WO2024000340A1 - Détergent alcalin comprimé protecteur de métaux non silicaté et additif de rinçage - Google Patents

Détergent alcalin comprimé protecteur de métaux non silicaté et additif de rinçage Download PDF

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WO2024000340A1
WO2024000340A1 PCT/CN2022/102600 CN2022102600W WO2024000340A1 WO 2024000340 A1 WO2024000340 A1 WO 2024000340A1 CN 2022102600 W CN2022102600 W CN 2022102600W WO 2024000340 A1 WO2024000340 A1 WO 2024000340A1
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composition
acid
solid
ppm
compositions
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PCT/CN2022/102600
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English (en)
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Jesus CABANAS
Zhenbo Gao
Xin Lu
Jin Ming Zhang
Ken NAIR
Erik C. Olson
Nathan D. Peitersen
Janel Marie Kieffer
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Ecolab Usa Inc.
Zhenbo Gao
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Priority to PCT/CN2022/102600 priority Critical patent/WO2024000340A1/fr
Publication of WO2024000340A1 publication Critical patent/WO2024000340A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C11D2111/16—

Definitions

  • the disclosure relates to solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions effective for reducing corrosion and providing metal protection while also improving drying times of surfaces. Methods of making the compositions and methods of using the same are provided.
  • Alkaline detergents are known to provide effective detergency.
  • the formulations can vary greatly in degree of corrosiveness, acceptance as consumer-friendly and/or environmentally-friendly products, as well as other detergent characteristics.
  • the alkalinity of these compositions increase, the difficulty in protecting metal surfaces also increases.
  • Silicates are known to precipitate from aqueous solution at alkaline pH, namely pH below 11, which reduces the effectiveness and consumer acceptance of these materials to prevent corrosion of the contacted surfaces when used in aqueous cleaning solutions having a lower pH. Additionally, when silicate-containing compositions or their residues are allowed to dry on surfaces, films or spots are often formed, which are visible and which are themselves very difficult to remove. The presence of these silicon-containing deposits can affect the texture of the cleaned surface, the appearance of the surface, and on cooking or storage surfaces, can affect the taste of the materials that come into contact with the cleaned surfaces. Further, such silicon-containing deposits can require an acid cleaning step over time to review the deposits and visual residue. It is desirable to eliminate the need for this step in cleaning surfaces.
  • An advantage of the solid 2-in-1 alkaline detergent and rinse aid compositions is the effective corrosion inhibition on metal surfaces, such as aluminum, without the use of silicate raw materials to eliminate the formation of films or precipitation of particulates onto the cleaned surfaces, while also providing improved drying times and water hardness protection.
  • solid 2-in-1 alkaline detergent and rinse aid compositions comprise: an alkali metal carbonate alkalinity source; a metal protecting combination of an acid chelant or a chelant and an acid, and at least one water conditioning agent; and at least one nonionic surfactant.
  • use solutions of the solid 2-in-1 alkaline detergent and rinse aid compositions comprise: the solid compositions described herein in a solution with an aqueous source, preferably water.
  • a method of using a 2-in-1 detergent and rinse additive composition comprises: contacting a use solution of the solid 2-in-1 alkaline detergent and rinse aid composition to an article or surface including a hard metal surface in need of cleaning and drying, and thereafter rinsing said hard metal surface, wherein the use solution of the composition provides both effective cleaning, rinsing and drying of the surface with water hardness protection and no filming on metal surfaces.
  • FIG. 1B is a scatterplot of corrosion (MPY) evaluated with varying concentrations of carbonate of exemplary compositions on aluminum alloys.
  • FIG. 1C is a scatterplot of corrosion (MPY) evaluated with varying pH of exemplary compositions on aluminum alloys.
  • FIG. 2A is a graph showing percent change in length of exemplary solid block compositions.
  • FIG. 2B is a graph showing percent change in width of exemplary solid block compositions.
  • FIG. 3 is a graph showing soil removal rate based on percentage of soil removal comparing efficacy of exemplary solid compositions according to the description.
  • FIG. 4A is a graph of drying time of an exemplary composition on ceramic and melamine surfaces.
  • FIG. 4B is a comparative graph of drying time of a commercial rinse aid formula on ceramic and melamine.
  • solid 2-in-1 alkaline detergent and rinse aid compositions provide effective corrosion inhibition on metal surfaces, such as aluminum, without the use of silicate raw materials to eliminate the formation of films or precipitation of particulates onto the cleaned surfaces, while also providing improved drying times and water hardness protection.
  • range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 11/2, and 43/4. This applies regardless of the breadth of the range.
  • the term “and/or” e.g., “X and/or Y” shall be understood to mean either “X and Y" or "X or Y” and shall be taken to provide explicit support for both meanings or for either meaning, e.g. A and/or B includes the options i) A, ii) B or iii) A and B.
  • compositions of the present disclosure may comprise, consist essentially of, or consist of the components and ingredients of the present disclosure as well as other ingredients described herein.
  • “consisting essentially of” means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.
  • invention or “present invention” are not intended to refer to any single embodiment of the particular invention but encompass all possible embodiments as described in the specification and the claims.
  • actives or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts. It is also sometimes indicated by a percentage in parentheses, for example, “chemical (10%) . ”
  • alkaline sensitive metal identifies those metals that exhibit corrosion and/or discoloration when exposed to an alkaline detergent in solution.
  • An alkaline solution is an aqueous solution having a pH that is greater than 8.
  • Exemplary alkaline sensitive metals include soft metals such as aluminum, nickel, tin, zinc, copper, brass, bronze, and mixtures thereof.
  • Aluminum and aluminum alloys are common alkaline sensitive metals that can be cleaned by the warewash detergent compositions of the invention.
  • alkyl or “alkyl groups” refers to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. ) , cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.
  • straight-chain alkyl groups e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.
  • cyclic alkyl groups or “cycl
  • alkyl includes both “unsubstituted alkyls” and “substituted alkyls.
  • substituted alkyls refers to alkyl groups having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone.
  • substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino) , acylamino (including alkylcarbonylamino, arylamino, diarylamino, and alky
  • substituted alkyls can include a heterocyclic group.
  • heterocyclic group includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated.
  • heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes) , thiirane (episulfides) , dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.
  • aziridine ethylene oxide (epoxides, oxiranes) , thiirane (episulfides) , dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.
  • cleaning refers to a method used to facilitate or aid in soil removal, bleaching, de-scaling, de-staining, microbial population reduction, rinsing, or any combination thereof.
  • exemplary refers to an example, an instance, or an illustration, and does not indicate a most preferred embodiment unless otherwise stated.
  • the term “free” refers to compositions completely lacking the component or having such a small amount of the component that the component does not affect the performance of the composition.
  • the compositions are free of silicates or silicone-containing materials.
  • polymer refers to a molecular complex comprised of a more than ten monomeric units and generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, and higher "x" mers, further including their analogs, derivatives, combinations, and blends thereof.
  • polymer shall include all possible isomeric configurations of the molecule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof.
  • polymer shall include all possible geometrical configurations of the molecule.
  • soil refers to any soil, including, but not limited to, non-polar oily and/or hydrophobic substances which may or may not contain particulate matter such as industrial soils, mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust, and/or food based soils such as blood, proteinaceous soils, starchy soils, fatty soils, cellulosic soils, etc.
  • non-polar oily and/or hydrophobic substances which may or may not contain particulate matter such as industrial soils, mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust, and/or food based soils such as blood, proteinaceous soils, starchy soils, fatty soils, cellulosic soils, etc.
  • a “solid” composition refers to a composition in the form of a solid such as a powder, an agglomerate, 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 term “solid” refers to the state of the composition under the expected conditions of storage and use of the solid composition. In general, it is expected that the composition will remain in solid form when exposed to elevated temperatures of above 120°F.
  • the solids described herein are dimensionally stable, meaning that they retain shape overtime. For example the width and height of a solid does not change (i.e. swelling) more than about 3%over the course of four weeks at room temperature, between 104 °F and 122 °F.
  • the term “substantially” refers to a great or significant extent. “Substantially” can thus refer to a plurality, majority, and/or a supermajority of said quantifiable variable, given proper context.
  • 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-%.
  • 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 compositions are substantially free of silicates or silicone-containing materials.
  • 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.
  • surfactant or "surface active agent” refers to an organic chemical that when added to a liquid changes the properties of that liquid at a surface.
  • ware refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors.
  • warewashing refers to washing, cleaning, or rinsing ware. Ware also refers to items made of plastic.
  • Types of plastics that can be cleaned with the compositions include but are not limited to, those that include polypropylene polymers (PP) , polycarbonate polymers (PC) , melamine formaldehyde resins or melamine resin (melamine) , acrylonitrile-butadiene-styrene polymers (ABS) , and polysulfone polymers (PS) .
  • Other exemplary plastics that can be cleaned using the compounds and compositions of the disclosure include polyethylene terephthalate (PET) polystyrene polyamide.
  • weight percent, " wt-%, “percent by weight, “ “%by weight, “ and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, “percent, “ “%, “ and the like are intended to be synonymous with “weight percent, " “wt-%, “ etc.
  • the solid alkaline 2-in-1 detergent and rinse aid compositions include an alkalinity source, a chelant, at least one water conditioning agent, and at least one nonionic surfactant.
  • the compositions can include various additional functional ingredients.
  • the solid compositions are substantially free of silicates or silicone-containing materials. In embodiments the solid compositions are free of silicates or silicone-containing materials.
  • the solid alkaline 2-in-1 detergent and rinse aid compositions can beneficially replace liquid detergents and separate liquid rinse aid compositions to provide a single 2-in-1 formulation.
  • the single 2-in-1 formulation can include a multi-use solid composition.
  • the solid composition overcomes formulation challenges conventionally associated with surfactant stability in solid compositions.
  • Exemplary solid compositions are shown in Table 1 in weight percentage. While the components may have a percent actives of 100%, it is noted that Table 1 does not recite the percent actives of the components, but rather, recites the total weight percentage of the raw materials (i.e. active concentration plus inert ingredients) .
  • the solid composition comprises one or more alkalinity sources.
  • the source of alkalinity can be any source of alkalinity that is compatible with the other components of the 2-in-1 detergent and rinse aid composition.
  • Exemplary sources of alkalinity include alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, alkali metal salts, phosphates, amines, and mixtures thereof, preferably alkali metal carbonates including sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate, or mixtures thereof, and most preferred is sodium carbonate.
  • the alkalinity source is an alkali metal carbonate that is a blend of dense and light carbonate, e.g. sodium carbonate, wherein the light carbonate is useful in aiding with absorption of liquid in the formulations for solidification.
  • the alkalinity source provides a solid composition that dilutes to an alkaline pH.
  • embodiments of the solid compositions will provide a pH of between about 9 and about 12.5 upon dilution.
  • embodiments of the solid compositions will provide a pH between about 9 and about 11 upon dilution, preferably between about 9 and about 10.5 upon dilution.
  • the alkalinity source is included in the detergent composition at an amount of at least about 40 wt-%to about 90 wt-%, about 50 wt-%to about 90 wt-%, about 50 wt-%to about 85 wt-%, about 60 wt-%to about 85 wt-%, or about 60 wt-%to about 80 wt-%.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the solid composition comprises a non-silicate chelant.
  • the chelant provides metal protection.
  • Suitable chelating agents can include aminocarboxylates, aminocarboxylic acids, succinic acid based compounds, phosphonates including amino phosphonates, condensed phosphates, polyfunctionally-substituted aromatic chelating agents, and mixtures thereof.
  • the chelant is included in the solid composition at an amount of at least about 2 wt-%to about 30 wt-%, about 2 wt-%to about 20 wt-%, about 4 wt-%to about 20 wt-%, about 6 wt-%to about 20 wt-%, or about 6 wt-%to about 16 wt-%.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • Exemplary aminocarboxylic acid chelants include glutamic acid-N, N-diacetic acid (GLDA) , methylglycine-N, N-diacetic acid (MGDA) , N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) , N-hydroxyethylethylenediaminetriacetic acid (HEDTA) , nitrilotriacetic acid (NTA) , hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetic acid (DTPA) , ethylenediamine disuccinic acid (EDDS) , 3-hydroxy-2, 2-iminodisuccinic acid (HIDS) , hydroxyethyliminodiacetic acid (HEIDA) and other similar acids having an amino group with a carboxylic acid substituent
  • the chelant is an aminocarboxylate or an aminocarboxylic acid.
  • the chelant is ethylenediaminetetraacetic acid (EDTA or acid EDTA) .
  • EDTA ethylenediaminetetraacetic acid
  • the acid chelant such as acid EDTA benefits solid block cohesion when there is a silicate-free formulation as demonstrated in the Examples.
  • a low solubility acid source can be included to provide desired pH and solid stability without decreasing the performance benefits of the solid compositions.
  • succinate based compound and “succinic acid based compound” are used interchangeably herein. These include; for example, aspartic acid-N-monoacetic acid (ASMA) , aspartic acid-N, N-diacetic acid (ASDA) , aspartic acid-N-monopropionic acid (ASMP) , iminodisuccinic acid (IDS) , Imino diacetic acid (IDA) , N- (2-sulfomethyl) aspartic acid (SMAS) , N- (2-sulfoethyl) aspartic acid (SEAS) , N- (2-sulfomethyl) glutamic acid (SMGL) , N- (2-sulfoethyl) glutamic acid (SEGL) , N-methyliminodiacetic acid (MIDA) , alanine-N, N-diacetic acid (ASMA) , aspartic acid-N, N-diacetic acid (ASDA) ,
  • chelants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts.
  • Preferred salts of the abovementioned compounds are the ammonium and/or alkali metal salts, i.e. the lithium, sodium, and potassium salts, and particularly preferred salts are the sodium salts.
  • 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 composition by fixing the free water present in the composition as water of hydration.
  • Amino phosphonates are also suitable for use as chelating agents and include ethylenediaminetetrakis (methylenephosphonates) (HEDP) . Preferred, these amino phosphonates that do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • the solid composition comprises at least one water conditioning agent.
  • at least two water conditioning agents are included in the solid composition.
  • Exemplary water conditioning agents include polycarboxylates and polycarboxylic acids, and polyacrylate, polymethacrylate, and/or polymaleate homopolymers, copolymers or terpolymers.
  • the solid composition includes about a 1: 1 wt-ratio (or a 0: 5: 1 to 1: 0.5 wt-ratio) of a first water conditioning agent that is a polycarboxylate or polycarboxylic acid, and a second water conditioning agent that is a polyacrylate, polymethacrylate, and/or polymaleate homopolymer, copolymer or terpolymer.
  • polycarboxylate homopolymers, copolymers and terpolymers are known and described in patent and other literature, and are available commercially.
  • Exemplary polycarboxylates that may be utilized according to the invention include for example: homopolymers, copolymers and terpolymers of polyacrylates; polymethacrylates; polymaleates.
  • Suitable polymers include acrylic acid homopolymers, maleic acid homopolymers, methacrylic acid homopolymers, acrylic/maleic copolymers, maelic acid copolymers, acrylic/methacrylic copolymers, maleic acid terpolymers, hydrophobically modified acrylic acid copolymers and terpolymers, hydrophobically modified maleic acid copolymers and terpolymers, hydrophobically modified methacrylic acid copolymers and terpolymers.
  • Suitable water conditioning polymers preferably have a molecular weight between about 500 to about 50,000 g/mol, more preferably between about 500 and about 25,000 g/mol and particularly between about 500 and about 10,000 g/mol.
  • Preferred polymers include, but are not limited to Acusol 445N, Acusol 425N, Acusol 441, Acusol 448 (available from Dow Chemical) ; Sokalan CP10, Sokalan CP12, Sokalan CP9, Sokalan CP50, Sokalan PA13PN, Sokalan PA15, Sokalan PA20, Sokalan PA25 (Available from BASF ) ; Carbosperse K-7058, Carbosperse K-7028, and Carbosperse K-775 (Available from Lubrizol) ; Belclene 200, Belclene 283, Belcene 810 (available from BWA Water Additives) .
  • Suitable polycarboxylic acids are acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, in which case they contain at least two carboxyl groups which are in each case separated from one another by, preferably, no more than two carbon atoms.
  • Polycarboxylates which comprise two carboxyl groups include, for example, water-soluble salts of, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid.
  • Polycarboxylates which contain three carboxyl groups include, for example, water-soluble citrate.
  • a suitable hydroxycarboxylic acid is, for example, citric acid.
  • Another suitable polycarboxylic acid is the homopolymer of acrylic acid. Preferred are the polycarboxylates end capped with sulfonates.
  • phosphonates such as phosphinosuccinic acid oligomer (PSO) described in US8871699, 2-phosphonobutane-l, 2, 4-tricarboxylic acid (PBTC) , 1-hydroxyethane-l, 1-diphosphonic acid (HEDP) , aminotri (methylenephosphonic acid) ; 2-hydroxyethyliminobis (methylenephosphonic acid) , diethylenetriaminepenta (methylenephosphonic acid) , diethylenetriaminepenta (methylenephosphonate) , sodium salt (DTPMP) , hexamethylenediamine (tetramethylenephosphonate) , potassium salt bis(hexamethylene) triamine (pentamethylenephosphonic acid) ; and phosphorus acid.
  • PSO phosphinosuccinic acid oligomer
  • PBTC 2-phosphonobutane-l, 2, 4-tricarboxylic acid
  • HEDP 1-hydroxyethane-l
  • HEDP 1-d
  • the solid composition comprises at least one nonionic surfactant.
  • nonionic surfactants A-E
  • polymer surfactants F-J
  • the at least one nonionic surfactant can include compounds of the general formula (I) , R 1 - (A) x - (B) y1 - (A) z - (B) y2 -R 2 (I) , wherein R 1 and R 2 independently denote H or linear or branched, substituted or unsubstituted C1-C22 alkyl,
  • A denotes CH 2 -CH 2 -O
  • B denotes CH 2 -CHR 3 -O, wherein R 3 denotes H or linear or branched, unsubstituted C1-C10 alkyl,
  • x is an integer in the range from 0 to 35
  • y 1 is an integer in the range from 0 to 60
  • y 2 is an integer in the range from 0 to 35
  • z is an integer in the range from 0 to 35, and
  • the sum of x+y 1 +z+y 2 is in the range of 1 to100, more preferably the sum of x+y 1 +z+y 2 is in the range of 1 to 75 even more preferably the sum of x+y 1 +z+y 2 is in the range of 2 to 75 and most preferably the sum of x+y 1 +z+y 2 is in the range of 2 to 70.
  • the term “alkyl” refers to acyclic saturated aliphatic residues, including linear or branched alkyl residues. Furthermore, the alkyl residue is preferably unsubstituted and includes as in the case of C 1 -C 22 alkyl 1 to 22 carbon atoms.
  • branched denotes a chain of atoms with one or more side chains attached to it. Branching occurs by the replacement of a substituent, e.g., a hydrogen atom, with a covalently bonded aliphatic moiety.
  • linear and branched, unsubstituted C 1 -C 22 alkyl include, but are not limited to methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta-decyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, isopropyl, isobutyl, iso-pentyl, isohexyl, isoheptyl,
  • the at least one nonionic surfactant of general formula (I) according to embodiments B, G and L are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating ethylene oxide (EO) units and a block of repeating propylene oxide (PO) unit interposed between first and second block of repeating ethylene units represented by formula (V) , HO- (CH 2 CH 2 O) x (CH (CH 3 ) CH 2 O) y1 (CH 2 CH 2 O) z -H (V) .
  • the nonionic surfactant of general formula (I) according to embodiments B, G and L have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.
  • EO ethylene oxide
  • PO propylene oxide
  • the nonionic surfactant of general formula (I) according to embodiments C, H and M are the block copolymers of ethylene oxide and higher alkylene oxide functionalized/capped with fatty alcohols.
  • Preferred higher alkylene oxides are propylene oxide, butylene oxide and pentylene oxide.
  • the preferred ratio of ethylene oxide to the higher alkylene oxide units is 1: 2 to 5: 2.
  • the nonionic surfactant of general formula (I) according to embodiments E, J and O are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating propylene oxide (PO) units and a block of repeating ethylene oxide (EO) unit interposed between first and second block of repeating propylene units as represented by formula (VI) , HO- (CH (CH 3 ) CH 2 O) y1 - (CH 2 CH 2 O) z - (CH (CH 3 ) CH 2 O) y2 -H (VI) .
  • the nonionic surfactant of general formula (I) according to embodiments E, J and O have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.
  • the at least one nonionic surfactant of the general formula (I) has a hydrophilic-lipophilic balance (HLB) value in the range of 2 to 17.
  • HLB hydrophilic-lipophilic balance
  • the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 11 when R 2 is H.
  • the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 17 when R 2 is linear or branched, substituted or unsubstituted C 1 -C 22 alkyl.
  • the HLB value represents the hydrophilic-lipophilic balance of the molecule. The lower the HLB value the more hydrophobic the material is, and vice versa.
  • Still further useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol.
  • any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent.
  • hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties.
  • Useful nonionic surfactants include:
  • Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound (1) are commercially available from BASF Corp.
  • One class of compounds is difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000.
  • Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10%by weight to about 80%by weight of the final molecule.
  • Another class of compounds are tetra-flinctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine.
  • the molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000; and, the hydrophile, ethylene oxide, is added to constitute from about 10%by weight to about 80%by weight of the molecule.
  • the alkyl group can, for example, be represented by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl.
  • These surfactants can be polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. Examples of commercial compounds of this chemistry are available on the market under the trade names manufactured by Rhone-Poulenc and manufactured by Union Carbide.
  • Condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide (3) .
  • the alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range.
  • the acid moiety can consist of mixtures of acids in the above defined carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range.
  • ester moieties In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this invention for specialized embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances. Care must be exercised when adding these fatty ester or acylated carbohydrates to compositions of the present invention containing amylase and/or lipase enzymes because of potential incompatibility.
  • nonionic low foaming surfactants examples include:
  • polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued Aug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains where the weight of the terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight of the linking hydrophilic units each represent about one-third of the condensate.
  • defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. having the general formula Z [ (OR) n OH] z wherein Z is alkoxylatable material, R is a radical derived from an alkylene oxide which can be ethylene and propylene and n is an integer from, for example, 10 to 2,000 or more and z is an integer determined by the number of reactive oxyalkylatable groups.
  • Y Compounds falling within the scope of the definition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and the like.
  • the oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.
  • Additional conjugated polyoxyalkylene surface-active agents which are advantageously used in the compositions of this invention correspond to the formula: P [ (C 3 H 6 O) n (C 2 H 4 O) m H] x wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10%to about 90%by weight.
  • the oxypropylene chains may contain optionally, but advantageously, small amounts of ethylene oxide and the oxyethylene chains may contain also optionally, but advantageously, small amounts of propylene oxide.
  • Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R 2 CON R1 Z in which: R1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R 2 is a C 5 -C 31 hydrocarbyl, which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from a reducing sugar in a reductive amination reaction; such as a glycityl moiety.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • ethoxylated C 6 -C 18 fatty alcohols and C 6 -C 18 mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are water soluble.
  • Suitable ethoxylated fatty alcohols include the C 6 -C 18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50.
  • Suitable nonionic alkylpolysaccharide surfactants particularly for use in the present compositions include those disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
  • the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
  • the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.
  • Fatty acid amide surfactants suitable for use the present compositions include those having the formula: R 6 CON (R 7 ) 2 in which R 6 is an alkyl group containing from 7 to 21 carbon atoms and each R 7 is independently hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, or -- (C 2 H 4 O) X H, where x is in the range of from 1 to 3.
  • a useful class of non-ionic surfactants includes the class defined as alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants.
  • These non-ionic surfactants may be at least in part represented by the general formulae: R 20 -- (PO) S N-- (EO) t H, R 20 -- (PO) S N-- (EO) t H (EO) t H, and R 20 --N (EO) t H; in which R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5.
  • Nonionic Surfactants edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds generally employed in the practice of the present invention.
  • a typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents and detergents" (Vol. I and II by Schwartz, Perry and Berch) .
  • the components of the solid composition can further be combined with various functional components suitable for uses disclosed herein, including metal safe alkaline detergents and rinse aids.
  • the solid compositions including the alkalinity source, chelant, at least one water conditioning agent, and at least one nonionic surfactant make up a large amount, or even substantially all of the total weight of the solid compositions.
  • few or no additional functional ingredients are disposed therein.
  • additional functional ingredients may be included in the solid compositions.
  • the functional ingredients provide desired properties and functionalities to the compositions.
  • 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.
  • the solid compositions may include defoaming agents, bleaching agents, solubility modifiers, dispersants, additional metal protecting agents, soil antiredeposition agents, stabilizing agents, corrosion inhibitors, additional builders/sequestrants/chelating agents, enzymes, aesthetic enhancing agents including fragrances and/or dyes, additional rheology and/or solubility modifiers or thickeners, hydrotropes or couplers, buffers including acids, solvents, hardening agents, additional cleaning agents and the like.
  • the various additional functional ingredients may be provided in a composition in the amount from about 0 wt-%and about 30 wt-%, from about 0 wt-%and about 25 wt-%, from about 0 wt-%and about 20 wt-%, from about 0.01 wt-%and about 30 wt-%, from about 0.1 wt-%and about 30 wt-%, from about 1 wt-%and about 30 wt-%, from about 1 wt-%and about 30 wt-%, from about 1 wt-%and about 25 wt-%, from about 1 wt-%and about 20 wt-%, or from about 1 wt-%and about 15 wt-%.
  • all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
  • the solid compositions can further comprise a solid acid or salt thereof.
  • the solid acid is a low solubility acid source and is preferably combined when the chelant of the solid composition is not an acid chelant.
  • the acid has an aqueous solubility between 0.1 g/L and 1500 g/L at 20 °C, more preferably between 0.25 g/L and 500 g/L at 20 °C, most preferably between 0.25 and 100 g/L at 20 °C.
  • the g/L description refers to the mass of acid added with sufficient aqueous medium (e.g., water) to form one liter of solution.
  • the acid is a solid polycarboxylic acid.
  • the acid is a polycarboxylic acid having between 2 and 4 carboxyl groups. More preferably the polycarboxylic acid is a dicarboxylic acid or a tricarboxylic acid.
  • Preferred acids include, but are not limited to, adipic acid, citric acid, ethylenediamine tetra acetic acid, isocitric acid, glutamic acid, glutaric acid, malic acid, propane-1, 2, 3-tricarboxylic acid, succinic acid, tartartic acid, salts of the foregoing, and mixtures thereof.
  • the acid is in an amount between about 0.01 wt-%and about 20 wt-%, between about 0.1 wt-%and about 20 wt-%, more preferably between about 1 wt-%and about 20 wt-%, or more preferably between about 1 wt-%and about 15 wt-%.
  • the solid compositions can further comprise one or more enzymes.
  • Preferred enzymes include, amylases, cellulases, lipases, proteases, and combinations of the same. Most preferably, the enzyme comprises a protease. If included, the enzyme is preferably in an amount between about 0.1 wt-%and about 25 wt-%, more preferably between about 0.5 wt-%and about 20 wt-%, and most preferably between about 1 wt-%and about 15 wt-%.
  • amylase or mixture of amylases can be used in the solid compositions, provided that the selected enzyme is stable in the desired pH range (between about 6 and about 9) .
  • the amylase enzymes can be derived from a plant, an animal, or a microorganism such as a yeast, a mold, or a bacterium.
  • Preferred amylase enzymes include, but are not limited to, those derived from a Bacillus, such as B. licheniformis, B. amyloliquefaciens, B. subtilis, or B. stearothermophilus.
  • Amylase enzymes derived from B. subtilis are most preferred.
  • the amylase can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant) .
  • Preferred amylases are commercially available under the trade name available from Novozymes.
  • any lipase or mixture of lipases, from any source, can be used in the solid compositions, provided that the selected enzyme is stable in the desired pH range (between about 6 and about 9) .
  • the lipase enzymes can be derived from a plant, an animal, or a microorganism such as a fungus or a bacterium.
  • Preferred protease enzymes include, but are not limited to, the enzymes derived from a Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, or from a Humicola, such as Humicola lanuginosa (typically produced recombinantly in Aspergillus oryzae) .
  • the lipase can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant) .
  • protease or mixture of proteases can be used in the solid compositions, provided that the selected enzyme is stable in the desired pH range (between about 6 and about 9) .
  • the protease enzymes can be derived from a plant, an animal, or a microorganism such as a yeast, a mold, or a bacterium.
  • Preferred protease enzymes include, but are not limited to, the enzymes derived from Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus. Protease enzymes derived from B. subtilis are most preferred.
  • protease can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant) .
  • Exemplary proteases are commercially available under the following trade names and Progress UNO TM (also sold under the name Everis DUO TM ) each available from Novozymes.
  • the solid compositions can comprise additional enzymes in addition to the foregoing.
  • Additional suitable enzymes can include, but are not limited to, cutinases, peroxidases, gluconases, or mixtures thereof.
  • additional hardening agents can be used in the solid compositions.
  • other hardening agents include an amide such stearic monoethanolamide or lauric diethanolamide, or an alkylamide, and the like; a solid polyethylene glycol, or a solid EO/PO block copolymer, and the like; starches that have been made water-soluble through an acid or alkaline treatment process; various inorganics that impart solidifying properties to a heated composition upon cooling, and the like.
  • Such compounds may also vary the solubility of the composition in an aqueous medium during use such that the rinse aid and/or other active ingredients may be dispensed from the solid composition over an extended period of time.
  • the composition may include a hardening agent in an amount in the range of up to about 30 wt-%.
  • hardening agents may be present in an amount in the range of about 5 wt-%to about 25 wt-%, often in the range of 10 wt-%to about 25 wt-%and sometimes in the range of about 5 wt-%to about 15 wt-%.
  • the solid compositions can be prepared as a cast solid, extruded solid, molded solid, or a pressed solid.
  • the compositions can be prepared by mixing the various components together and applying the solidification process desired.
  • the solid compositions are preferably pressed solids.
  • Pressed solids overcome the various limitations of other solid formulations for which there is a need for making solid compositions. Moreover, pressed solid compositions retain their shape under conditions where the compositions may be stored or handled.
  • a flowable solid such as granular solids or other particle solids are combined under pressure to form the solid composition.
  • 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, or the like.
  • Pressure may be applied at about 1 to about 3000 psi, about 1 to about 2000 psi, about 1 to about 1000 psi, about 1 to about 500 psi, about 1 to about 300 psi, about 5 psi to about 200 psi, or about 10 psi to about 100 psi.
  • the methods can employ pressures as low as greater than or equal to about 1 psi, greater than or equal to about 2, greater than or equal to about 5 psi, or greater than or equal to about 10 psi.
  • 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.
  • Solid block and cast solid block materials can be made by introducing into a container a castable liquid formulation of the ingredients 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 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.
  • 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.
  • 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.
  • the solid compositions may be formed using a batch or continuous mixing system to combine ingredients.
  • a single-or twin-screw extruder is used to combine and mix one or more components at high shear to form a homogeneous mixture.
  • 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 cleaning 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.
  • a solid composition processed according to these methods is substantially homogeneous with regard to the distribution of ingredients throughout its mass and is dimensionally stable.
  • 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.
  • the formed composition begins to harden to a solid form in between approximately 1 minute and approximately 3 hours.
  • 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.
  • the methods can optionally include a curing step to produce the solid compositions.
  • a curing step to produce the solid compositions.
  • 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 composition.
  • a sufficient quantity of particles (e.g. granules) in contact with one another provides a binding of particles effective for making a stable solid composition.
  • a curing step may be included, allowing the pressed solid to solidify for a period of time, such as a few hours, or about 1 day (or longer) .
  • Methods of use employing the solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions are particularly suitable for consumer or institutional ware washing.
  • Beneficially the methods of first contacting a use solution of the composition to a hard metal surface in need of cleaning and drying, and thereafter rinsing the hard metal surface provide both effective cleaning, rinsing and drying of the surface with water hardness protection and no filming on metal surfaces.
  • These methods overcome limitations of silicates or silicone-containing materials that leave detrimental white films or residues on treated metal surfaces.
  • the solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions are particularly suitable for treating hard metal surfaces that include an alkaline sensitive metal surface, such as aluminum.
  • the methods provide metal protection for using of alkaline cleaning and rinsing compositions, without leaving white films or residues on treated metal surfaces.
  • the methods of use eliminate the need for occasional acid rinse steps to remove the films or residues on treated metal surfaces that accumulate over time. These benefits are achieved while providing at least substantially similar cleaning and rinsing/drying performance as silicated compositions or two-part compositions.
  • Exemplary disclosure of warewashing applications is set forth in U.S. Patent Nos. 8,758,520, 9,139,800, and 10,905,305.
  • the method may be carried out in any consumer or institutional dish machine, including for example those described in U.S. Patent No. 8,092,613, which is incorporated herein by reference in its entirety, including all figures and drawings.
  • dish machines include door machines or hood machines, conveyor machines, undercounter machines, glasswashers, flight machines, pot and pan machines, utensil washers, and consumer dish machines.
  • the dish machines may be either single tank or multi-tank machines.
  • a door dish machine also called a hood dish machine, refers to a commercial dish machine wherein the soiled dishes are placed on a rack and the rack is then moved into the dish machine.
  • Door dish machines clean one or two racks at a time. In such machines, the rack is stationary and the wash and rinse arms move.
  • a door machine includes two sets arms, a set of wash arms and a rinse arm, or a set of rinse arms.
  • Door machines may be a high temperature or low temperature machine. In a high temperature machine the dishes are sanitized by hot water. In a low temperature machine the dishes are sanitized by the chemical sanitizer.
  • the door machine may either be a recirculation machine or a dump and fill machine. In a recirculation machine, the detergent solution is reused, or "recirculated" between wash cycles. The concentration of the detergent solution is adjusted between wash cycles so that an adequate concentration is maintained. In a dump and fill machine, the wash solution is not reused between wash cycles. New detergent solution is added before the next wash cycle.
  • the methods of use of the solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions are also suitable for CIP and/or COP processes to replace the use of bulk detergents leaving hard water residues on treated surfaces.
  • the methods of use may be desirable in additional applications where industrial standards are focused on the quality of the treated surface, such that the prevention of corrosion, film, and hard water scale accumulation provided by a detergent composition, and even a 2-in-1 composition are desirable.
  • Additional examples of applications of use for the solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions include, for example, applications for cleaning and rinsing various metal surfaces, grill and oven cleaners, ware wash detergents, laundry detergents and rinse aids, other metal hard surface cleaners, etc.
  • cleaning compositions having a very high alkalinity are most desirable and efficacious, however the damage caused by corrosion of metal is undesirable.
  • the efficient drying of the surfaces is desirable.
  • the solid is contacted with an aqueous source, preferably water, or may be mixed with an aqueous source, preferably water, prior to or at the point of use.
  • a water source contacts the composition to convert solid compositions (or a portion thereof for a multiuse solid composition) , into use solutions. Additional dispensing systems may also be utilized which are more suited for converting alternative solid compositions into use solutions.
  • the methods of the present invention include use of a variety of solid detergent compositions, including, for example, blocks or ” capsule” types of packages.
  • the solid compositions or use solutions thereof can contact the surface or article by numerous methods for applying a composition, such as spraying the composition, immersing the object in the composition, or a combination thereof.
  • a concentrate or use concentration of a composition can be applied to or brought into contact with an article by any conventional method or apparatus for applying a cleaning composition to an object.
  • the object can be wiped with, sprayed with, and/or immersed in the composition, or a use solution made from the composition.
  • the composition can be sprayed, or wiped onto a surface; the composition can be caused to flow over the surface, or the surface can be dipped into the composition.
  • Contacting can be manual or by machine. Preferred embodiments contact a use solution of the solid composition in a warewash machine.
  • a use solution of the solid compositions applied to surfaces in need of treatment can include at least about 100 ppm, at least about 200 ppm, at least about 250 ppm, at least about 300 ppm, and preferably at least about 350 ppm to about 1000 ppm.
  • a use solution of the solid compositions applied to surfaces in need of treatment can include from about 350 ppm to about 3000 ppm, from about 350 ppm to about 2000 ppm, from about 350 ppm to about 1500 ppm, or about 350 ppm to about 1000 ppm to beneficially provide detergency and rinsing while protecting the treated metal surfaces.
  • Exemplary articles for treatment with the compositions disclosed herein are in the warewashing industry, including ware, such as metal ware, plastics, dishware, cups, glasses, flatware, and cookware.
  • ware such as metal ware, plastics, dishware, cups, glasses, flatware, and cookware.
  • the terms "dish” and "ware” are used in the broadest sense to refer to various types of articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room.
  • these types of articles can be referred to as food or beverage contacting articles because they have surfaces which are provided for contacting food and/or beverage.
  • the solid polymer surfactant systems provide effective sheeting action, low foaming properties and fast drying.
  • the solid compositions aid in drying the article or surface (e.g. ware) within about 30 seconds to a few minutes, or within about 30 to about 90 seconds after the aqueous use solution is applied.
  • Embodiments of the present disclosure are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the disclosure to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the disclosure, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
  • Exemplary formulations were prepared to evaluate corrosiveness to aluminum in silicated versus non-silicated formulations. This procedure has been developed according to the National Association of Corrosion Engineers Standard TM-01-69.
  • Aluminum test strips (Al1100, North American aluminum alloy standard; and Al1050P, Japanese aluminum alloy standard) were placed in 4 oz glass bottles containing concentrated liquid formulations. The aluminum strips were weighed, labeled, put into the bottles, and placed in a 130°F water bath for eight hours. The aluminum strips were then cleaned by immersion in 70%HNO 3 for 3 minutes and rinsed thoroughly with distilled water. Then, the aluminum strips were weighed and the weight loss was calculated by comparison to control aluminum strips. A standard equation which equates weight loss, time, surface area, and metal density is used to calculate a corrosion rate expressed as mils per year. A corrosion rate exceeding 250 MPY is classified as corrosive to the metal.
  • Formulations P6, P10, P12, and P13 compared to the Control and water are shown in the Figures.
  • the remaining exemplary formulations in Table 3 did provide performance below the 250 MPY threshold and therefore not depicted in the figures.
  • FIGS. 1A-1C compare these formulations when concentration is increased (0-3000ppm) , concentration of carbonate is increased (0-2500ppm) , and pH is increased (7-11) .
  • the corrosion graphs show a 250 MPY threshold indicator line to readily compare the results of the formulations.
  • Two additional comparison MPY threshold indicator lines, at 67 MPY and 20 MPY, are included in the scatterplots figures.
  • the 67 MPY threshold compares to a commercially available non-silicated control
  • the 20 MPY threshold compares a commercially available silicated metal safe corrosion product.
  • FIG. 1A shows a scatter plot of the corrosiveness (MPY) of water, the control formula, P6, P10, P12, and P13 formulas at 7 pH to 11 pH. This figure shows that the exemplary formulations perform substantially below the 250 MPY limit in alkaline solutions.
  • FIG. 1B shows a scatter plot of the corrosiveness (MPY) of water, the control formula, P6, P10, P12, and P13 formulas based on concentration of carbonate. Again, the figure shows that the exemplary formulations remain under the 250 MPY limit and remain under through the concentration range when used on Al1100.
  • MPY corrosiveness
  • FIG. 1C shows a scatter plot of the corrosiveness (MPY) of water, the control formula, P6, P10, P12, and P13 formulas based on concentration of the formulas. This figure demonstrates that all the formulas are below the 250 MPY limit when at 1000ppm or lower. Yet, this figure also shows that formulas P10, P12, and P13 remain below the limit at higher concentrations when used on Al1100.
  • MPY corrosiveness
  • Exemplary formulations were prepared to evaluate overall stability in block form.
  • Formulations P6-P10, P12, and P13 were compared based on performance seen in Example 1.
  • Formulas P6-P9 contained MGDA instead of acid EDTA
  • Formula P10 contains 6%
  • P12 contains 12%
  • P13 contains 16%acid EDTA in the formulation, as described in Table 5.
  • All formulation blocks were dipped into water for 3 minutes at a water temperature of about 110-120°F. Approximately 1 inch of the solid blocks were submerged in the water. The formulation blocks were then air dried for 3 days and measured for structural block change. The length and width of the block were measured both before being submerged in water and then again after 3 days of air drying. The %difference (based on the block swelling) in swelling was measured. The lower the swelling, the better block integrity.
  • FIG. 2A demonstrates the percent change in length of the formulation blocks and FIG. 2B shows the percent change in width of the formulation blocks.
  • the addition of acid EDTA to the formulation significantly improved the percent block swelling measured through wicking tests when the formulations were non-silicated.
  • the non-silicated formulations P6-P9 that included MGDA instead of the acid EDTA in P10, P12, and P13 showed the most swelling and crumbling of the solid blocks. This shows that when the formulations do not include a silicone-containing material (such as the silicates conventionally used for metal protection) , the addition of the acid EDTA improves the stability and cohesion of the solid formula.
  • a solid formulation that does not crumble, like the exemplary formulations with acid EDTA, is ideal to prevent clogging or accumulation in the washing machine dispenser or drainage system.
  • the term “clog” and variations thereof, in relation to use of a solid composition in a dispenser or other drainage system, refers to a dispenser in which a solid or an aggregate of solids has formed and can decrease or prevent the solid from being dispensed, i.e. introduced into a device for use, e.g. dish machine. Often a concentrated composition builds up in a dispenser until it overflows, meanwhile the machine continues to operate without the composition, e.g. detergent. This can be caused by a number of things including, but not limited to, the precipitation of certain chemicals in the presence of hard water. According to the example described herein, formulation with the acid EDTA (or another low solubility acid) can overcome this limitation.
  • the soil removal rate is quantified based on a standard image analysis program (Image J, Fiji) that converts the picture to a gray scale (i.e. black indicating soil, white indicating soil removal or being clean) , where the more pixels that change from black to lighter gray or white, the cleaner the test coupon.
  • Image J, Fiji image analysis program
  • FIG. 3 shows the soil removal rate of water, the control formulation, formula P6, formula P10 and P13.
  • Formulas P6, P10 and P13 removed approximately 65-90%of the soil, whereas the control formula only removed 10-25%of the soil at three times the concentration.
  • Exemplary formulation P6 as described in Table 3 was compared to a commercial rinse aid formulation, as described in Table 5 below, in rinse and drying performance.
  • FIG. 4A shows the drying time of formula P6 from 450-1000ppm on ceramic and melamine.
  • FIG. 4B shows the drying time of the commercial rinse aid formula at 500ppm on ceramic and melamine.

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  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un détergent solide 2-en-1 protecteur de métaux alcalins et des compositions d'auxiliaire de rinçage permettant de réduire la corrosion et assurant une protection des métaux tout en améliorant les temps de séchage de surfaces. L'invention concerne également des procédés de fabrication des compositions et des procédés d'utilisation de ces dernières.
PCT/CN2022/102600 2022-06-30 2022-06-30 Détergent alcalin comprimé protecteur de métaux non silicaté et additif de rinçage WO2024000340A1 (fr)

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