the mixing system can be sufciently low to enable the mixture to be cast or extruded directly into a packaging system without frst cooling the mixture. The time between extrusion discharge and packaging can be adjusted to allow the hardening ofthe cleaning composition fr better handling during frther processing and packaging. The mixture at the point of discharge can be about 20-90 C, and about 25-55 C. The composition can be allowed to harden to a solid frm that may range fom a low densit, sponge-like, malleable, caulky consistency to a high densit, fused solid, concrete-like block.

Optionally, heating and cooling devices may be mounted adjacent to mixing apparatus to apply or remove heat in order to obtain a desired temperature profle in the mixer. For example, an extemal source ofheat may be applied to one or more barrel sections ofthe mixer, such as the ingredient inlet section, the fnal outlet section, and the like, to increase fuidit ofthe mixture during processing. Prefrably, the temperature of the mixture during processing, including at the dischage port, is maintained preferably at about 20-90 C.

When processing of the ingredients is completed, the mixture may be discharged fom the mixer through a discharge die. The solidifcation process may last fom a fw minutes to about six hours, depending, fr example, on the size ofthe cast or extruded composition, the ingredients ofthe composition, the temperature ofte composition, and other like fctors. Prefrably, the cast or extruded composition "sets up" or begins to harden to a solid frm within about 1 minute to about 3 hours, prefrably about 1 minute to about 2 hours, most prefrably about 1 minute to about 1. O hours minutes.

The concentrate can be provided in the frm of a liquid. Various liquid frms include gels and pastes. Of course, when the concentrate is provided in the frm of a liquid, it is not necessay to harden the composition to frm a solid. In fct, it is expected that the amount ofwater in the composition will be sufcient to preclude solidifcation. In addition, dispersants and other components can be incorporated into the concentrate in order to maintain a desired distribution of components.

In aspects ofthe invention employing packaged solid cleaing compositions, the products may frst require removal fom any applicable packaging (e.g flm). Thereafter, according to certain methods of use, the compositions can be inserted directly into a dispensing apparatus and/or provided to a water source fr cleaning according to the invention. Examples ofsuch dispensing systems include fr example U.S. PatentNos. 4,826,661, 4,690,305, 4,687,121, 4,426,362 and U.S. PatentNos. Re 32,763 and 32,818, the disclosures ofwhich are incorporated by refrence herein in its entiret. Ideally, a solid cleaning composition is confgured or produced to closely ft the particular shape(s) of a dispensing system in order to prevent the introduction and dispensing of an incorrect solid product into te apparatus of the present invention. The packaging receptacle or container may be rigid or fexible, and composed of any material suitable fr containing the compositions produced according to the invention, as fr example glass, metal, plastic flm or sheet, cardboard, cardboard composites, paper, and the like. The composition is processed at around 150-170 F and are generally cooled to 100-150 befre packaging. so that processed mixture may be cast or extruded directly into the container or other packaging system without structurally damaging the material. As a result, a wider variet of materials may be used to manufacture the container than those used fr compositions that processed and dispensed under molten conditions.

In certain embodiments, the cleaning composition may be mixed with a water source prior to or at the point of use. In other embodiments, the cleaning compositions do not require the frmation of a use solution and/or further dilution and may be used without frther dilution.

In aspects of the invention employing solid cleaning compositions, a water source 1 O contacts the cleaning composition to convert solid cleaning compositions, particularly powders, into use solutions. Additional dispensing systems may also be utilized which are more suited fr converting atemative solid detergents composit ions into use solutions. The methods of the present invention include use of a variet of solid cleaning compositions, including, fr exaple, extruded blocks or "capsule" tpes of package.

In a aspect, a dispenser may be employed to spray water (e.g in a spray pattem fom anozzle) to frm a cleaning use solution. For example, water may be sprayed toward an apparatus or other holding reservoir with the cleaning composit ion, wherein te water reacts with the solid cleaning composition to form the use solution. In certain embodiments ofthe methods ofthe invention, a use solution may be confgured to drip downwardly due to gravit until the dissolved solution of the cleaning composition is dispensed fr use according to the invention. In an aspect, the use solution may be dispensed into a wash solution of a ware wash machine.

In an aspect of the invention the compositions can be prepared prior to or at a hard surface being cleaned. For example, the compositions can be combined silmulateneously or in a sequential arder at a hard surfce fr cleaning. In such method of preparation, the composition can be frmed when the components contact the hard surface to be cleaned.

Further, this can occur prior to or with addition of water of dilution. In an aspect of the invention, a system having a pluralit of inlents can introduce one or more of the components at a desired dosage to the hard surfce such that the composition frms at the hard surface.

Methods of the Cleaning The cleaning compositions of the invention are frther suitable for use in cleaning surfaces fom vaious applications and methods, including but not limited to, cleaning of clean-in-place (CIP) surfaces, clean-out-of-place (COP) surfaces, fod processing surfaces (such as evaporators, heat exchangers, tanks, lines, separators, clarifiers, fine savers, contherms, scrape surfces, and boilers). In addition, the methods of the invention are well suited fr preventing andor reducing staining and discoloration of alunum and its alloys, nickel and its alloys, tin and its alloys, and some grades of stainless steel, including, 300 series stainless, 400 series stainless steel, and their alloys. The methods ofthe invention can reduce andor prevent moderate to heavy staining, discoloration, and pitting 1 O of the cleaned surfaces.

In a benefcia! aspect ofthe invention, the methods ofthe invention reduce and/or prevent discoloration and staining of stainless steel fod and beverage equipment caused by combination of alkalinity and high temperature during the cleaning of the surfce.

Without being bound by the theory, it is believed that the combination ofhigh temperature and alkalinit in existing cleaning methods can disrupt the passivation layer on te surface allowing the alkalinity to discolor, stain, and even pit the surface. It was fund that the passivation layer was disrupted at both the liquid-gas interface and at the surface submerged in the liquid phase. It is believed that the passivation layer is disrupted as the liquid evaporates into the gas phase thereby increasing alkalinit concentration. This was evidenced by discoloration and corrosion at the interfce. As the passivation layer protects the surfce fom staining, discoloration, and pitting, the disruption of the passivation layer leaves the surfce vulnerable to the corrosive nature of the caustic ingredients. The corroded surfce damages the aesthetic appearance ofthe surfce. Without wishing to be bound by the theory, it is believed that the cleaning compositions and methods ofthe invention prevent disruption ofthe passivation layer on the surfce thereby preventing and/or reducing the discoloration, staining, and pitting ofthe surfce. lt is believed that the cleaning compositions ofthe invention can provide a protective layer over the passivation layer, thereby preventing and/or reducing the discoloration, staining, and pitting of the surface.

The cleaning compositions of the invention may be in the frm of a liquid or solid.

Solid compositions include extruded, pressed or cast solids. The compositions are suitable fr use at temperature ranges tpically used in warewash applications (e.g., about 120 ºF to about 180 ºF) or the temperature range fr the surface being cleaned (e.g., a boiler at temperatures near or exceeding te boiling temperature of water, i.e., around or even greater than about 212 ºF).

According to an embodiment ofthe invention, a metal surfce is contacted by a cleaning composition. The cleaning composition may be in a concentrate or a diluted frm. Contacting can include any of numerous methods known by those of skill in the art fr applying a compound or composition of the invention, such as spraying, immersing the metal surfce in the cleaning composition or use solution, dispensing the cleaning composition over a surfce in granular or paticulate frm, simply pouring the cleaning 1 O composition or a use solution onto or into the fod process surfce, rinsing te fod processing surfce with a use solution, or a combination thereof The methods can be perfrmed by adding the compositions to a CIP unit, COP unit, warewash machine, or directly to ware or the soiled metal surfce.

The compositions according to the invention can be provided as a solid, liquid, or a combination tereof As set frth in te description of te compositions, the compositions can be provided in one or more parts, such as the frmulation ofthe composition to include the alkalinity source, hydroxyphosphono carboxylic acid, surfctant, water, and optional ingredients. Altematively, the cleaning composition may be provided in two or more parts (non-premix), such that the overall composition is frmed in the use solution upon combination oftwo or more compositions. Each ofthese embodiments are included within the fllowing description of the methods of the invention.

If using a non-premixed composition, e.g., a composition that does not contan the hydroxyphosphono carboxylic acid or the optional oxidizer, then the composition can be mixed immediately prior to use or at the point of use. For example, a use solution can be prepared and then contacted to the soiled metal surfce. Another example is that the diferent components can be added separately directly to the soiled surfce to frm the use solution.

A beneft ofthe compositions ad methods of the invention is the prevention and/or reduction of discoloration, staining, corrosion, and/or pitting of the hard surfce being cleaned. For example, in embodiments of the invention, a hard surfce ca have less than %, prefrably less than 10%, more prefrably less than 5%, most prefrably less than 3% of its surfce area increase in discoloration, staining, corrosion, and/ or pitting ater at least two cleaning cycles with a cleaning solution having a pH between about 9 and about 14 containing a hydroxide-based alkalinit source.

EXAMPLES Embodiments of the present invention are further def ned in the fllowing non- limiting Examples. It should be understood that these Examples, while indicating certain embodiments ofthe 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 ofthis invention, and without depating fom the spirit and scope thereof, can mae various changes and modifcations ofte embodiments ofthe invention to adapt it to various usages and conditions. Thus, various modifcations ofthe embodiments ofthe invention, in addition to those shown and described herein, will be apparent to tose skilled in the art fom the fregoing description. Such modifcations are also intended to fall witin the scope of the appended claims.

Materiais and Suppliers The fllowing materials were employed in the Examples fr evaluation of stanless steel corrosion inhibition ofthe compositions.

Belcor 575 - hydroxyphosphono acetic acid avalable fom Water Additives.

NaOH - sodium hydroxide Procedure to Test Stainless Steel Corrosion Preparation of Coupons Stainless steel coupons were obtained having a size of approxirtely 3"xl "xl/16".

The coupons were cleaned and passivated prior to testing to simulate feld equipment. The coupons were scrubbed wit a polishing cleanser ad then rinsed with distilled water.

Next, the coupons were placed in a beaker, covered with tolu ene and sonicated at ambient temperature fr 30 minutes to remove any adhesive or oils. After the coupons were rinsed with acetone and then dried. The coupons were ten sonicated in a 15% diamonium citrate solution fr 20 minutes at 150 ºF. After sonication they were rinsed with distilled water and stored in a desiccator until dr.

Stock solutions ofthe compositions to be tested were prepared. Next a sample bottle was flled wit approximately 115g of a test solution and a stainless steel coupon was suspended into the solution so that approxim ately ¾ ofthe coupon on all sides was immersed in the solution. Each test solution was run in triplicate fr each tpe of stainless steel coupon.

Dr-Down Test For Examples 1, 2, and 4 below, a dry-down test was performed. The procedure wa to place saple bottles in a uncovered oven at 80 ºC to allow the test solutions to until suffcient evaporation occurred to create a high concentration "dry-down" efect.

Solutions and coupons remained uncovered in the oven fr a test period. After the test period, the coupons were removed from the bottles and rinsed with distilled water.

Soak Test For Example 3 below a soa test was perfrmed. The procedure was to place sample bottles in an uncovered oven at 80 ºC ovemight. After one ovemight soak, the coupons were removed fom the bottles, rinsed with distilled water, and the solution was replaced to maintain an active amount ofthe oxidizer, EXCELERATE HS (available fom Ecolab). This was repeated fr 12 cycles; each ovemight soak was considered one cycle.

Evaluation of Coupons The coupons were then evaluated fr any staining/discoloration and photographed.

Image anaysis was perfrmed with Figi Image J Software fr quantitative comparisons.

Stainless steel images were scanned using color and grey scale. The grey scale images were used for the Fiji image analysis evaluation.

During image analysis, a threshold value of 145 was chosen. The total threshold range is fom O to 255, where a value of 255 reads all black pixels and a vaue of O reads all white pixels on the coupon. A threshold value of 145 maxirzes the dynac range across the compositions in te result analysis. This value allowed fr no/rnimal discoloration on a new coupon and adequately captured te discoloration on the negative control.

Once the treshold value was set, the entire coupon area was selected and the area wa measured fr percent discoloration. The percent discoloration was averaged across the three coupons in each frmulation. Formulations with a lower percent discoloration across the coupon denotes improved perfrmanc e.

EXAMPLE 1 Belcor 575 (hydroxyphosphono acetic acid), an exemplary hydroxyphosphono caboxylic acid, was used in a solution of about 1 % (active) Belcor 575 and about 4% (active) NaOH. The effect ofhydroxyphosphono acetic acid contained in Belcor 575 on stainless steel corrosion was evaluated and the results were compared with the result obtained with a control solution, i.e. a 4% NaOH solution. The evaluation was carried out fr an 8 week period on stainless steel series 304 and stainless steel series 316, the stain fr each solution was read and analyzed at te end of each week as described in te general procedure described above. The results of the quatifcation analysis are provided in Figures 1 and 2. Figure 1 shows the results on stainless steel series 304 and Figure 2 1 O shows the results on stainless steel series 316. Both fgures demonstrate a dramatic reduction in discoloration.

EXAMPLE2 The efect ofthe concentration of hydroxyphosphono carboxylic acid was examined. Belcor 575 was again used as the exempla hydroxyphosphono carboxylic acid and varying concentrations were compared with a control solution, i.e. a 4% (active) NaOH solution. Five exempl compositions ofthe invention were prepared with 4% (active) NaOH and concentrations ofthe Belcor 575 in active amounts of 0.01 %, 0.1 %, 0.25%, 0.5%, and 1 %. The evaluation was carried out fr a two week period, the stain fr each solution on stainless steel series 304 and stainless steel series 316 was read and analyzed at the end ofthe second week. The results ofthe quantifcation analysis are provided in Figure 3. The results show that the frmulations containing the hydroxycarboxylic acid each reduced the discoloration compared with the control.

EXAMPLE3 An exemplary composition ofte invention was tested with the use of an oxidizer.

The exemplary composition ofthe invention contained 0.5% (active) Belcor 575, 4% (active) NaOH, and 0.1 % of an oxidizer. The results were compared with a control solution of a 4% (active) NaOH solution and 0.1 wt.% oxidizer. The oxidizer solution used was EXCELERATE HS, available from Ecolab, Inc. The evaluation was carried out for a 12 cycle period on stanless steel series 304 and stainless steel series 316. The stain fr each solution was read and analyzed at the end of the 12th cycle, respectively. The test results fr the control solution and each tested solution are summarized in Figure 4. The results show that the frmulations containing te hydroxycarboxylic acid each reduced the discoloration compared wit the control. This is signifcant as oxidizer's will typically accelerate corrosion and discoloration, particularly as the concentration of oxidizer maintaned over the 12 cycles.

EXAMPLE4 An exemplary composition of te invention was tested in comparison to a control solution of a 4% (active) NaOH and 1% (active) EDTA and a control solution of 4% (active) NaOH. The exemplary composition of the invention contained 1 % (active) Belcor 575, 4% (active) NaOH. The evaluation was carried out fr a 6 week period on stainless steel series 304 and stainless steel series 316. The stain fr each solution was read and analyzed at the end ofthe sixth week. The test results fr te control solutions and the exemplary solution is summarized in Figure 5. As can be seen in Figure 5, the hydroxyphosphono carboxylic acid provided a dramatic reduction in discoloration versus the control and EDT A frmulation.

The inventions being thus described, it will be obvious that the same may be varied in many ways. Such variations ae not to be regaded as a departure fom the spirit and scope ofthe inventions and all such modifcations are intended to be included within the scope ofthe following claims. The above specifcation provides a description ofthe manufacture and use ofthe disclosed compositions and methods. Since may embodiments can be made without departing fom the spirit and scope ofthe invention, the invention resides in the claims.

Claims (19)

WE CLAIM :

1. A method for cleaning a hard surface comprising: contacting a hard surface with a cleaning composition comprising an alkalinity source and a hydroxyphosphono carboxylic acid; wherein the alkalinity source comprises an alkali metal hydroxide; diluting the cleaning composition to form an aqueous cleaning solution; adding an oxidizer to the aqueous cleaning solution, wherein the aqueous cleaning solution has a pH of at least about 9; and rinsing the hard surface.

2. The method of claim 1, wherein the cleaning composition is formed prior to or at the hard surface being cleaned; and wherein the contacting step is performed prior to or simultaneously with the diluting step.

3. The method of claim 1 or 2, wherein the concentration of hydroxyphosphono carboxylic acid in the aqueous cleaning solution is between about 0.001% (active) and about 4% (active); and wherein the concentration of alkalinity source in the aqueous cleaning solution is between about 0.001% (active) and about 12% (active).

4. The method of any one of claims 1-3, wherein the aqueous cleaning solution has a pH of between about 10 and about 14.

5. The method of any one of claims 1-4, wherein the aqueous cleaning solution further comprises a surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, anionic surfactants, and combinations thereof in a concentration of between about 0 ppm to about 1000 ppm.

6. The method of any one of claims 1-5, wherein the oxidizer is in a concentration from about 50 ppm to about 5000 ppm.

7. The method of any one of claims 1-6, wherein the hard surface is a stainless steel clean-in- place surface, clean-out-of-place surface, or heat processing surface. (27394967_1):RTK

8. The method of any one of claims 1-7, wherein the cleaning composition is a pre-mix solid or a pre-mix liquid.

9. The method of any one of claims 1-8, wherein the concentration of hydroxyphosphono carboxylic acid in the aqueous cleaning solution is between about 0.01% (active) and about 1% (active), and wherein the concentration of alkalinity source in the aqueous cleaning solution is between about 0.1% (active) and about 6% (active).

10. A hard surface cleaning composition comprising: between about 5 wt.% and about 99 wt.% (active) of an alkalinity source, wherein the alkalinity source comprises an alkali metal hydroxide; between about 0.01 wt.% to about 40 wt.% of a hydroxyphosphono carboxylic acid; and an oxidizer, wherein the oxidizer is in a separate part from the alkalinity source.

11. The hard surface cleaning composition of claim 10, further comprising a surfactant between about 0.01 wt.% and about 40 wt.%, wherein the surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, anionic surfactants, and combinations thereof.

12. The hard surface cleaning composition of claim 10 or 11, wherein the composition is a concentrated liquid composition and has between about 20 wt.% and about 90 wt.% water.

13. The hard surface cleaning composition of any one of claims 10-12, wherein the cleaning composition is a pre-mix solid or a pre-mix liquid.

14. The hard surface cleaning composition of any one of claims 10-12, wherein the composition is a multi-part system where the hydroxyphosphono carboxylic acid and the alkalinity source are in separate parts.

15. A method of making a hard surface cleaning composition comprising: combining a hydroxyphosphono carboxylic acid, an oxidizer, and an alkalinity source to form a cleaning composition; (27394967_1):RTK wherein the alkalinity source is between about 5 wt.% and about 99 wt.% (active) of the composition and comprises an alkali metal hydroxide; and wherein the hydroxyphosphono carboxylic acid is between about 0.01 wt.% to about 40 wt.% of the composition, and wherein the composition is prepared from a multi-part system and the oxidizer is in a separate part from the alkalinity source.

16. The method of claim 15, wherein the composition is a solid pre-mix or a liquid pre-mix.

17. The method of claim 15 or 16, wherein the composition is a multi-part system and the hydroxyphosphono carboxylic acid is in a separate part than the alkalinity source.

18. The method of any one of claims 15-17, wherein the composition further comprises a surfactant between about 0.01 wt.% and about 40 wt.% of the composition, and wherein the surfactant is in the same part as hydroxyphosphono carboxylic acid.

19. The method of any one of claims 15-18, further comprising adding water to the composition. Ecolab USA Inc. By the Attorneys for the Applicant SPRUSON & FERGUSON Per: (27394967_1):RTK