EP3114197B1

EP3114197B1 - Detergent composition that performs both a cleaning and rinsing function

Info

Publication number: EP3114197B1
Application number: EP15759090.2A
Authority: EP
Inventors: Monique ROERDINK-LANDER; Carter M. Silvernail; Erin Jane DAHLQUIST HOWLETT; Kerrie E. WALTERS
Original assignee: Ecolab USA Inc
Current assignee: Ecolab USA Inc
Priority date: 2014-03-07
Filing date: 2015-03-02
Publication date: 2023-06-07
Anticipated expiration: 2035-03-02
Also published as: EP3114197C0; MX2016011249A; KR20180071422A; EP3114197A1; BR112016020336A2; WO2015134404A1; AU2015225441B2; JP2017507236A; AU2015225441A1; KR101982707B1; JP6871452B2; JP2020109193A; EP3114197A4; CA2941511C; CN106103679A; BR112016020336B1; CA2941511A1; CN113736588A; JP2018188653A; ES2949191T3

Description

FIELD OF THE INVENTION

The invention relates to an industrial 2-in-1 cleaning composition providing both detergency and rinse aid efficacy in a single cleaning composition. In particular, compositions and methods of both making and using the same provide a user-friendly, solid, detergent composition without the need for using a separate rinse aid composition. The compositions and methods are particularly well suited for use in industrial cleaning using alkali metal carbonate compositions that beneficially provide cleaning and rinseability to permit the use of a potable water rinse without the addition of a separate rinse agent.

BACKGROUND OF THE INVENTION

Alkaline detergents are used extensively to clean articles in both consumer and industrial dish machines. Alkaline detergents are extensively used because of their ability to remove and emulsify fatty, oily, hydrophobic soils. However, alkaline detergents have the disadvantage of requiring a rinse aid to prevent the formation of films on glass and other substrate surfaces contacted by the alkaline detergent. Filming is caused in part by using alkaline detergents in combination with certain water types (including hard water), and water temperatures. A solution to the generation of hard water films has been to employ rinse aids to remove such films. However, the need for rinse aids increases the cost associated with alkaline detergents for both the formulation of the cleaning compositions as well as the additional costs associated with heated water for rinsing steps.
Additionally, rinse aids are used in a rinse cycle following the wash cycle to enhance drying time, as well as reduce any cleaning imperfections (including the removal of films). Additional benefits and methods of using rinse aids are described in U.S. Patent No. RE 38262 . The addition of rinse aids to a ware wash rinse cycle requires use of GRAS (generally recognized as safe) ingredients as well as wall space for the installation of both a detergent dispenser and a rinse aid dispenser.
There is a need for alternative, effective cleaning compositions that provide the desired cleaning results and at the same time reduce the number of components required for cleaning and rinsing.
Accordingly, it is an objective of the claimed invention to develop an alkaline detergent composition that provides good cleaning performance and good rinseability in a potable water rinse without the use of an added rinse aid in the rinse cycle.
A further object of the invention is to provide a carbonate-based alkaline detergent employing a combination of surfactants, and optionally polymers, to provide good cleaning performance and rinseability without the use of a rinse aid in the cleaning composition.
A further object of the invention is to provide a carbonate-based alkaline detergent employing a combination of surfactants, and optionally polymers, providing at least substantially similar cleaning and rinsing efficacy as a conventional two part detergents and rinse aids.
Other objects, advantages and features of the present invention will become apparent from the following specification taken in conjunction with the accompanying drawings.
US R E38 262 E discloses a detergent which can include a cleansing source of alkalinity, a rinsing source of nonionic and can contain additional ingredients such as surfactants, rinse agents, builders, hardness sequestering agents, etc.
US 2010/065090 A1 relates to a phosphate-containing machine dishwasher detergent comprising 0.01-20% by weight of at least one alcohol alkoxylate, 0.01-10% by weight of at least one alcohol ethoxylate, 0-15% by weight of at least one sulfonate-containing polymer, 0-15% by weight of at least one hydrophilically modified polycarboxylate, 0-8% by weight of at least one polycarboxylate, 1-70% by weight of at least one phosphate and 0.1-60% by weight of at least one further additive, where the sum of components (A), (B), (C), (D), (E), (F) and (G) is 100% by weight.
EP 0 687 720 A2 disclose a machine dishwashing composition wherein two specifically defined nonionic surfactants are utilized which in combination have been shown through empirical research to surprisingly yield improved results.

BRIEF SUMMARY OF THE INVENTION

An advantage of the invention is industrial detergent compositions providing both detergency and rinseability in a single cleaning composition, thus eliminating the need for an additional rinse aid composition. The composition of the invention provides thus a user-friendly, solid, 2-in-1 cleaning and rinsing action, beneficially eliminating a distinct rinse aid from the industrial warewashing compositions and methods of use. The alkaline detergent compositions according to the invention beneficially provide both good cleaning performance and rinseability in a potable water rinse without the use of an added rinse aid in the rinse cycle.
In an embodiment, the present invention provides an alkaline detergent and rinsing composition comprising from 45 wt-% to 75 wt-% of an alkalinity source comprising an alkali metal carbonate; and at least two nonionic surfactants, wherein said nonionic surfactants comprise from 1 wt-% to 10 wt-% of the alkaline detergent composition of a C10-C12 alcohol alkoxylate with 15 to 25 moles of alkyl oxide and from 1 wt-% to 10 wt-% of the alkaline detergent composition of an EO/PO copolymer represented by the formula (PO)y(EO)x(PO)y, where x is in the range of 5 to 50, y is in the range of 1 to 50, and x plus y is in the range of 6 to 200; and from 5 wt-% to 50 wt-% of a builder selected from the group consisting of condensed phosphates, alkali metal silicates and metasilicates, phosphonates and aminocarboxylic acids; wherein said composition performs both a cleaning and rinsing function. The detergent compositions can also include polymers, such as a polycarboxylic acid polymer, water conditioning agents, neutralizing agents, sanitizers. The composition may further comprise an enzyme. The enzyme may be a protease, lipase and/or amylase. The composition may further comprise a polymer comprising a polycarboxylic acid polymer, copolymer, and/or terpolymer.
In another embodiment, the present invention provides a method of cleaning and rinsing ware comprising contacting ware with an alkaline detergent composition as defined above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a graph of the average dynamic surface tension of an experimental formulation (Exp. 1) in comparison to phosphate-based alkaline detergents as well as nonionic-based rinse aids at a temperature of 71. 1°C (160°F) as a function of the average bubble life time at use concentrations. The values shown are averages of three independent measurements. According to an embodiment of the invention, the experimental formulation demonstrates a quick decrease and significant drop in surface tension, similar to a well-performing commercial rinse aid, such as rinse aid control 2.
FIG. 2 shows a graph of the average dynamic surface tension of an experimental formulation (Exp. 2) in comparison to phosphate-based alkaline detergents as well as nonionic-based rinse aids at a temperature of 71. 1°C (160°F) as a function of the average bubble life time at use concentrations. The values shown are averages of three independent measurements. According to an embodiment of the invention, the experimental formulation demonstrates a quick decrease and significant drop in surface tension, similar to a well-performing commercial rinse aid, such as rinse aid control 2.

Various embodiments of the present invention will be described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The present invention relates to a 2-in-1 industrial alkaline cleaning compositions which provide suitable cleaning and rinseability while employing a carbonate-based alkaline detergent and a combination of surfactants. In an exemplary embodiment, the nonionic surfactants create an efficacious aqueous rinse with potable water.
For example, as used in this specification and the appended claims, the singular forms "a," "an" and "the" can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.
Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this invention are presented in a range format. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 , as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
So that the present invention may be more readily understood, certain terms are first defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain.In describing and claiming the embodiments of the present invention, the following terminology will be used in accordance with the definitions set out below.
The term "actives" or "percent actives" or "percent by weight actives" or "actives concentration" are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts.
As used herein, the term "alkyl" refers to a straight or branched chain monovalent hydrocarbon group optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N. Alkyl groups generally include those with one to twenty atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example. Examples of "alkyl" as used herein include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, isopropyl, and C8-C20 alkyl chains .
As used herein, the term "alkylene" refers to a straight or branched chain divalent hydrocarbon group optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N. Alkylene groups generally include those with one to twenty atoms. Alkylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example. Examples of "alkylene" as used herein include, but are not limited to, methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl .
As used herein, the term "alkenylene" refers to a straight or branched chain divalent hydrocarbon group having one or more carbon-carbon double bonds and optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N. Alkenylene groups generally include those with one to twenty atoms. Alkenylene groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example. As used herein, the term "alkylyne" refers to a straight or branched chain divalent hydrocarbon group having one or more carbon-carbon triple bonds and optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N. Alkylyne groups generally include those with one to twenty atoms. Alkylyne groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
As used herein, the term "alkoxy", refers to --O--alkyl groups wherein alkyl is as defined above. As used herein, the term "cleaning" refers to a method used to facilitate or aid in soil removal, bleaching, microbial population reduction, and any combination thereof.
The term "generally recognized as safe" or "GRAS," as used herein refers to components classified by the Food and Drug Administration as safe for direct human food consumption or as an ingredient based upon current good manufacturing practice conditions of use, as defined for example in 21 C.F.R. Chapter 1, §170.38 and/or 570.38.
As used herein, the term "soil" or "stain" refers to a polar or non-polar substances which may or may not contain particulate matter such as, but not limited to mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust and food soils such as polyphenols starches, proteins, oils and fats.
As used herein, the term "substantially free" refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and shall be less than 0.5 wt-%. In another embodiment, the amount of the component is less than 0.1 wt-% and in yet another embodiment, the amount of component is less than 0.01 wt-%.
The term "substantially similar cleaning performance" refers generally to achievement by a substitute cleaning product or substitute cleaning system of generally the same degree (or at least not a significantly lesser degree) of cleanliness or with generally the same expenditure (or at least not a significantly lesser expenditure) of effort, or both.
The term "threshold agent" refers to a compound that inhibits crystallization of water hardness ions from solution, but that need not form a specific complex with the water hardness ion. Threshold agents include but are not limited to a polyacrylate, a polymethacrylate, an olefin/maleic copolymer.
As used herein, the term "ware" refers to items such as eating and cooking utensils, and dishes. As used herein, the term "warewashing" refers to washing, cleaning, or rinsing ware. Ware also refers to items made of plastic. Types of plastics that can be cleaned with the compositions according to the invention include but are not limited to, those that include polycarbonate polymers (PC), acrilonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Other exemplary plastics that can be cleaned using the compounds and compositions of the invention include polyethylene terephthalate (PET) and plastics from melamine resin.
The term "weight percent," "wt-%," "percent by weight," "% by weight," and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, "percent," "%," are intended to be synonymous with "weight percent," "wt-%," .
The methods and compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.

Alkaline 2-in-1 Detergent Compositions

Alkalinity Source

The alkaline detergent compositions include from 45 wt-% to 75 wt-% of an alkalinity source. The alkalinity source comprises an alkali metal carbonate. Examples of suitable alkalinity sources include but are not limited to: alkali metal carbonates, such as sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, and mixtures thereof. In an aspect, the alkaline detergent compositions do not include a hydroxide alkalinity source. The alkalinity source controls the pH of the use solution when water is added to the detergent composition to form a use solution. The pH of the use solution must be maintained in the alkaline range in order to provide sufficient detergency properties. In one embodiment, the pH of the use solution is between 9 and 12. Particularly, the pH of the use solution is between 9.5 and 11.5.
In certain embodiments, the alkalinity source may also function as a hydratable salt to form a solid composition. The hydratable salt can be referred to as substantially anhydrous. By substantially anhydrous, it is meant that the component contains less than 2% by weight water based upon the weight of the hydratable component. The amount of water can be less than 1% by weight, and can be less than 0.5% by weight. As one skilled in the art will ascertain, there is no requirement that the hydratable salt be completely anhydrous. In certain embodiments, there is also water of hydration to hydrate the alkalinity source (i.e. hydratable salt). It should be understood that the reference to water includes both water of hydration and free water. The phrase "water of hydration" refers to water which is somehow attractively bound to a non-water molecule. An exemplary form of attraction includes hydrogen bonding. The water of hydration also functions to increase the viscosity of the mixture during processing and cooling to prevent separation of the components. The amount of water of hydration in the detergent composition will depend on the alkalinity source/hydratable salt. In addition to water of hydration, the detergent composition may also have free water which isn't attractively bound to a non-water molecule.

Surfactants

The 2-in-1 alkaline compositions according to the invention employ a combination of at least two nonionic surfactants, wherein said nonionic surfactants comprise from 1 wt-% to 10 wt-% of the alkaline detergent composition of a C10-C12 alcohol alkoxylate with 15 to 25 moles of alkyl oxide and from 1 wt-% to 10 wt-% of the alkaline detergent composition of an EO/PO copolymer represented by the formula (PO)y(EO)x(PO)y, where x is in the range of 5 to 50, y is in the range of 1 to 50, and x plus y is in the range of 6 to 200 to provide good cleanability and rinseability. In an aspect, the alkaline detergent compositions include from 5 wt-% - 10 wt-% surfactants.
In some embodiments, the ratio of the alcohol alkoxylate to the EO/PO copolymer is from 1:5 to 5:1, from 1:3 to 3:1, from 1:2 to 2:1, and preferably 1:1.

Alcohol Alkoxylates

The 2-in-1 alkaline compositions according to the invention employ at least two nonionic surfactant comprising an alcohol alkoxylate. Suitable alcohol alkoxylates include ethylene oxide, propylene oxide, and butylene oxide groups and mixtures thereof. The alcohol alkoxylate is a C10-C12 alcohol alkoxylate with 15 to 25 moles of alkyl oxide. Examples of preferred alcohol alkoxylates are available under the brands Surfonic (available from Huntsman), Rhodasurf (available from Rhodia), Novel (available from Sasol), Lutensol (available from BASF).
The alkaline detergent compositions include from 1 wt-% to 10 wt-% alcohol alkoxylate, or from 1 wt-% to 7 wt-%.

EO/PO copolymers

The 2-in-1 alkaline compositions according to the invention employ an EO/PO copolymer. Exemplary commercially available surfactants are available, for example, under the tradename Pluronic^® and Pluronic R, (commercially available from BASF), Tetronic (available from Dow) and Surfonic (available from Huntsman).
Ethylene oxide and propylene oxide derivative surfactants that are used are polyoxyethylene-polyoxypropylene block copolymers having the following formula:

(PO)y(EO)x(PO)y

wherein EO represents an ethylene oxide group, PO represents a propylene oxide group, and x and y reflect the average molecular proportion of each alkylene oxide monomer in the overall block copolymer composition: x is in the range of 5 to 50, y is in the range of 1 to 50, and x plus y is in the range of 6 to 200. It should be understood that each x and y in a molecule can be different. In some embodiments, the material can have a molecular weight greater than 200 and less than 25,000. For example, in some embodiments, the material can have a molecular weight in the range of 500 to 25,000, or in the range of 1000 to 20,000.
In some embodiments, the material can have a molecular weight greater than 400, and in some embodiments, greater than 500. For example, in some embodiments, the material can have a molecular weight (g/mol) in the range of 500 to 7000 or more, or in the range of 950 to 4000 or more, or in the range of 1000 to 3100 or more, or in the range of 2100 to 6700 or more, or in the range of 2500 to 4200 or more.
The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 provides further description of nonionic compounds generally employed in the practice of the present invention. A typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975 . Further examples are given in "Surface Active Agents and detergents" (Vol. I and II by Schwartz, Perry and Berch).
The alkaline detergent compositions include from 1wt-% to 10 wt-% of the alkyl alkoxylate, or from 1 wt-% to 7 wt-% the alkyl alkoxylate.

Polymer

The present invention can include a polymer comprised of at least one polycarboxylic acid polymer, copolymer, and/or terpolymer. Particularly suitable polycarboxylic acid polymers of the present invention, include, but are not limited to, polyacrylic acid polymers and copolymers, polymaleic polymers and copolymers, and acrylic/maleic copolymers. Other suitable polycarboxylic acid polymers include polymaleic acid homopolymers, polyacrylic acid copolymers, and maleic anhydride/olefin copolymers. In a preferred embodiment, the polymer comprises, consists essentially of, or consists of a polyacrylic acid polymer, copolymer, terpolymer and/or salts thereof.
The detergent compositions of the present invention can use polyacrylic acid polymers, copolymers, and/or terpolymers. Polyacrylic acids have the following structural formula:
where n is any integer. Examples of suitable polyacrylic acid polymers, copolymers, and/or terpolymers, include but are not limited to, the polymers, copolymers, and/or terpolymers of polyacrylic acids, (C₃H₄O₂)_n or 2-Propenoic acid, acrylic acid, polyacrylic acid, propenoic acid.
In an embodiment of the present invention, particularly suitable acrylic acid polymers, copolymers, and/or terpolymers have a molecular weight between 100 and 10,000, in a preferred embodiment between 500 and 7,000, in an even more preferred embodiment between 1,000 and 5,000, and in a most preferred embodiment between 1,500 and 4,500.
Polymaleic acid (C₄H₂O₃)x or hydrolyzed polymaleic anhydride or cis-2-butenedioic acid homopolymer, has the structural formula:
where n and m are any integer. Examples of polymaleic acid homopolymers, copolymers, and/or terpolymers (and salts thereof) which may be used for the invention are particularly preferred are those with a molecular weight of 100 and 10,000, more preferably between 500 and 7,000, in an even more preferred embodiment between 1,000 and 5,000, and in a most preferred embodiment between 1,500 and 4,500. Commercially available polymaleic acid homopolymers include the Belclene 200 series of maleic acid homopolymers from BWA^™ Water Additives, 979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA and Aquatreat AR-801 available from AkzoNobel.
In a preferred embodiment, the polymer is a copolymer of acrylic acid and maleic acid. Preferably, an acrylic/maleic acid copolymer an acrylic/maleic copolymer has a molecular weight from 1,000 to 10,000 g/mol, preferably a molecular weight between 1,000 to 5,000 g/mol. An example of a suitable acrylic/maleic acid copolymer includes, but is not limited to, Acusol 448 from The Dow Chemical Company, Wilmington Delaware, USA.
In embodiments employing a polymer, it is expected that the compositions will include the polymer in an amount between 0.1 wt-% and 50 wt-%, between 0.1 wt-% and 40 wt-%, between 0.1 wt-% and 30 wt-%, or 1 wt-% and 20 wt-%. All ranges recited are inclusive of the numbers contained therein. The polymer of the present invention can comprise, consist essentially of, or consist of at least one polyacrylic acid polymer, copolymer, and/or terpolymer. In addition, without being limited according to the invention, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Additional Functional Ingredients

The 2-in-1 alkaline compositions according to the invention can further be combined with various functional components suitable for use in industrial ware wash applications. In some embodiments, the alkaline detergent and rinse aid compositions including the carbonate-based alkalinity source and nonionic surfactants (and/or polymers) make up a large amount, or even substantially all of the total weight of the detergent composition. For example, in some embodiments few or no additional functional ingredients are disposed therein.
In other embodiments, additional functional ingredients may be included in the compositions. The functional ingredients provide desired properties and functionalities to the compositions. For the purpose of this application, the term "functional ingredient" includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only, and that a broad variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning, specifically ware wash applications. However, other embodiments may include functional ingredients for use in other applications.
In preferred embodiments, the compositions do not include additional alkalinity sources, namely alkali metal hydroxides. In further preferred embodiments, the compositions do not include rinse aids.
The compositions include builders, and may include water conditioning agents, stabilizers, defoaming agents, anti-redeposition agents, bleaching agents, sanitizers, solubility modifiers, dispersants, anticorrosion agents and metal protecting agents, stabilizing agents, corrosion inhibitors, enzymes, additional sequestrants and/or chelating agents, fragrances and/or dyes, rheology modifiers or thickeners, hydrotropes or couplers, buffers, solvents, solidifying agents .

Builders

The alkaline detergent composition includes from 5 wt-% to 50 wt-% of one or more building agents, also called chelating or sequestering agents (e.g. builders) to treat or soften water and to prevent formation of precipitates or other salts, selected from the group consisting of condensed phosphates, alkali metal silicates and metasilicates, phosphonates and aminocarboxylic acidsIn general, a chelating agent is a molecule capable of coordinating (i.e., binding) the metal ions commonly found in natural water to prevent the metal ions from interfering with the action of the other detersive ingredients of a cleaning composition. Levels of addition for builders that can also be chelating or sequestering agents are between 5% to 50% by weight, or 20% to 50% by weight. If the solid detergent is provided as a concentrate, the concentrate can include between 6% to 45% by weight of the builders. Additional ranges of the builders include between 6% to 15% by weight, and between 25% to 50% by weight.
Examples of condensed phosphates include, but are not limited to: sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. A condensed phosphate may also assist, to a limited extent, in solidification of the detergent composition by fixing the free water present in the composition as water of hydration. A preferred builder is sodium tripolyphosphate anhydrous.
Examples of phosphonates include, but are not limited to: 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid, CH₂C(OH)[PO(OH)₂]₂; aminotri(methylenephosphonic acid), N[CH₂PO(OH)₂]₃; aminotri(methylenephosphonate), sodium salt (ATMP), N[CH2PO(ONa)₂]₃; 2-hydroxyethyliminobis(methylenephosphonic acid), HOCH₂CH₂N[CH₂PO(OH)₂]₂; diethylenetriaminepenta(methylenephosphonic acid), (HO)₂POCH₂N[CH₂CH₂N[CH₂ PO(OH)₂]₂]₂; diethylenetriaminepenta(methylenephosphonate), sodium salt (DTPMP), C₉H_(28-x)N₃Na_xO₁₅P₅ (x=7); hexamethylenediamine(tetramethylenephosphonate), potassium salt, C₁₀H_(28-x)N₂KxO₁₂P₄ (x=6); bis(hexamethylene)triamine(pentamethylenephosphonic acid), (HO₂)POCH₂N[(CH₂)₂N[CH₂PO(OH)₂]₂]₂; and phosphorus acid, H₃PO₃. A preferred phosphonate combination is ATMP and HEDP. A neutralized or alkali phosphonate, or a combination of the phosphonate with an alkali source prior to being added into the mixture such that there is little or no heat or gas generated by a neutralization reaction when the phosphonate is added is preferred. In one embodiment, however, the detergent composition is phosphorous-free.
Useful aminocarboxylic acid materials containing little or no NTA include, but are not limited to: N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), aspartic acid-N,N-diacetic acid (ASDA), methylglycinediacetic acid (MGDA), glutamic acid-N,N-diacetic acid (GLDA), ethylenediaminesuccinic acid (EDDS), 2-hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), 3-hydroxy-2-2'-iminodisuccinic acid (HIDS) and other similar acids or salts thereof having an amino group with a carboxylic acid substituent. In one embodiment, however, the composition is free of aminocarboxylates.
Water conditioning polymers can also be used as non-phosphorus containing builders (not according to the invention). Exemplary water conditioning polymers include, but are not limited to: polycarboxylates. Exemplary polycarboxylates that can be used as builders and/or water conditioning polymers include, but are not limited to: those having pendant carboxylate (-CO_2-) groups such as polyacrylic acid, maleic acid, maleic/olefin copolymer, sulfonated copolymer or terpolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, and hydrolyzed acrylonitrile-methacrylonitrile copolymers. Other suitable water conditioning polymers include starch, sugar or polyols comprising carboxylic acid or ester functional groups. Exemplary carboxylic acids include but are not limited to maleic, acrylic, methacrylic and itaconic acid or salts thereof. Exemplary ester functional groups include aryl, cyclic, aromatic and C₁-C₁₀ linear, branched or substituted esters. For a further discussion of chelating agents/sequestrants, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339-366 and volume 23, pages 319-320. These materials may also be used at substoichiometric levels to function as crystal modifiers.

Water Conditioning Agents

The alkaline detergent compositions can include one or more water conditioning agents. In an aspect, phosphonic acids can be employed. Phosphonic acids can be used in the form of water soluble acid salts, particularly the alkali metal salts, such as sodium or potassium; the ammonium salts; or the alkylol amine salts where the alkylol has 2 to 3 carbon atoms, such as mono-, di-, or triethanolamine salts. Preferred phosphonates include the organic phosphonates. Preferred organic phosphonates include phosphono butane tricarboxylic acid (PBTC) available from Bayer Corp. in Pittsburgh Pa. under the tradename of BAYHIBIT^™ and hydroxy ethylidene diphosphonic acid (HEDP) such as that sold under the tradename of DEQUEST ^™2010 available from Monsanto Chemical Co. Additional description of suitable water conditioning agents for use in the invention is described in U.S. Patent No. 6,436,893 .
In an aspect, the compositions include from 0.1 wt-% - 50 wt-% water conditioning agent, from 1 wt-% - 40 wt-% water conditioning agent, from 1 wt-% - 30 wt-% water conditioning agent, preferably from 5 wt-% - 20 wt-% water conditioning agent. In addition, without being limited according to the invention, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Neutralizing Agents

The alkaline detergent compositions may also include a neutralizing agent. For example, in certain embodiments an alkaline neutralizing agent may be employed to neutralize acidic components, such as a water conditioning agent. Suitable alkaline neutralizing agents may include for example alkali metal hydroxides, including but not limited to: sodium hydroxide, potassium hydroxide, lithium hydroxide, and combinations thereof. An alkali metal hydroxide neutralizing agent may be added to the composition in any form known in the art, including as solid beads, dissolved in an aqueous solution, or a combination thereof. Additionally, more than one neutralizing agent may be used according to certain embodiments. In an aspect of the invention, the compositions of the invention do not include hydroxides as alkalinity sources but only to neutralize acidic ingredients in the composition, including for example water conditioning agents such as HEDP.
In an aspect, the compositions include from 0.1 wt-% - 50 wt-% neutralizing agent, from 0.1 wt-% - 30 wt-% neutralizing agent, from 1 wt-% - 25 wt-% neutralizing agent, preferably from 10 wt-% - 25 wt-% neutralizing agent. In an embodiment of the invention, the neutralizing agent comprises alkali metal hydroxide in an amount of up to 10 wt-%, preferably between 0.01 wt-% and 10 wt-%.

Anti-Etch Agents

The alkaline detergent compositions may also include an anti-etch agent capable of preventing etching in glass. Examples of suitable anti-etch agents include adding metal ions to the composition such as zinc, zinc chloride, zinc gluconate, aluminum, and beryllium. The corrosion inhibitor can refer to the combination of a source of aluminum ion and a source of zinc ion. The source of aluminum ion and the source of zinc ion provide aluminum ion and zinc ion, respectively, when the solid detergent composition is provided in the form of a use solution. The amount of the corrosion inhibitor is calculated based upon the combined amount of the source of aluminum ion and the source of zinc ion. Anything that provides an aluminum ion in a use solution can be referred to as a source of aluminum ion, and anything that provides a zinc ion when provided in a use solution can be referred to as a source of zinc ion. It is not necessary for the source of aluminum ion and/or the source of zinc ion to react to form the aluminum ion and/or the zinc ion. Aluminum ions can be considered a source of aluminum ion, and zinc ions can be considered a source of zinc ion. The source of aluminum ion and the source of zinc ion can be provided as organic salts, inorganic salts, and mixtures thereof. Exemplary sources of aluminum ion include, but are not limited to: aluminum salts such as sodium aluminate, aluminum bromide, aluminum chlorate, aluminum chloride, aluminum iodide, aluminum nitrate, aluminum sulfate, aluminum acetate, aluminum formate, aluminum tartrate, aluminum lactate, aluminum oleate, aluminum bromate, aluminum borate, aluminum potassium sulfate, aluminum zinc sulfate, and aluminum phosphate. Exemplary sources of zinc ion include, but are not limited to: zinc salts such as zinc chloride, zinc sulfate, zinc nitrate, zinc iodide, zinc thiocyanate, zinc fluorosilicate, zinc dichromate, zinc chlorate, sodium zincate, zinc gluconate, zinc acetate, zinc benzoate, zinc citrate, zinc lactate, zinc formate, zinc bromate, zinc bromide, zinc fluoride, zinc fluorosilicate, and zinc salicylate.
The composition preferably includes from 0.001 wt-% to 10 wt-%, more preferably from 0.01 wt-% to 7 wt-%, and most preferably from 0.01 wt-% to 1 wt-% of an anti-etch agent. In addition, without being limited according to the invention, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.

Anticorrosion Agents

The alkaline detergent compositions may optionally include an anticorrosion agent. Anticorrosion agents provide compositions that generate surfaces that are shinier and less prone to biofilm buildup than surfaces that are not treated with compositions having anticorrosion agents.
Preferred anticorrosion agents which can be used according to the invention include phosphonates, phosphonic acids, triazoles, organic amines, sorbitan esters, carboxylic acid derivatives, sarcosinates, phosphate esters, zinc, nitrates, chromium, molybdate containing components, and borate containing components. Exemplary phosphates or phosphonic acids are available under the name Dequest (i.e., Dequest 2000, Dequest 2006, Dequest 2010, Dequest 2016, Dequest 2054, Dequest 2060, and Dequest 2066) from Solutia, Inc. of St. Louis, Mo. Exemplary triazoles are available under the name Cobratec (i.e., Cobratec 100, Cobratec TT-50-S, and Cobratec 99) from PMC Specialties Group, Inc. of Cincinnati, Ohio. Exemplary organic amines include aliphatic amines, aromatic amines, monoamines, diamines, triamines, polyamines, and their salts. Exemplary amines are available under the names Amp (i.e. Amp-95) from Angus Chemical Company of Buffalo Grove, Ill.; WGS (i.e., WGS-50) from Jacam Chemicals, LLC of Sterling, Kans.; Duomeen (i.e., Duomeen O and Duomeen C) from Akzo Nobel Chemicals, Inc. of Chicago, Ill.; DeThox amine (C Series and T Series) from DeForest Enterprises, Inc. of Boca Raton, Fla.; Deriphat series from Henkel Corp. of Ambler, Pa.; and Maxhib (AC Series) from Chemax, Inc. of Greenville, S.C. Exemplary sorbitan esters are available under the name Calgene (LA-series) from Calgene Chemical Inc. of Skokie, Ill. Exemplary carboxylic acid derivatives are available under the name Recor (i.e., Recor 12) from Ciba-Geigy Corp. of Tarrytown, N.Y. Exemplary sarcosinates are available under the names Hamposyl from Hampshire Chemical Corp. of Lexington, Mass.; and Sarkosyl from Ciba-Geigy Corp. of Tarrytown, N.Y.
The composition optionally includes an anticorrosion agent for providing enhanced luster to the metallic portions of a dish machine and/or providing shinier surfaces. When an anticorrosion agent is incorporated into the composition, it is preferably included in an amount of between 0.01 wt-% and 7.5 wt-%, between 0.01 wt-% and 5 wt-% and between 0.01 wt-% and 3 wt-%.

Antiredeposition Agents

The alkaline detergent compositions may also include an antiredeposition agent capable of facilitating sustained suspension of soils in a cleaning solution and preventing the removed soils from being redeposited onto the substrate being cleaned. Examples of suitable antiredeposition agents include fatty acid amides, complex phosphate esters, styrene maleic anhydride copolymers, and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose. The composition preferably includes from 0.5 wt-% to 10 wt-% and more preferably from 1 wt-% to 5 wt-% of an antiredeposition agent.

Enzymes

The alkaline detergent compositions can include one or more enzymes, which can provide desirable activity for removal of protein-based, carbohydrate-based, or triglyceride-based soils from substrates such as flatware, cups and bowls, and pots and pans. Enzymes suitable for the inventive composition can act by degrading or altering one or more types of soil residues encountered on a surface thus removing the soil or making the soil more removable by a surfactant or other component of the cleaning composition. Both degradation and alteration of soil residues can improve detergency by reducing the physicochemical forces which bind the soil to the surface or textile being cleaned, i.e. the soil becomes more water soluble. For example, one or more proteases can cleave complex, macromolecular protein structures present in soil residues into simpler short chain molecules which are, of themselves, more readily desorbed from surfaces, solubilized, or otherwise more easily removed by detersive solutions containing said proteases.
Suitable enzymes include a protease, an amylase, a lipase, a gluconase, a cellulase, a peroxidase, or a mixture thereof of any suitable origin, such as vegetable, animal, bacterial, fungal or yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders . In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. In some embodiments preferably the enzyme is a protease, a lipase, an amylase, or a combination thereof. A valuable reference on enzymes is "Industrial Enzymes," Scott, D., in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, (editors Grayson, M. and EcKroth, D.) Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980.
In embodiments employing an enzyme the composition preferably includes from 0.001 wt-% to 10 wt-%, from 0.01 wt-% to 10 wt-%, from 0.05 wt-% to 5 wt-%, and more preferably from 0.1 wt-% to 1 wt-% of enzyme(s).

Antimicrobial Agent

The alkaline detergent compositions may optionally include an antimicrobial agent or preservative. Antimicrobial agents are chemical compositions that can be used in the composition to prevent microbial contamination and deterioration of commercial products material systems, surfaces. Antimicrobial agents may also be sanitizing agents. Generally, these materials fall in specific classes including phenolics, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanol amines, nitro derivatives, analides, organosulfur and sulfur-nitrogen compounds and miscellaneous compounds. The given antimicrobial agent depending on chemical composition and concentration may simply limit further proliferation of numbers of the microbe or may destroy all or a substantial proportion of the microbial population. The terms "microbes" and "microorganisms" typically refer primarily to bacteria and fungus microorganisms. In use, the antimicrobial agents are formed into the final product that when diluted and dispensed using an aqueous stream forms an aqueous disinfectant or sanitizer composition that can be contacted with a variety of surfaces resulting in prevention of growth or the killing of a substantial proportion of the microbial population. Common antimicrobial agents that may be used include phenolic antimicrobials such as pentachlorophenol, orthophenylphenol; halogen containing antibacterial agents that may be used include sodium trichloroisocyanurate, sodium dichloroisocyanurate (anhydrous or dihydrate), iodine-poly(vinylpyrolidin-onen) complexes, bromine compounds such as 2-bromo-2-nitropropane-1,3-diol; quaternary antimicrobial agents such as benzalconium chloride, cetylpyridiniumchloride; amines and nitro containing antimicrobial compositions such as hexahydro-1,3,5-tris(2-hydr- oxyethyl)-s-triazine, dithiocarbamates such as sodium dimethyldithiocarbamate, and a variety of other materials known in the art for their microbial properties. Antimicrobial agents may be encapsulated to improve stability and/or to reduce reactivity with other materials in the detergent composition.
When an antimicrobial agent or preservative is incorporated into the composition, it is preferably included in an amount between 0.01 wt-% to 5 wt-%, between 0.01 wt-% to 2 wt-%, and between 0.1 wt-% to 1.0 wt-%.

Foam Inhibitors

A foam inhibitor may be included in addition to the nonionic surfactants of the alkaline cleaning compositions for reducing the stability of any foam that is formed. Examples of foam inhibitors include silicon compounds such as silica dispersed in polydimethylsiloxane, fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, polyoxyethylene-polyoxypropylene block copolymers, alkyl phosphate esters such as monostearyl phosphate . A discussion of foam inhibitors may be found, for example, in U.S. Pat. No. 3,048,548 to Martin et al. , U.S. Pat. No. 3,334,147 to Brunelle et al. , and U.S. Pat. No. 3,442,242 to Rue et al. The composition preferably includes from 0.0001 wt-% to 5 wt-% and more preferably from 0.01 wt-% to 3 wt-% of the foam inhibitor.

Additional Surfactants

The compositions of invention may include additional surfactants. Particularly suitable surfactants include nonionic surfactants, amphoteric surfactants, and zwitterionic surfactants. In a preferred embodiment the compositions are substantially free of cationic and/or anionic surfactants. In an aspect, the compositions can include from 0.01 wt-% - 40 wt-% additional surfactants, preferably from 0.1 wt-% - 30 wt-% additional surfactant, more preferably from 1 wt-% - 25 wt-% additional surfactant.

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 for other types of surfactants. A basic nitrogen and an acidic carboxylate group are the typical functional groups employed as the basic and acidic hydrophilic groups. In a few surfactants, sulfonate, sulfate, phosphonate or phosphate provide the negative charge.
Amphoteric surfactants 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 of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono. Amphoteric surfactants are subdivided into two major classes known to those of skill in the art and described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989. The first class includes acyl/dialkyl ethylenediamine derivatives (e.g. 2-alkyl hydroxyethyl imidazoline derivatives) and their salts. The second class includes N-alkylamino acids and their salts. Some amphoteric surfactants can be envisioned as fitting into both classes.
Amphoteric surfactants 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 surfactants are derivatized by subsequent hydrolysis and ring-opening of the imidazoline ring by alkylation -- for example with chloroacetic acid or ethyl acetate. During alkylation, one or two carboxy-alkyl groups react to form a tertiary amine and an ether linkage with differing alkylating agents yielding different tertiary amines.
Long chain imidazole derivatives having application in the present invention generally have the general formula:
wherein R is an acyclic hydrophobic group containing from 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion, generally sodium. Commercially prominent imidazoline-derived amphoterics that can be employed in the present compositions include for example: Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate, Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, and Cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid and/or dipropionic acid.
The carboxymethylated compounds (glycinates) described herein above frequently are called betaines. Betaines are a special class of amphoteric discussed herein below in the section entitled, Zwitterion Surfactants.
Long chain N-alkylamino acids are readily prepared by reaction RNH₂, in which R=C₈-C₁₈ straight or branched chain alkyl, fatty amines with halogenated carboxylic acids. Alkylation of the primary amino groups of an amino acid leads to secondary and tertiary amines. Alkyl substituents may have additional amino groups that provide more than one reactive nitrogen center. Most commercial N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine. Examples of commercial N-alkylamino acid ampholytes having application in this invention include alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ and RNHC₂H₄COOM. In an embodiment, R can be an acyclic hydrophobic group containing from 8 to 18 carbon atoms, and M is a cation to neutralize the charge of the anion.
Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acid. Additional suitable coconut derived surfactants include as part of their structure an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, e.g., glycine, or a combination thereof; and an aliphatic substituent of from 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can also be considered an alkyl amphodicarboxylic acid. These amphoteric surfactants can include chemical structures represented as: C₁₂-alkyl-C(O)-NH-CH₂-CH₂-N⁺(CH₂-CH₂-CO₂Na)₂-CH₂-CH₂-OH or C₁₂-alkyl-C(O)-N(H)-CH₂-CH₂-N⁺(CH₂-CO₂Na)₂-CH₂-CH₂-OH. Disodium cocoampho dipropionate is one suitable amphoteric surfactant and is commercially available under the tradename Miranol^™ FBS from Rhodia Inc., Cranbury, N.J. Another suitable coconut derived amphoteric surfactant with the chemical name disodium cocoampho diacetate is sold under the tradename Mirataine^™ JCHA, also from Rhodia Inc., Cranbury, N.J.
A typical listing of amphoteric classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975 . Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphoteric surfactants and can include an anionic charge. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Typically, a zwitterionic surfactant includes a positive charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion; a negative charged carboxyl group; and an alkyl group. Zwitterionics generally contain cationic and anionic groups which ionize to a nearly equal degree in the isoelectric region of the molecule and which can develop strong" inner-salt" attraction between positive-negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic radicals can be straight chain or branched, and wherein one of the aliphatic substituents contains from 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. A general formula for these compounds is:
wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.
Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-l-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate; 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-l-carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in said detergent surfactants can be straight or branched and saturated or unsaturated.
The zwitterionic surfactant suitable for use in the present compositions includes a betaine of the general structure:
These surfactant betaines typically do not exhibit strong cationic or anionic characters at pH extremes nor do they show reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionics. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C_12-14 acylamidopropylbetaine; C_8-14 acylamidohexyldiethyl betaine; 4-C_14-16 acylmethylamidodiethylammonio-1-carboxybutane; C_16-18 acylamidodimethylbetaine; C_12-16 acylamidopentanediethylbetaine; and C_12-16 acylmethylamidodimethylbetaine.
Sultaines useful in the present invention include those compounds having the formula (R(R¹)₂ N⁺ R²SO^3-, in which R is a C₆ -C₁₈ hydrocarbyl group, each R¹ is typically independently C₁-C₃ alkyl, e.g. methyl, and R² is a C₁-C₆ hydrocarbyl group, e.g. a C₁-C₃ alkylene or hydroxyalkylene group.
A typical listing of zwitterionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975 . Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch).
In an embodiment, the compositions of the present invention include a betaine. For example, the compositions can include cocoamido propyl betaine.

Embodiments

Exemplary ranges of the 2-in-1 alkaline detergent compositions according to the invention are shown in Tables 1A and 1B in weight percentage of the solid detergent compositions.

TABLE 1A

Material				Fourth Exemplary Range wt-%
Alkalinity Source				45-75
Builders				10-35
Surfactants				2-20
Additional Functional Ingredients				0-20

TABLE 1B

Material				Fourth Exemplary Range wt-%
Alkalinity Source				45-75
Polymer				1-20
Builders				10-35
Surfactants				2-20
Additional Functional Ingredients				0-20

The detergent compositions may include concentrate compositions or may be diluted to form use compositions. In general, a concentrate refers 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. The detergent composition that contacts the articles to be washed can be referred to as a concentrate or a use composition (or use solution) dependent upon the formulation employed in methods according to the invention. It should be understood that the concentration of the aminocarboxylate, water conditioning agent, alkalinity, water and other optional functional ingredients in the detergent composition will vary depending on whether the detergent composition is provided as a concentrate or as a use solution.
A use solution may be prepared from the concentrate by diluting the concentrate with water at a dilution ratio that provides a use solution having desired detersive properties. The water that is used to dilute the concentrate to form the use composition can be referred to as water of dilution or a diluent, and can vary from one location to another. The typical dilution factor is between approximately 1 and approximately 10,000 but will depend on factors including water hardness, the amount of soil to be removed . In an embodiment, the concentrate is diluted at a ratio of between 1:10 and 1:10,000 concentrate to water. Particularly, the concentrate is diluted at a ratio of between 1:100 and 1:5,000 concentrate to water. More particularly, the concentrate is diluted at a ratio of between 1:250 and 1:2,000 concentrate to water.

Method of Use - Cleaning an Article in a Dish Machine

In an embodiment, methods of the present invention involve using the steps of providing an alkaline 2-in-1 detergent composition as disclosed herein. In particular, methods of use preferably employ a solid alkaline 2-in-1 detergent composition, wherein a solid composition is inserted into a dispenser in or associated with an dish machine, particularly an industrial warewash machine. In an embodiment of the invention, the solid composition may be provided as a multiple-use dosage having between 10 and 10,000 doses per solid composition. In another aspect of the invention, the solid composition can be formulated in a single-use composition, where it is used one time in a wash. The methods also include forming a wash solution with the alkaline 2-in-1 detergent composition and water, contacting a soil on an article in the dish machine with the wash solution, removing the soil, and rinsing the article with potable water without requiring the use of a separate rinse aid composition. The rinse is with potable water only.
In another embodiment, the methods of the present invention may involve providing the individual components of the 2-in-1 detergent composition separately and mixing the individual components in situ with water to form a desired wash solution.
When carrying out the methods of the invention, the 2-in-1 detergent compositions described above are inserted into a dispenser of a dish machine. The dispenser may be selected from a variety of different dispensers depending of the physical form of the composition. For example, a liquid composition may be dispensed using a pump, either peristaltic or bellows for example, syringe/plunger injection, gravity feed, siphon feed, aspirators, unit dose, for example using a water soluble packet such as polyvinyl alcohol, or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface. If the composition is a gel or a thick liquid, it may be dispensed using a pump such as a peristaltic or bellows pump, syringe/plunger injection, caulk gun, unit dose, for example using a water soluble packet such as polyvinyl alcohol or a foil pouch, evacuation from a pressurized chamber, or diffusion through a membrane or permeable surface. Preferably, when the composition is a solid or powder, the composition may be dispensed using a spray, flood, auger, shaker, tablet-type dispenser, unit dose using a water soluble packet such as polyvinyl alcohol or foil pouch, or diffusion through a membrane or permeable surface. The dispenser may also be a dual dispenser in which one component, is dispensed on one side and another component is dispensed on another side. These exemplary dispensers may be located in or associated with a variety of dish machines including under the counter dish machines, bar washers, door machines, conveyor machines, or flight machines. The dispenser may be located inside the dish machine, remote, or mounted outside of the dishwasher. A single dispenser may feed one or more dish machines.
Once the 2-in-1 detergent composition is inserted into the dispenser, the wash cycle of the dish machine is started and a wash solution is formed. The wash solution comprises the alkaline 2-in-1 detergent composition and water from the dish machine. The water may be any type of water including hard water, soft water, clean water, or dirty water. The most preferred wash solution is one that maintains the preferred pH ranges of 7 to 11.5, more preferably 9.5 to 11.5, as measured by a pH probe based on a solution of the composition in a 16 gallon dish machine. The same probe may be used to measure millivolts if the probe allows for both functions, simply by switching the probe from pH to millivolts. The dispenser or the dish machine may optionally include a pH probe to measure the pH of the wash solution throughout the wash cycle. The actual concentration or water to detergent ratio depends on the particular surfactant used. Exemplary concentration ranges may include up to 3000 ppm, preferably 1 to 3000 ppm, more preferably 100 to 3000 ppm and most preferably 300 to 2000 ppm. Again, the actual concentration used depends on the surfactant chosen.
A use solution can have an elevated temperature (i.e. heated to an elevated temperature when used according to the methods of the invention. In one example, a use solution having a temperature between approximately 48.9°C (120°F) and 85°C (185°F), between 60°C (140°F) and approximately 85°C (185°F) is contacted with the substrate to be cleaned. In another example, a use solution having a temperature between approximately 65.6°C (150°F) and approximately 71.1°C (160°F) is contacted with the substrate to be cleaned.
After the wash solution is formed, the wash solution contacts a soil on an article in the dish machine. Examples of soils include soils typically encountered with food such as proteinaceous soils, hydrophobic fatty soils, starchy and sugary soils associated with carbohydrates and simple sugars, soils from milk and dairy products, fruit and vegetable soils. Soils can also include minerals, from hard water for example, such as potassium, calcium, magnesium, and sodium. Articles that may be contacted include articles made of glass, plastic, aluminum, steel, copper, brass, silver, rubber, wood, ceramic. Articles include things typically found in a dish machine such as glasses, bowls, plates, cups, pots and pans, bakeware such as cookie sheets, cake pans, muffin pans, silverware such as forks, spoons, knives, cooking utensils such as wooden spoons, spatulas, rubber scrapers, utility knives, tongs, grilling utensils, serving utensils. The wash solution may contact the soil in a number of ways including spraying, dipping, sump-pump solution, misting and fogging.
Once the wash solution has contacted the soil, the soil is removed from the article. The removal of the soil from the article is accomplished by the chemical reaction between the wash solution and the soil as well as the mechanical action of the wash solution on the article depending on how the wash solution is contacting the article.
Once the soil is removed, the articles are rinsed as part of the dish machine wash cycle employing potable water without the use of a separate or additional rinse aid composition.
The methods can include more steps or fewer steps than laid out here. For example, the method can include additional steps normally associated with a dish machine wash cycle. For example, the method can also optionally include the use of an acidic detergent. For example, the method can optionally include alternating the acidic detergent with an alkaline detergent as described.

Method of Manufacturing the Composition

The compositions of the present invention may include liquid products, thickened liquid products, gelled liquid products, paste, granular and pelletized solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block composition and others.
Solid particulate materials can be made by merely blending the dry solid ingredients in appropriate ratios or agglomerating the materials in appropriate agglomeration systems. Pelletized materials can be manufactured by compressing the solid granular or agglomerated materials in appropriate pelletizing equipment to result in appropriately sized pelletized materials. Solid block and cast solid block materials can be made by introducing into a container either a prehardened block of material or a castable liquid that hardens into a solid block within a container. Preferred containers include disposable plastic containers or water soluble film containers. Other suitable packaging for the composition includes flexible bags, packets, shrink wrap, and water soluble film such as polyvinyl alcohol.
The solid detergent compositions may be formed using a batch or continuous mixing system. In an exemplary embodiment, a single- or twin-screw extruder is used to combine and mix one or more components at high shear to form a homogeneous mixture. In some embodiments, the processing temperature is at or below the melting temperature of the components. The processed mixture may be dispensed from the mixer by forming, casting or other suitable means, whereupon the detergent composition hardens to a solid form. The structure of the matrix may be characterized according to its hardness, melting point, material distribution, crystal structure, and other like properties according to known methods in the art. Generally, a solid detergent composition processed according to the method of the invention is substantially homogeneous with regard to the distribution of ingredients throughout its mass and is dimensionally stable.
In an extrusion process, the liquid and solid components are introduced into final mixing system and are continuously mixed until the components form a substantially homogeneous semi-solid mixture in which the components are distributed throughout its mass. The mixture is then discharged from the mixing system into, or through, a die or other shaping means. The product is then packaged. In an exemplary embodiment, the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours. Particularly, the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 2 hours. More particularly, the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 20 minutes.
In a casting process, the liquid and solid components are introduced into the final mixing system and are continuously mixed until the components form a substantially homogeneous liquid mixture in which the components are distributed throughout its mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once the mixing is complete, the product is transferred to a packaging container where solidification takes place. In an exemplary embodiment, the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours. Particularly, the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 2 hours. More particularly, the cast composition begins to harden to a solid form in between approximately 1 minute and approximately 20 minutes.
In a pressed solid process, a flowable solid, such as granular solids or other particle solids including binding agents (e.g. hydrated chelating agent, such as a hydrated aminocarboxylate, a hydrated polycarboxylate or hydrated anionic polymer, a hydrated citrate salt or a hydrated tartrate salt together with an alkali metal carbonate) are combined under pressure. In a pressed solid process, flowable solids of the compositions are placed into a form (e.g., a mold or container). The method can include gently pressing the flowable solid in the form to produce the solid cleaning composition. Pressure may be applied by a block machine or a turntable press. Pressure may be applied at 0.069 bar to 138 bar (1 to 2000 psi), 0.069 bar to 21 bar (1 to 300 psi), 0.34 bar to 13.8 bar (5 psi to 200 psi), or 0.69 bar to 6.9 bar (10 psi to 100 psi). In certain embodiments, the methods can employ pressures as low as greater than or equal to 1 psi, greater than or equal to 2, greater than or equal to 5 psi, or greater than or equal to 10 psi. As used herein, the term "psi" or "pounds per square inch" refers to the actual pressure applied to the flowable solid being pressed and does not refer to the gauge or hydraulic pressure measured at a point in the apparatus doing the pressing. The method can include a curing step to produce the solid cleaning composition. As referred to herein, an uncured composition including the flowable solid is compressed to provide sufficient surface contact between particles making up the flowable solid that the uncured composition will solidify into a stable solid cleaning composition. A sufficient quantity of particles (e.g. granules) in contact with one another provides binding of particles to one another effective for making a stable solid composition. Inclusion of a curing step may include allowing the pressed solid to solidify for a period of time, such as a few hours, or 1 day (or longer). In additional aspects, the methods could include vibrating the flowable solid in the form or mold, such as the methods disclosed in U.S. Patent No. 8,889,048 .
The use of pressed solids provide numerous benefits over conventional solid block or tablet compositions requiring high pressure in a tablet press, or casting requiring the melting of a composition consuming significant amounts of energy, and/or by extrusion requiring expensive equipment and advanced technical know-how. Pressed solids overcome such various limitations of other solid formulations for which there is a need for making solid cleaning compositions. Moreover, pressed solid compositions retain its shape under conditions in which the composition may be stored or handled.
By the term "solid", it is meant that the hardened composition will not flow and will substantially retain its shape under moderate stress or pressure or mere gravity. A solid may be in various forms such as a powder, a flake, a granule, a pellet, a tablet, a lozenge, a puck, a briquette, a brick, a solid block, a unit dose, or another solid form 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 from that of a fused solid product which is relatively dense and hard, for example, like concrete, to a consistency characterized as being a hardened paste. In addition, the term "solid" refers to the state of the detergent composition under the expected conditions of storage and use of the solid detergent composition. In general, it is expected that the detergent composition will remain in solid form when exposed to temperatures of up to approximately 37.8°C (100°F) and particularly up to approximately 48.9°C (120°F).
The resulting solid detergent composition may take forms including, but not limited to: a cast solid product; an extruded, molded or formed solid pellet, block, tablet, powder, granule, flake; pressed solid; or the formed solid can thereafter be ground or formed into a powder, granule, or flake. In an exemplary embodiment, extruded pellet materials formed by the solidification matrix have a weight of between approximately 50 grams and approximately 250 grams, extruded solids formed by the composition have a weight of approximately 100 grams or greater, and solid block detergents formed by the composition have a mass of between approximately 1 and approximately 10 kilograms. The solid compositions provide for a stabilized source of functional materials. In some embodiments, the solid composition may be dissolved, for example, in an aqueous or other medium, to create a concentrated and/or use solution. The solution may be directed to a storage reservoir for later use and/or dilution, or may be applied directly to a point of use.
The following patents disclose various combinations of solidification, binding and/or hardening agents that can be utilized in the solid cleaning compositions of the present invention.
Liquid compositions can typically be made by forming the ingredients in an aqueous liquid or aqueous liquid solvent system. Such systems are typically made by dissolving or suspending the active ingredients in water or in compatible solvent and then diluting the product to an appropriate concentration, either to form a concentrate or a use solution thereof. Gelled compositions can be made similarly by dissolving or suspending the active ingredients in a compatible aqueous, aqueous liquid or mixed aqueous organic system including a gelling agent at an appropriate concentration.

EXAMPLES

Embodiments of the present invention are further defined in the following nonlimiting Examples.

EXAMPLES 1-4

The materials used in the Examples 1-4 are provided herein:

Pluronic^® 25R2: an EO/PO copolymer available from BASF.
Novel^® II 1012GB-21: an alcohol alkoxylate available from Sasol.

Additional materials commercially-available from multiple sources include: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP, and KOH.

For Examples 1-4, an exemplary 2-in-1 detergent was prepared and is shown in Table 2. Throughout Examples 1-4, the formulation is referred to as Experimental Formula 1 (Exp. 1).

TABLE 2

Raw material	Exp. 1
Alkalinity source	45-75
Builder	10-30
Alkyl alkoxylate (EO/PO copolymer)	1-10
Alcohol alkoxylate	1-10
Sanitizing agent	1-10
Corrosion inhibitor	0.01-0.5
Phosphonate builder, 60%	1-10
KOH, 45%	1-10
Total	100

Existing detergents, rinse aids, and Experimental Formula 1 were tested against distilled water. Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate-based detergents). Rinse Aid Control 1 and Rinse Aid Control 2 are two commercially available rinse aids (employing higher amounts of active ingredients and surfactants of at least two ionic categories (e.g. nonionic and cationic)). The use concentrations for all experiments described below are provided in the following table: TABLE 3

Sample Use concentration [ppm]

DI water N/A

Detergent Control

1 1500

Detergent Control 2 1000

Rinse Aid Control 1 536

Rinse Aid Control 2 536

Exp. 1 1415
All warewash testing was performed with 296 mL (10 oz.) Libbey glasses on a Hobart AM-15 warewash machine. The specifications of the Hobart AM-15 warewash machine are as follows:

Hobart AM-15 warewash machine specifications.

Washbath volume:	53L
Rinse volume:	2.8L
Wash time:	50 sec.
Rinse time:	9 sec.

EXAMPLE 1

DYNAMIC SURFACE TENSION

The SITA science line t60 measures the dynamic surface tension of liquids up to the semi-static range. Air bubbles are generated from a capillary with known radius. The bubble pressure is measured as a function of bubble life time, which can be correlated to the surface tension according to the Young-Laplace equation. Dynamic surface tension provides insight into the dynamic behavior of surfactants and other surface active compounds under dynamic conditions, i.e. how quick surfactants can reach a surface. The dynamic surface tension is a function of concentration, temperature and type of surfactant. The dynamic surface tension behavior of surfactants is particularly important in applications where a quick response of surfactants is required, for example, in the short rinse cycles of automated dishwashing.

APPARATUS AND MATERIALS:

1.: SITA T60 (Sita Messtechnik, Germany)
2.: Oil bath with stir bar
3.: Heating and stirring plate
4.: Glass beakers
5.: Glass vials (20 mL)

The SITA science line t60 was calibrated with DI water. Clean water samples after calibration should have a surface tension of 72.0±1.0mN/m (depending on water quality and temperature). Following calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, and 9.1 seconds). Three separate solutions at the desired ppm were prepared for each composition (described as Samples A-C) to be tested (e.g., three samples of Exp. 1, three samples of Detergent Control 1). 10-15 mL were transferred into 20 mL vials and immersed in a heated oil bath to 72 °C (160 °F) ± 2°C. The samples were equilibrated for 10-15 minutes. The samples were individually removed from the oil bath and the tested in the SITA. After each sample was tested the SITA's cleaning procedure was run, then the surface tension of DI water was checked to ensure the SITA was adequately clean. If the DI water measurements were not within 72.0 ±1.0 mN/m, then the cleaning procedure was run again. The surface tension (mN/m) versus bubble life time at 71.1°C (160 °F) experimental data is provided in Tables 4A through 4F below, wherein τ: bubble life time (s); γ: surface tension (mN/m).

TABLE 4A

Detergent Control 1
Sample A		Sample B		Sample C
τ	γ	τ	γ	τ	γ
0.031	65.1	0.031	67.9	0.03	66.4
0.041	65	0.042	65.9	0.041	66.2
0.058	64.5	0.058	65.8	0.058	65
0.083	64.1	0.082	65.3	0.081	64.1
0.116	63.4	0.116	64.6	0.116	64.4
0.159	62.8	0.161	63.8	0.162	64.3
0.223	63	0.223	63.9	0.226	63.7
0.313	62.6	0.313	63.7	0.315	63.8
0.421	62.5	0.426	63.5	0.149	63.2
0.624	62.3	0.622	62.7	0.621	62.7
0.857	61.4	0.878	62.7	0.883	62.9
1.164	62	1.148	62.4	1.149	62.2
1.659	61.7	1.648	62.1	1.656	62.3
2.495	61.2	2.527	61.1	2.532	61.4
3.217	60.7	3.145	60.9	3.185	61.3
4.388	59.7	4.28	60.3	4.162	60.6
6.463	57.6	6.62	57.3	6.166	59.2
8.781	54.7	9.156	53.7	8.342	55.5
11.244	52	13.403	52.1	11.972	52.7
18.795	45.7	15.816	45.7	16.933	51
21.721	44.4	21.895	47.7	22.163	47.4

TABLE 4B

Detergent Control 2
Sample A		Sample B		Sample C
τ	Γ	τ	γ	τ	γ
0.031	65.8	0.03	66.6	0.03	65.8
0.041	65.9	0.041	66	0.042	65.6
0.058	65.5	0.058	65.1	0.058	64.6
0.082	64.7	0.082	64.7	0.082	64.1
0.115	63.9	0.115	63.9	0.116	63.8
0.161	64	0.162	63.6	0.16	63.5
0.226	63.5	0.223	62.9	0.225	63.2
0.317	63.6	0.316	62.4	0.315	63
0.429	63.3	0.428	61.9	0.42	62.4
0.629	62.2	0.623	61	0.632	61.7
0.888	61.7	0.882	59.7	0.867	60.9
1.171	61.5	1.145	59.2	1.114	60.4
1.673	60.5	1.57	58.2	1.607	59.5
2.515	58.8	2.451	55.1	2.409	58.4
2.993	57.4	2.878	54	2.945	57
4.326	54.8	4.113	51.5	4.015	55.6
6.455	52.6	5.751	49.9	6.017	53.2
8.989	49.9	9.861	46.7	7.906	50.4
11.373	44.3	12.865	44.1	12.578	46.6
16.815	43.1	15.861	43.8	17.397	45
23.12	40.9	22.161	41.5	26.01	44.7

TABLE 4C

Rinse Aid Control 1
Sample A		Sample B		Sample C
τ	Γ	τ	γ	τ	γ
0.031	66.3	0.03	65.6	0.03	65.6
0.042	66.2	0.041	65.6	0.042	65.6
0.058	65.1	0.058	64.8	0.058	64.8
0.082	64.8	0.081	63.9	0.081	63.9
0.114	65.1	0.115	63.6	0.113	63.4
0.161	64.3	0.16	63.5	0.159	63.1
0.227	63.8	0.227	62.7	0.225	62.7
0.317	63.1	0.317	62.5	0.313	62.3
0.44	62.4	0.426	61.9	0.425	61.8
0.619	61.5	0.626	61.4	0.622	60.8
0.848	59.8	0.866	60	0.879	59.7
1.173	58.8	1.152	59	1.143	58.8
1.641	56.7	1.601	57.5	1.592	57.5
2.491	54.8	2.381	55.3	2.336	55.3
3.126	53.9	2.862	54.6	2.979	54.4
4.692	52.2	4.014	52.9	4.46	52.4
6.112	51.7	5.869	51.5	6.398	50.9
8.935	51	8.418	51	9.057	50.7
11.571	51	12.22	49.9	12.613	49.9
18.684	49.9	18.629	49.9	17.07	49.1
29.293	48.3	24.928	48.7	21.252	49

TABLE 4D

Rinse Aid Control 2
Sample A		Sample B		Sample C
τ	Γ	τ	γ	τ	γ
0.031	65.6	0.03	66	0.03	66.1
0.041	65.5	0.041	64.6	0.042	65.7
0.058	64.5	0.058	64.5	0.057	63.8
0.082	64.8	0.082	64.2	0.082	64
0.113	64.2	0.113	63.1	0.116	63.7
0.16	63.6	0.162	62.7	0.162	62.5
0.225	62.9	0.228	61.9	0.22	61.5
0.313	61.8	0.312	60	0.314	60.5
0.424	60.2	0.417	58.6	0.424	58.7
0.592	57.2	0.621	56.4	0.609	55.9
0.856	55.4	0.874	54.3	0.854	53.9
1.119	53.9	1.097	52.4	1.115	52
1.612	52.4	1.609	50.5	1.539	50.6
2.476	49.9	2.363	48.1	2.26	44.8
3.115	48.2	2.835	47.7	2.831	43.9
4.619	45.7	4.461	43.3	4.588	40.9
7.16	41.8	5.675	41	5.839	39.4
8.653	41.5	8.914	39.1	8.727	37.7
11.358	40.7	11.159	38	12.111	35.3
		15.255	36.4	15.955	34.8
				21.85	33.1

TABLE 4E

Experimental Formulation (Exp1)
Sample A		Sample B		Sample C
τ	Γ	τ	γ	τ	γ
0.03	65.5	0.031	65.4	0.03	64.8
0.041	64.6	0.041	64.6	0.041	65.2
0.057	63.8	0.058	64.5	0.058	63.8
0.081	63.1	0.08	63.5	0.082	62.8
0.113	61.7	0.116	62.7	0.115	61.5
0.162	60.7	0.16	61.9	0.16	60.2
0.221	59.2	0.226	60.4	0.222	59.2
0.312	57.4	0.315	58.8	0.315	57.7
0.423	56.2	0.42	57.2	0.419	56.3
0.618	54	0.622	55.6	0.612	54.6
0.888	52.4	0.883	54.1	0.846	53.1
1.147	51.2	1.151	52.8	1.166	52
1.701	50.3	1.628	51.6	1.712	50.9
2.56	48.9	2.54	50.1	2.329	49.6
3.123	48.5	3.047	49.4	2.973	48.6
4.063	46.8	4.343	48.3	4.017	47.3
7.141	44.7	6.97	46.2	5.615	45.7
9.383	43	10.408	43.1	8.816	43.9
12.358	41.6	12.122	44.3	11.387	42.5
19.243	29.5	19.097	42	15.941	41.2
21.458	38.4	21.608	40.7	23.455	39.5

TABLE 4F

DI
Sample A
τ	γ
0.031	66.5
0.041	65
0.058	65.5
0.082	64.7
0.115	65.3
0.159	64.6
0.226	64.7
0.308	64.8
0.424	64.5
0.613	64.7
0.876	64.2
1.168	64.5
1.711	64.2
2.647	64.3
3.191	64.5
4.628	63.8
6.705	64.1
10.707	64

The average surface tension at 71.1°C (160 °F) for the average bubble life times of 0.3, 1.6, 3.0, and 9.1 seconds was tested. The results are provided in Table 5.

TABLE 5

Sample	Avg. Surface Tension at 0.3 s	Avg. Surface Tension at 1.6 s	Avg. Surface Tension at 3.0 s	Avg. Surface Tension at 9.1 s
DI water	64.8	64.2	64.5	64.0
Detergent Control 1	63.0	59.4	56.1	49.0
Detergent Control 2	63.4	62.0	61.0	54.6
Rinse Aid Control 1	62.6	57.2	54.3	50.9
Rinse Aid Control 2	60.8	51.2	46.6	39.2
Exp. 1	58.0	50.9	48.8	43.3

The data demonstrates the surface tension of Experimental Formulation 1 decreases quickly with a significant drop in surface tension at the bubble life time of 9.1 seconds. This is similar to a well-performing rinse aid, such as Rinse Aid Control 2. These results are demonstrated in Figure 1.

EXAMPLE 2

ONE HUNDRED-CYCLE FILM EVALUATION FOR INSTITUTIONAL WAREWASH DETERGENTS

To determine the ability of various detergent compositions to remove spots and film from ware, six Libby 296 ml (10 oz.) glass tumblers were prepared by removing all film and foreign material from the surfaces of the glasses. A Hobart AM-15 warewash machine was then filled with an appropriate amount of water and the water was tested for hardness. After recording the hardness value, the tank heaters were turned on. On the day of the experiments, the water hardness was 1.1 g (17 grains). The warewash machine was turned on and wash/rinse cycles were run through the machine until a wash temperature of between 65.6°C (150°F) and 71.1°C (160°F) and a rinse temperature of between 79.4°C (175°F) and 87.8 °C (190°F) were reached. The controller was then set to dispense an appropriate amount of detergent into the wash tank. The detergent was dispensed such that when the detergent was mixed with water during the cycle to form a use solution, the detergent concentration in the use solution was 750 parts per million (ppm). The solution in the wash tank was titrated to verify detergent concentration. The warewash machine had a washbath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds, and a rinse time of 9 seconds.
The six clean glass tumblers were placed diagonally in a Raburn rack and four Newport 296 mL (10 oz.) plastic tumblers were placed off-diagonally in the Raburn rack (see figure below for arrangement) and the rack was placed inside the warewash machine. (P=plastic tumbler; G=glass tumbler).

G

G

G

G

G P

G
The 100 cycle test was then started. At the beginning of each wash cycle, the appropriate amount of detergent was automatically dispensed into the warewash machine to maintain the initial detergent concentration. The detergent concentration was controlled by conductivity.

Upon completion of 100 cycles, the rack was removed from the warewash machine and the glass and plastic tumblers were allowed to dry. The glass and plastic tumblers were then graded for spot and film accumulation using film ratings and using an analytical light box evaluation. The film rating scale is provided in Table 6.

TABLE 6

Rating	Spots	Film
1	No spots	No Film
2	Spots at random	20% of surface covered in film
3	1/4 glass spotted	40% of the surface covered in film
4	1/2 glass spotted	60% of the surface covered in film
5	Whole glass spotted	At least 80% of the surface covered in film

The light box test used a digital camera, a light box, a light source, a light meter and a control computer employing "Spot Advance" and "Image Pro Plus" commercial software. A glass to be evaluated was placed on its side on the light box, and the intensity of the light source was adjusted to a predetermined value using the light meter. A photographic image of the glass was taken and saved to the computer. The software was then used to analyze the upper half of the glass, and the computer displayed a histogram graph with the area under the graph being proportional to the thickness of the film.
Generally, a lower light box score indicates that more light was able to pass through the tumbler. Thus, the lower the light box score, the more effective the composition was at preventing scale on the surface of the tumbler. A clean, unused glass tumbler has a light box score of approximately 12,000, which corresponds to a score of 72,000 for the six glass tumblers, and a clean, unused plastic tumbler has a light box score of approximately 25,500, which corresponds to a light box score of approximately 102,000 for the four plastic tumblers. The minimum obtainable light box score (i.e., sum of six clean glass tumblers and four clean plastic tumblers) is approximately 174,000. Generally, a detergent composition is considered effective for controlling hard water scale if the sum of the light box scores for six glass tumblers and four plastic tumblers is approximately 360,000 or less.

The results of the 100-Cycle test are provided in Tables 7-8 providing average film ratings for glasses and plastic tumbler.

TABLE 7

100-cycle Film							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	4.5	3.0	3.5	4.5	3.5	4.0	3.8 (0.6)	1.5
Detergent Control 2	5.0	3.5	4.0	4.5	4.5	4.0	4.3 (0.5)	2.5
Detergent Control 1 + Rinse Aid Control 2	4.5	4.0	4.5	4.5	4.0	5.0	4.4 (0.3)	3.5
Detergent Control 2 + Rinse Aid Control 1	4.5	3.0	4.0	4.0	3.5	4.0	3.8 (0.5)	2.5
Exp. 1	2.0	2.0	2.0	2.0	2.0	2.5	2.1 (0.2)	2.0

TABLE 8

100-cycle Light box							Summe d Glass Score	Plastic Score	Summe d Total Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	Maxed (65535)	38906	55734	62998	47238	59893	330304	17681	347985
Detergent Control 2	Maxed (65535)	55061	59141	63854	63879	59859	367329	31530	398859
Detergent Control 1 + Rinse Aid Control 2	Maxed (65535)	63291	65304	65226	65412	Maxed (65535)	390303	46448	436751
Detergent Control 2 + Rinse Aid Control 1	Maxed (65535)	42699	54556	56364	50826	59589	329589	30727	360296
Exp. 1	22329	19107	19692	19122	20387	22797	123434	23554	146988

EXAMPLE 3

FIFTY CYCLE REDEPOSITION EXPERIMENT FOR INSTITUTIONAL WAREWASH DETERGENTS

The cleaning efficacy of the compositions according to the invention and controls were further evaluated using a 50 cycle redeposition experiment for institutional ware wash detergents. To test the ability of compositions to clean glass and plastic, 6 296 mL (10 oz.) Libby heat resistant glass tumblers and 1 plastic tumblers were used. The glass tumblers were cleaned prior to use. New plastic tumblers were used for each experiment.
A food soil solution was prepared using a 50/50 combination of beef stew and hot point soil and employed at 2000 ppm soil. The soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams). The hot point soil was added to the machine to maintain a sump concentration of 2000 ppm.
After filling the dishmachine with 1.1 g (17 grain) water, the heaters were turned on. The wash temperature was adjusted to 65.6°C to 71.1°C (150-160°F). The final rinse temperature was adjusted to 79.4°C to 87.8°C (175-190°F). The controller was set to disclose the amount of detergent in the wash tank. The glass and plastic tumblers were placed in the Raburn rack (see figure below for arrangement; P=plastic tumbler; G=glass tumbler) and the rack was placed inside the dishmachine.

G6

G5

G4

G3

G2 P

G1
T he dishmachine was then started and run through an automatic cycle. At the beginning of each cycle the appropriate amount of hot point sol was added to maintain the sump concentration of 2000 ppm. The detergent concentration is controlled by conductivity.
When the 50 cycles ended, the glasses were allowed to dry overnight. Thereafter they were graded for spots and film accumulation (visual).
The glass and plastic tumblers were then graded for protein accumulation using Commassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution. The Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
The amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining - no spots/no film. A rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining - spots at random (or 20% surface covered in film). A rating of 3 indicated that a quarter to half of the surface was covered with protein after destaining (or 40% surface covered in film). A rating of 4 indicated that half of the glass/plastic surface was covered with protein after destaining (or 60% surface covered in film). A rating of 5 indicated that the entire surface was coated with protein after destaining (or at least 80% surface covered in film).
The ratings of the glass tumblers tested for soil removal were averaged to determine an average soil removal rating from glass surfaces and the ratings of the plastic tumblers tested for soil removal were averaged to determine an average soil removal rating from plastic surfaces. Similarly, the ratings of the glass tumblers tested for redeposition were averaged to determine an average redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for redeposition were averaged to determine an average redeposition rating for plastic surfaces.

The results are shown in following tables, demonstrating that the detergent compositions according to the invention provide at least substantially similar cleaning efficacy and in various embodiments provide superior efficacy over commercial products. The rating scale is shown in Table 9.

TABLE 9

The results of the 50-Cycle test are provided in Tables 10-11.

TABLE 10

50-cycle Spots							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	1.5	1.5	1.0	1.5	1.0	1.0	1.3 (0.3)	4.0
Detergent Control 2	2.0	1.5	1.5	1.0	2.0	1.5	1.6 (0.3)	1.5
Detergent Control 1 + Rinse Aid Control 2	1.5	1.5	1.0	1.0	1.5	1.5	1.3 (0.3)	5.0
Detergent Control 2 + Rinse Aid Control 1	1.5	1.0	1.0	1.0	1.0	1.5	1.2 (0.2)	1.0
Exp. 1	1.5	1.0	1.0	1.0	1.0	1.0	1.1 (0.2)	5.0

TABLE 11

50-cycle Film							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	2.0	3.0	2.0	2.0	3.0	4.5	2.8 (1.0)	1.5
Detergent Control 2	5.0	4.5	4.5	5.0	4.5	5.0	4.8 (0.3)	3.0
Detergent Control 1 + Rinse Aid Control 2	5.0	2.0	2.0	3.0	2.5	4.5	3.2 (1.3)	3.0
Detergent Control 2 + Rinse Aid Control 1	5.0	4.5	5.0	5.0	4.5	5.0	4.9 (0.3)	3.0
Exp. 1	5.0	3.0	4.0	4.5	3.5	5.0	4.2 (0.7)	1.0

EXAMPLE 4

7-CYCLE SPOT, FILM & SOIL REMOVAL EVALUATION FOR INSTITUTIONAL WAREWASH DETERGENTS OR RINSE AIDS

To test the ability of compositions to clean glass and plastic, twelve 296 mL (10 oz.) Libbey heat resistant glass tumblers and four Newport plastic tumblers were used. The glass tumblers were cleaned prior to use.
A food soil solution was prepared using a 50/50 combination of beef stew and hot point soil. The concentration of the solution was 2000 ppm. The soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
The dishmachine was then filled with an appropriate amount of water. After filling the dishmachine with the water, the heaters were turned on. The final rinse temperature was adjusted to 82°C ( 180.degree. F). The glasses and plastic tumblers were soiled by rolling the glasses in a 1:1 (by volume) mixture of Campbell's Cream of Chicken Soup: Kemp's Whole Milk three times. The glasses were then placed in an oven at 71.1°C (160.degree. F.) for 8 minutes. While the glasses were drying, the dishmachine was primed with 120 grams of the food soil solution, which corresponds to 2000 ppm of food soil in the pump.
The soiled glass and plastic tumblers were placed in the Raburn rack (see figure below for arrangement; P=plastic tumbler; G=glass tumbler) and the rack was placed inside the dishmachine. The first two columns with the tumblers were tested for soil removal while the second two columns with the tumblers were tested for redeposition.
The dishmachine was then started and run through an automatic cycle. When the cycle ended, the top of the glass and plastic tumblers were mopped with a dry towel. The glass and plastic tumblers being tested for soil removal were removed and the soup/milk soiling procedure was repeated. The redeposition glass and plastic tumblers were not removed.
At the beginning of each cycle, an appropriate amount of detergent and food soil were added to the wash tank to make up for the rinse dilution. The soiling and washing steps were repeated for seven cycles.
The glass and plastic tumblers were then graded for protein accumulation using Coommassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution. The Coommassie Brilliant Blue R stain was prepared by combining 1.25 g of Coommassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The destaining solution consisted of 45% methanol and 10% acetic acid in distilled water. The amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining. A rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining. A rating of 3 indicated that a quarter of the surface was covered with protein after destaining. A rating of 4 indicated that half of the glass/plastic surface was covered with protein after destaining. A rating of 5 indicated that the entire surface was coated with protein after destaining.
The ratings of the glass tumblers tested for protein removal were averaged to determine an average protein removal rating from glass surfaces and the ratings of the plastic tumblers tested for protein removal were averaged to determine an average protein removal rating from plastic surfaces. Similarly, the ratings of the glass tumblers tested for redeposition were averaged to determine an average protein redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for protein redeposition were averaged to determine an average protein redeposition rating for plastic surfaces.

Glasses are rated visually in the glass viewing area against a black background. Rate each set of glasses as a set, i.e., all redeposition glasses for all products tested. An overall average can be determined for each set. The rating scale used is shown in Table 12.

TABLE 12

Rating	Spots	Film	Protein
1	No spots	No Film	No Protein
2	Spots at random	20% of surface covered in film	20% remains
3	1/4 glass spotted	40% of the surface covered in film	40% remains
4	1/2 glass spotted	60% of the surface covered in film	80% remains
5	Whole glass spotted	At least 80% of the surface covered in film	100% remains

The results of the 7-Cycle test are provided in Tables 13-14 showing average spotting, film, and protein staining ratings (with standard deviation) for glasses and plastic tumblers:

TABLE 13

7-cycle Redeposition	Exp.	Detergent Control 1	Detergent Control 2	Detergent Control 1 + Rinse Aid Control 2	Detergent Control 2 + Rinse Aid Control 1	Exp. 1
Avg. Glass Score Spots	1	5.0 (0.0)	5.0 (0.0)	1.0 (0.0)	5.0 (0.0)	2.3 (0.6)
	2					3.9 (1.5)
	3					1.9 (1.0)
Avg. Glass Score Film	1	1.0 (0.0)	1.2 (0.2)	1.77 (0.2)	1.0 (0.0)	3.6 (0.4)
	2					2.1 (1.5)
	3					4.0 (1.0)
Avg. Protein Glass Score	1	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)
	2					1.0 (0.0)
	3					1.0 (0.0)
Avg. Protein Plastic Score	1	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)
	2					1.5 (0.5)
	3					1.0 (0.0)

TABLE 14

7-cycle Soil removal	Exp.	Detergent Control 1	Detergent Control 2	Detergent Control 1 + Rinse Aid Control 2	Detergent Control 2 + Rinse Aid Control 1	Exp. 1
Avg. Glass Score Spots	1	5.0 (0.0)	4.8 (0.2)	1.0 (0.0)	4.2 (1.1)	3.5 (1.2)
	2					4.1 (0.9)
	3					1.5 (0.7)
Avg. Glass Score Film	1	1.1 (0.2)	4.4 (0.2)	4.1 (0.9)	4.8 (0.2)	2.8 (1.2)
	2					2.7 (1.0)
	3					4.3 (1.1)
Avg. Protein Glass Score	1	1.3 (0.3)	5.0 (0.0)	1.3 (0.3)	5.0 (0.0)	3.0 (1.0)
	2					1.0 (0.0)
	3					1.0 (0.0)
Avg. Protein Plastic Score	1	1.0 (0.0)	5.0 (0.0)	1.0 (0.0)	5.0 (0.0)	1.8 (0.3)
	2					1.0 (0.0)
	3					1.5 (0.0)

EXAMPLES 5-8

The materials used in the Examples 5-8 are provided herein:

Acusol^® 448: a polyacrylic acid copolymer, available from the Dow Chemical Company.
Additional materials commercially-available from multiple sources include: sodium carbonate, ash monohydrate, sodium tripolyphosphate (anhydrous), zinc chloride, HEDP, and KOH.

An exemplary 2-in-1 detergent (not according to the invention) comprising a polymer was prepared and is shown in Table 15. Throughout Examples, the formulation is referred to as Experimental Formula 2 (Exp. 2).

TABLE 15

Raw material	Exp. 2
Alkalinity source	45-75
Builder	10-30
EO/PO copolymer	1-10
Alcohol alkoxylate	1-10
Polycarboxylic acid polymer	1-10
Corrosion inhibitor	0.01-0.5
Phosphonate builder, 60%	1-10
KOH, 45%	1-10
Total	100

Existing detergents, rinse aids, and Experimental Formula 2 were tested against distilled water. Detergent Control 1 and Detergent Control 2 are commercially available detergents (phosphate-based detergents). Rinse Aid Control 1 and rinse Aid Control are two commercially available rinse aids (employing higher amounts of active ingredients surfactants of at least two ionic categories (e.g., nonionic and cationic)). The use concentrations for all experiments described below are provided in Table 16: TABLE 16

Sample Use concentration [ppm]

DI water N/A

Detergent Control

1 1500

Detergent Control 2 1000

Rinse Aid Control 1 536

Rinse Aid Control 2 536

Exp. 2 1415
All warewash testing was performed with 296 mL (10 oz.) Libbey glasses on a Hobart AM-15 warewash machine. The specifications of the Hobart AM-15 warewash machine are as follows:

Hobart AM-15 warewash machine specifications.

Washbath volume:	53L
Rinse volume:	2.8L
Wash time:	50 sec.
Rinse time:	9 sec.

EXAMPLE 5

DYNAMIC SURFACE TENSION

APPARATUS AND MATERIALS:

1. SITA T60 (Sita Messtechnik, Germany)
2. Oil bath with stir bar
3. Heating and stirring plate
4. Glass beakers
5. Glass vials (20 mL)

The SITA science line t60 was calibrated with DI water. Clean water samples after calibration should have a surface tension of 72.0±1.0mN/m (depending on water quality and temperature). Following calibration, the SITA was programmed to take readings at the desired time intervals (i.e., 0.3, 1.6, 3.0, and 9.1 seconds). Three separate solutions at the desired ppm were prepared for each composition (described as A-C) to be tested (e.g., three samples of Exp. 2, three samples of Detergent Control 1). 10-15 mL were transferred into 20 mL vials and immersed in a heated oil bath to 72 °C (160 °F) ± 2°C. The samples were equilibrated for 10-15 minutes. The samples were individually removed from the oil bath and the tested in the SITA. After each sample was tested the SITA's cleaning procedure was run, then the surface tension of DI water was checked to ensure the SITA was adequately clean. If the DI water measurements were not within 72.0 ±1.0 mN/m, then the cleaning procedure was run again. The surface tension (mN/m) versus bubble life time at 71.1°C (160 °F) experimental data is provided in Tables 17-A through 17-F below, where τ is the bubble life time in seconds and γ is the surface tension in mN/m.

TABLE 17-A

Detergent Control 1
Sample A		Sample B		Sample C
τ	γ	τ	γ	τ	γ
0.031	65.1	0.031	67.9	0.03	66.4
0.041	65	0.042	65.9	0.041	66.2
0.058	64.5	0.058	65.8	0.058	65
0.083	64.1	0.082	65.3	0.081	64.1
0.116	63.4	0.116	64.6	0.116	64.4
0.159	62.8	0.161	63.8	0.162	64.3
0.223	63	0.223	63.9	0.226	63.7
0.313	62.6	0.313	63.7	0.315	63.8
0.421	62.5	0.426	63.5	0.419	63.2
0.624	62.3	0.622	62.7	0.621	62.7
0.857	61.4	0.878	62.7	0.883	62.9
1.164	62	1.148	62.4	1.149	62.2
1.659	61.7	1.648	62.1	1.656	62.3
2.495	61.2	2.527	61.1	2.532	61.4
3.217	60.7	3.145	60.9	3.185	61.3
4.388	59.7	4.28	60.3	4.162	60.6
6.463	57.6	6.62	57.3	6.166	59.2
8.781	54.7	9.156	53.7	8.342	55.5
11.244	52	13.403	52.1	11.972	52.7
18.795	45.7	15.816	45.7	16.933	51
21.721	44.4	21.895	47.7	22.163	47.4

TABLE 17-B

TABLE 17-C

TABLE 17-D

TABLE 17-E

Experimental Formulation (Exp.2)
Sample A		Sample B		Sample C
τ	Γ	τ	γ	τ	γ
0.03	64.7	0.03	66.7	0.031	65.6
0.41	64.3	0.43	65.3	0.043	64.3
0.058	66.1	0.058	64.4	0.058	63.2
0.083	63.9	0.081	62.5	0.082	62.5
0.118	62	0.116	61.5	0.116	60.6
0.167	59.9	0.161	60.2	0.161	59.3
0.221	58.5	0.225	58.8	0.225	57.8
0.313	57.6	0.313	57.1	0.313	56.3
0.427	57.6	0.43	525.6	0.423	55
0.627	54.3	0.622	54.4	0.632	53.7
0.871	54.4	0.867	53.3	0.886	52.7
1.169	52.8	1.161	52.3	1.145	52.2
1.727	536	1.652	51.5	1.656	51
2.467	52.5	2.543	50.4	2.572	50.3
3.145	52	3.515	49.9	3.092	50.2
4.234	20.9	4.49	49.1	4.389	49.3
6.126	50.3	6.261	48.3	6.106	48.4
9.11	48.1	8.886	47.7	8.891	47.3
12.609	48.2	11.701	46.7	12.448	46.5
18.514	47.1	17.215	45.4	17.854	45.5
22.164	45.3	23.579	44.9	23.081	44.7

TABLE 17-F

The average surface tension at 71.1°C (160 °F) for the average bubble life times of 0.3, 1.6, 3.0, and 9.1 seconds was tested. The results are provided in Table 18.

TABLE 18

Sample	Avg. Surface Tension at 0.3 s	Avg. Surface Tension at 1.6 s	Avg. Surface Tension at 3.0 s	Avg. Surface Tension at 9.1 s
DI water	64.8	64.2	64.5	64.0
Detergent Control 1	63.0	59.4	56.1	49.0
Detergent Control 2	63.4	62.0	61.0	54.6
Rinse Aid Control 1	62.6	57.2	54.3	50.9
Rinse Aid Control 2	60.8	51.2	46.6	39.2
Exp. 2	57.0	52.0	50.7	47.7

The data demonstrates the surface tension of Experimental Formulation 2 decreases quickly with a significant drop in surface tension at the bubble life time of 9.1 seconds. This is similar to a well-performing rinse aid, such as Rinse Aid Control 2. These results are demonstrated in Figure 2.

EXAMPLE 6

ONE HUNDRED-CYCLE FILM EVALUATION FOR INSTITUTIONAL WAREWASH DETERGENTS

To determine the ability of various detergent compositions to remove spots and film from ware, six Libby 296 mL (10 oz.) glass tumblers were prepared by removing all film and foreign material from the surfaces of the glasses. A Hobart AM-15 warewash machine was then filled with an appropriate amount of water and the water was tested for hardness. After recording the hardness value, the tank heaters were turned on. On the day of the experiments, the water hardness was 1.1 g (17 grains). The warewash machine was turned on and wash/rinse cycles were run through the machine until a wash temperature of between 65.6°C (150°F) and 71.1°C (160°F) and a rinse temperature of between 79.4°C (175°F) and 87.8°C (190°F) were reached. The controller was then set to dispense an appropriate amount of detergent into the wash tank. The detergent was dispensed such that when the detergent was mixed with water during the cycle to form a use solution, the detergent concentration in the use solution was 750 parts per million (ppm). The solution in the wash tank was titrated to verify detergent concentration. The warewash machine had a washbath volume of 58 liters, a rinse volume of 2.8 liters, a wash time of 50 seconds, and a rinse time of 9 seconds.
The six clean glass tumblers were placed diagonally in a Raburn rack and four Newport 296 mL (10 oz.) plastic tumblers were placed off-diagonally in the Raburn rack (see figure below for arrangement) and the rack was placed inside the warewash machine. (P=plastic tumbler; G=glass tumbler).

G

G

G

G

G P

G
The 100 cycle test was then started. At the beginning of each wash cycle, the appropriate amount of detergent was automatically dispensed into the warewash machine to maintain the initial detergent concentration. The detergent concentration was controlled by conductivity.

Upon completion of 100 cycles, the rack was removed from the warewash machine and the glass and plastic tumblers were allowed to dry. The glass and plastic tumblers were then graded for spot and film accumulation using film ratings and using an analytical light box evaluation. The film rating scale is provided in Table 19:

TABLE 19

The results of the 100-Cycle test are provided in Tables 20 and 21.

TABLE 20

100-cycle Film							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	4.5	3.0	3.5	4.5	3.5	4.0	3.8 (0.6)	1.5
Detergent Control 2	5.0	3.5	4.0	4.5	4.5	4.0	4.3 (0.5)	2.5
Detergent Control 1 + Rinse Aid Control 2	4.5	4.0	4.5	4.5	4.0	5.0	4.4 (0.3)	3.5
Detergent Control 2 + Rinse Aid Control 1	4.5	3.0	4.0	4.0	3.5	4.0	3.8 (0.5)	2.5
Exp. 2	3.0	1.5	1.5	1.5	1.5	2.0	1.8 (0.6)	2.0

TABLE 21

100-cycle Light box							Summe d Glass Score	Plastic Score	Summed Total Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	Maxed (65535)	38906	55734	62998	47238	59893	330304	17681	347985
Detergent Control 2	Maxed (65535)	55061	59141	63854	63879	59859	367329	31530	398859
Detergent Control 1 + Rinse Aid Control 2	Maxed (65535)	63291	65304	65226	65412	Maxed (65535)	390303	46448	436751
Detergent Control 2 + Rinse Aid Control 1	Maxed (65535)	42699	54556	56364	50826	59589	329589	30727	360296
Exp. 2	34088	18832	18644	18790	19312	20966	130632	18685	149317

EXAMPLE 7

FIFTY CYCLE REDEPOSITION EXPERIMENT FOR INSTITUTIONAL WAREWASH DETERGENTS

The cleaning efficacy of the compositions according to the invention and controls were further evaluated using a 50 cycle redeposition experiment for institutional ware wash detergents. To test the ability of compositions to clean glass and plastic, 6 296 mL (10 oz.) Libby heat resistant glass tumblers and 1 plastic tumblers were used. The glass tumblers were cleaned prior to use. New plastic tumblers were used for each experiment.
A food soil solution was prepared using a 50/50 combination of beef stew and hot point soil and employed at 2000 ppm soil. The soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams). The hot point soil was added to the machine to maintain a sump concentration of 2000 ppm.
After filling the dishmachine with 1.1 g (17 grain) water, the heaters were turned on. The wash temperature was adjusted to 65.6°C to 71.1°C (150-160°F). The final rinse temperature was adjusted to 79.4°C to 87.8 °C (175-190°F). The controller was set to disclose the amount of detergent in the wash tank. The glass and plastic tumblers were placed in the Raburn rack (see figure below for arrangement; P=plastic tumbler; G=glass tumbler) and the rack was placed inside the dishmachine.

G6

G5

G4

G3

G2 P

G1
The dishmachine was then started and run through an automatic cycle. At the beginning of each cycle the appropriate amount of hot point sol was added to maintain the sump concentration of 2000 ppm. The detergent concentration is controlled by conductivity.
When the 50 cycles ended, the glasses were allowed to dry overnight. Thereafter they were graded for spots and film accumulation (visual).
The glass and plastic tumblers were then graded for protein accumulation using Commassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution. The Commassie Brilliant Blue R stain was prepared by combining 1.25 g of Commassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The destaining solution consisted of 45% methanol and 10% acetic acid in distilled water.
The amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining - no spots/no film. A rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining - spots at random (or 20% surface covered in film). A rating of 3 indicated that a quarter to half of the surface was covered with protein after destaining (or 40% surface covered in film). A rating of 4 indicated that half of the glass/plastic surface was covered with protein after destaining (or 60% surface covered in film). A rating of 5 indicated that the entire surface was coated with protein after destaining (or at least 80% surface covered in film).
The ratings of the glass tumblers tested for soil removal were averaged to determine an average soil removal rating from glass surfaces and the ratings of the plastic tumblers tested for soil removal were averaged to determine an average soil removal rating from plastic surfaces. Similarly, the ratings of the glass tumblers tested for redeposition were averaged to determine an average redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for redeposition were averaged to determine an average redeposition rating for plastic surfaces.

The results are shown in following tables, demonstrating that the detergent compositions according to the invention provide at least substantially similar cleaning efficacy and in various embodiments provide superior efficacy over commercial products. The rating scale is shown in Table 22.

TABLE 22

The results of the 50-Cycle test are provided in Tables 23 and 24:

TABLE 23.

50-cycle Redeposition Spots							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	1.5	1.5	1.0	1.5	1.0	1.0	1.3 (0.3)	4.0
Detergent Control 2	2.0	1.5	1.5	1.0	2.0	1.5	1.6 (0.3)	1.5
Detergent Control 1 + Rinse Aid Control 2	1.5	1.5	1.0	1.0	1.5	1.5	1.3 (0.3)	5.0
Detergent Control 2 + Rinse Aid Control 1	1.5	1.0	1.0	1.0	1.0	1.5	1.2 (0.2)	1.0
Exp. 2	1.5	2.0	1.5	1.0	1.5	1.5	1.5 (0.3)	5.0

TABLE 24.

50-cycle Redeposition Film							Avg. Glass Score (St. Dev.)	Plastic Score
	G1	G2	G3	G4	G5	G6		P1
Detergent Control
1	2.0	3.0	2.0	2.0	3.0	4.5	2.8 (1.0)	1.5
Detergent Control 2	5.0	4.5	4.5	5.0	4.5	5.0	4.8 (0.3)	3.0
Detergent Control 1 + Rinse Aid Control 2	5.0	2.0	2.0	3.0	2.5	4.5	3.2 (1.3)	3.0
Detergent Control 2 + Rinse Aid Control 1	5.0	4.5	5.0	5.0	4.5	5.0	4.9 (0.3)	3.0
Exp. 2	4.0	3.5	3.5	4.0	4.0	4.5	3.9 (0.3)	1.0

EXAMPLE 8

To test the ability of compositions to clean glass and plastic, twelve 296 mL (10 oz.) Libbey heat resistant glass tumblers and four Newport plastic tumblers were used. The glass tumblers were cleaned prior to use.
A food soil solution was prepared using a 50/50 combination of beef stew and hot point soil. The concentration of the solution was 2000 ppm. The soil included two cans of Dinty Moore Beef Stew (1360 grams), one large can of tomato sauce (822 grams), 15.5 sticks of Blue Bonnet Margarine (1746 grams) and powered milk (436.4 grams).
The dishmachine was then filled with an appropriate amount of water. After filling the dishmachine with the water, the heaters were turned on. The final rinse temperature was adjusted to 82°C (180.degree. F). The glasses and plastic tumblers were soiled by rolling the glasses in a 1:1 (by volume) mixture of Campbell's Cream of Chicken Soup: Kemp's Whole Milk three times. The glasses were then placed in an oven at 71.1°C (160.degree. F.) for 8 minutes. While the glasses were drying, the dishmachine was primed with 120 grams of the food soil solution, which corresponds to 2000 ppm of food soil in the pump.
The soiled glass and plastic tumblers were placed in the Raburn rack (see figure below for arrangement; P=plastic tumbler; G=glass tumbler) and the rack was placed inside the dishmachine. The first two columns with the tumblers were tested for soil removal while the second two columns with the tumblers were tested for redeposition.
The dishmachine was then started and run through an automatic cycle. When the cycle ended, the top of the glass and plastic tumblers were mopped with a dry towel. The glass and plastic tumblers being tested for soil removal were removed and the soup/milk soiling procedure was repeated. The redeposition glass and plastic tumblers were not removed.
At the beginning of each cycle, an appropriate amount of detergent and food soil were added to the wash tank to make up for the rinse dilution. The soiling and washing steps were repeated for seven cycles.
The glass and plastic tumblers were then graded for protein accumulation using Coommassie Brilliant Blue R stain followed by destaining with an aqueous acetic acid/methanol solution. The Coommassie Brilliant Blue R stain was prepared by combining 1.25 g of Coommassie Brilliant Blue R dye with 45 mL of acetic acid and 455 mL of 50% methanol in distilled water. The destaining solution consisted of 45% methanol and 10% acetic acid in distilled water. The amount of protein remaining on the glass and plastic tumblers after destaining was rated visually on a scale of 1 to 5. A rating of 1 indicated no protein was present after destaining. A rating of 2 indicated that random areas (barely perceptible) were covered with protein after destaining. A rating of 3 indicated that a quarter of the surface was covered with protein after destaining. A rating of 4 indicated that half of the glass/plastic surface was covered with protein after destaining. A rating of 5 indicated that the entire surface was coated with protein after destaining.
The ratings of the glass tumblers tested for protein removal were averaged to determine an average protein removal rating from glass surfaces and the ratings of the plastic tumblers tested for protein removal were averaged to determine an average protein removal rating from plastic surfaces. Similarly, the ratings of the glass tumblers tested for redeposition were averaged to determine an average protein redeposition rating for glass surfaces and the ratings of the plastic tumblers tested for protein redeposition were averaged to determine an average protein redeposition rating for plastic surfaces.

EVALUATION RESULTS:

Glasses are rated visually in the glass viewing area against a black background. Rate each set of glasses as a set, i.e., all redeposition glasses for all products tested. An overall average can be determined for each set. The rating scale used is shown in Table 25.

TABLE 25

The results of the 7-Cycle test are provided in Tables 26 and 27 showing average spotting, film, and protein staining ratings (with standard deviation) for glasses and plastic tumblers.

TABLE 26.

7-cycle Redeposition	Exp.	Detergent Control 1	Detergent Control 2	Detergent Control 1 + Rinse Aid Control 2	Detergent Control 2 + Rinse Aid Control 1	Exp. 2
Avg. Glass Score Spots	1	5.0 (0.0)	5.0 (0.0)	1.0 (0.0)	5.0 (0.0)	3.5 (1.4)
	2					2.3 (0.4)
	3					5.0 (0.0)
Avg. Glass Score Film	1	1.0 (0.0)	1.2 (0.2)	1.77 (0.2)	1.0 (0.0)	2.9 (1.1)
	2					2.6 (0.5)
	3					1.0 (0.0)
Avg. Protein Glass Score	1	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)
	2					1.0 (0.0)
	3					1.0 (0.0)
Avg. Protein Plastic Score	1	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)	1.0 (0.0)
	2					1.0 (0.0)
	3					1.0 (0.0)

TABLE 27.

7-cycle Soil removal	Exp.	Detergent Control 1	Detergent Control 2	Detergent Control 2 + Rinse Aid Control 2	Detergent Control 2 + Rinse Aid Control 1	Exp. 2
Avg. Glass Score Spots	1	5.0 (0.0)	4.8 (0.2)	1.0 (0.0)	4.2 (1.1)	2.1 (0.6)
	2					2.4 (0.6)
	3					5.0 (0.0)
Avg. Glass Score Film	1	1.1 (0.2)	4.4 (0.2)	4.1 (0.9)	4.8 (0.2)	4.7 (0.5)
	2					2.3 (0.2)
	3					1.8 (0.4)
Avg. Protein Glass Score	1	1.3 (0.3)	5.0 (0.0)	1.3 (0.3)	5.0 (0.0)	3.5 (0.5)
	2					1.3 (0.3)
	3					2.0 (0.5)
Avg. Protein Plastic Score	1	1.0 (0.0)	5.0 (0.0)	1.0 (0.0)	5.0 (0.0)	1.0 (0.0)
	2					2.0 (0.0)
	3					1.5 (0.0)

These Examples demonstrate that the compositions of the present invention, provided similar, substantially similar, or better performance when compared with existing detergents and existing detergents and rinse aids in most categories of cleaning and antiredeposition in a traditional warewash procedure.

Claims

An alkaline detergent and rinsing composition comprising:
from 45 wt-% to 75 wt-% of an alkalinity source comprising an alkali metal carbonate; and

at least two nonionic surfactants, wherein said nonionic surfactants comprise from 1 wt-% to 10 wt-% of the alkaline detergent composition of a C10-C12 alcohol alkoxylate with 15 to 25 moles of alkyl oxide and from 1 wt-% to 10 wt-% of the alkaline detergent composition of an EO/PO copolymer represented by the formula (PO)y(EO)x(PO)y, where x is in the range of 5 to 50, y is in the range of 1 to 50, and x plus y is in the range of 6 to 200; and

from 5 wt-% to 50 wt-% of a builder selected from the group consisting of condensed phosphates, alkali metal silicates and metasilicates,

phosphonates and aminocarboxylic acids;

wherein said composition performs both a cleaning and rinsing function.
The composition of claim 1, wherein said alcohol alkoxylate and EO/PO copolymer are in a ratio of between 3:1 to 1:3.
The composition of claim 1 wherein the alkalinity source comprises an alkali metal carbonate, wherein the alkalinity source is substantially free of alkali metal hydroxide, and wherein the composition comprises a neutralizing agent comprising up to 10 wt-% alkali metal hydroxide.
The composition of claim 1, further comprising an enzyme.
The composition of claim 4, wherein the enzyme is a protease, lipase and/or amylase.
An alkaline detergent and rinsing composition according to claim 1, further comprising:
a polymer comprising a polycarboxylic acid polymer, copolymer, and/or terpolymer.
The composition of claim 6, wherein the polymer is present from 0.1 wt-% to 40 wt-% and comprises a polyacrylic acid polymer, copolymer, and/or terpolymer.
The composition of claim 7, wherein the polyacrylic acid polymer, copolymer, and/or terpolymers is an acrylic/maleic acid copolymer.
A method of cleaning and rinsing ware comprising:
contacting ware with an alkaline detergent composition of claim 1.
The composition of claim 1, wherein the alkaline detergent is a cast, extruded, or pressed solid.