WO2024000340A1 - Non-silicated metal protectant pressed alkaline detergent and rinse additive - Google Patents
Non-silicated metal protectant pressed alkaline detergent and rinse additive Download PDFInfo
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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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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 58
- 239000002184 metal Substances 0.000 title claims abstract description 58
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- 230000000996 additive effect Effects 0.000 title claims description 4
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- 125000000217 alkyl group Chemical group 0.000 claims description 26
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- 239000011574 phosphorus Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229940071207 sesquicarbonate Drugs 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 150000004666 short chain fatty acids Chemical class 0.000 description 1
- 235000021391 short chain fatty acids Nutrition 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000007916 tablet composition Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XSROQCDVUIHRSI-UHFFFAOYSA-N thietane Chemical compound C1CSC1 XSROQCDVUIHRSI-UHFFFAOYSA-N 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- ODBLHEXUDAPZAU-UHFFFAOYSA-N threo-D-isocitric acid Natural products OC(=O)C(O)C(C(O)=O)CC(O)=O ODBLHEXUDAPZAU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/16—Metals
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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Abstract
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 are provided. Methods of making the compositions and methods of using the same are also provided.
Description
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. However the formulations can vary greatly in degree of corrosiveness, acceptance as consumer-friendly and/or environmentally-friendly products, as well as other detergent characteristics. Generally, as the alkalinity of these compositions increase, the difficulty in protecting metal surfaces also increases. A need therefore exists for detergent compositions that minimize and/or eliminate metal corrosion of items within systems employing these detergents beyond known corrosion inhibitors, such as silicates like sodium silicate.
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.
There is also a need for providing 2-in-1 detergent and rinse aid compositions to eliminate the need for multiple formulations, multiple steps, and overall product cost and consumption.
A further object of the invention is to provide methods for employing alkaline detergents between pHs from about 9 to about 12.5 without causing significant corrosion of metal surfaces.
It is therefore an object of this disclosure to provide 2-in-1 alkaline detergent and rinse aid compositions with improved metal protection.
It is a further object of this disclosure to provide 2-in-1 alkaline detergent and rinse aid compositions with improved metal protection that do not precipitate films or particulates onto the cleaned surfaces.
It is a further object of the disclosure to provide 2-in-1 alkaline detergent and rinse aid compositions with the various improvements described herein that further provide enhanced drying of the surfaces and water hardness protection.
It is another object of this disclosure to formulate the 2-in-1 alkaline detergent and rinse aid compositions into solid blocks, including pressed solids.
Other objects, embodiments and advantages of this disclosure will be apparent to one skilled in the art in view of the following disclosure, the drawings, and the appended claims.
BRIEF SUMMARY
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.
According to some aspects of the present disclosure, 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.
According to additional aspects of the present disclosure, 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.
According to additional aspects of the present disclosure, 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.
These and/or other objects, features, advantages, aspects, and/or embodiments will become apparent to those skilled in the art after reviewing the following brief and detailed descriptions of the drawings. Furthermore, the present disclosure encompasses aspects and/or embodiments not expressly disclosed but which can be understood from a reading of the present disclosure, including at least: (a) combinations of disclosed aspects and/or embodiments and/or (b) reasonable modifications not shown or described.
While multiple embodiments are disclosed, still other embodiments will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive.
Several embodiments in which the present disclosure can be practiced are illustrated and described in detail, wherein like reference characters represent like components throughout the several views. The drawings are presented for exemplary purposes and may not be to scale unless otherwise indicated.
FIG. 1A is a scatterplot of corrosion (MPY) evaluated with varying pH of exemplary compositions on aluminum alloys.
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.
Various embodiments of the present disclosure will be described in detail with reference to the drawings, wherein like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the disclosure. Figures represented herein are not limitations to the various embodiments according to the disclosure and are presented for exemplary illustration of the invention. An artisan of ordinary skill in the art need not view, within isolated figure (s) , the near infinite number of distinct permutations of features described in the following detailed description to facilitate an understanding of the present invention.
The present disclosure is not to be limited to that described herein, which can vary and are understood by skilled artisans. No features shown or described are essential to permit basic operation of the present disclosure unless otherwise indicated. As disclosed herein, 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.
It is further to be understood that all terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a, " "an" and "the" can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.
Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this disclosure are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosure. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges, fractions, and individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 11/2, and 43/4. This applies regardless of the breadth of the range.
As used herein, the term “and/or” , e.g., “X and/or Y” shall be understood to mean either "X and Y" or "X or Y" and shall be taken to provide explicit support for both meanings or for either meaning, e.g. A and/or B includes the options i) A, ii) B or iii) A and B.
It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub-combination.
The methods and compositions of the present disclosure may comprise, consist essentially of, or consist of the components and ingredients of the present disclosure as well as other ingredients described herein. As used herein, “consisting essentially of” means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.
Unless defined otherwise, all technical and scientific terms used above have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the present disclosure pertain.
The terms “invention” or “present invention” are not intended to refer to any single embodiment of the particular invention but encompass all possible embodiments as described in the specification and the claims.
The term “about, ” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, temperature, pH, and log count of bacteria or viruses. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like. The term “about” also encompasses these variations. Whether or not modified by the term “about, ” the claims include equivalents to the quantities.
The term "actives" or "percent actives" or "percent by weight actives" or "actives concentration" are used interchangeably herein and refers to the concentration of those ingredients involved in cleaning expressed as a percentage minus inert ingredients such as water or salts. It is also sometimes indicated by a percentage in parentheses, for example, “chemical (10%) . ”
The phrase "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.
As used herein, the term “alkyl” or “alkyl groups” refers to saturated hydrocarbons having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. ) , cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc. ) , branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc. ) , and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups) . Unless otherwise specified, the term “alkyl” includes both “unsubstituted alkyls” and “substituted alkyls. ” As used herein, the term “substituted alkyls” refers to alkyl groups having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, amino (including alkyl amino, dialkylamino, arylamino, diarylamino, and alkylarylamino) , acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido) , imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.
In some embodiments, substituted alkyls can include a heterocyclic group. As used herein, the term “heterocyclic group” includes closed ring structures analogous to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes) , thiirane (episulfides) , dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.
As used herein, the term “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.
As used herein, the term “exemplary” refers to an example, an instance, or an illustration, and does not indicate a most preferred embodiment unless otherwise stated.
As used herein, the 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. In exemplary embodiments, the compositions are free of silicates or silicone-containing materials.
The term “generally” encompasses both “about” and “substantially. ”
As used herein the term "polymer" refers to a molecular complex comprised of a more than ten monomeric units and generally includes, but is not limited to, homopolymers, copolymers, such as for example, block, graft, random and alternating copolymers, terpolymers, and higher "x" mers, further including their analogs, derivatives, combinations, and blends thereof. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible isomeric configurations of the molecule, including, but are not limited to isotactic, syndiotactic and random symmetries, and combinations thereof. Furthermore, unless otherwise specifically limited, the term "polymer" shall include all possible geometrical configurations of the molecule.
As used herein, the term “soil” or “stain” refers to any soil, including, but not limited to, non-polar oily and/or hydrophobic substances which may or may not contain particulate matter such as industrial soils, mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust, and/or food based soils such as blood, proteinaceous soils, starchy soils, fatty soils, cellulosic soils, etc.
The “scope” of the present disclosure is defined by the appended claims, along with the full scope of equivalents to which such claims are entitled. The scope of the disclosure is further qualified as including any possible modification to any of the aspects and/or embodiments disclosed herein which would result in other embodiments, combinations, subcombinations, or the like that would be obvious to those skilled in the art.
As used herein, 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. 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-%. In exemplary embodiments, the compositions are substantially free of silicates or silicone-containing materials.
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 "surfactant" or "surface active agent" refers to an organic chemical that when added to a liquid changes the properties of that liquid at a surface.
As used herein, the term “ware” refers to items such as eating and cooking utensils, dishes, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. As used herein, the term “warewashing” refers to washing, cleaning, or rinsing ware. Ware also refers to items made of plastic. Types of plastics that can be cleaned with the compositions include but are not limited to, those that include polypropylene polymers (PP) , polycarbonate polymers (PC) , melamine formaldehyde resins or melamine resin (melamine) , acrylonitrile-butadiene-styrene polymers (ABS) , and polysulfone polymers (PS) . Other exemplary plastics that can be cleaned using the compounds and compositions of the disclosure include polyethylene terephthalate (PET) polystyrene polyamide.
The term "weight percent, " "wt-%, " "percent by weight, " "%by weight, " and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100. It is understood that, as used here, "percent, " "%, " and the like are intended to be synonymous with "weight percent, " "wt-%, " etc.
COMPOSITIONS
According to embodiments, 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. In embodiments 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. Moreover, 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) .
TABLE 1
Alkali Metal Carbonate Alkalinity Source
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. In embodiments 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. For example, embodiments of the solid compositions will provide a pH of between about 9 and about 12.5 upon dilution. In a preferred embodiment, 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.
In some embodiments, 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-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
Chelants
The solid composition comprises a non-silicate chelant. In a non-limiting embodiment 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.
In some embodiments an acid chelant, such as acid EDTA is employed in the solid compositions. In other embodiments a chelant is combined with a low solubility acid. In each embodiment the solid composition beneficially is a stable solid and provides the reduced corrosion from the combined acid and chelant performance.
In some embodiments, 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-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
Exemplary 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. In a preferred aspect, the aminocarboxylates include aminocarboxylic acid materials containing little or no NTA.
In a preferred embodiment the chelant is an aminocarboxylate or an aminocarboxylic acid. In a still further preferred embodiment the chelant is ethylenediaminetetraacetic acid (EDTA or acid EDTA) . Without being limited ot a particular mechanism of action, the acid chelant, such as acid EDTA benefits solid block cohesion when there is a silicate-free formulation as demonstrated in the Examples. However, one skilled in the art will ascertain that other chelants can be incorporated in the solid compositions and a low solubility acid source can be included to provide desired pH and solid stability without decreasing the performance benefits of the solid compositions.
Exemplary amino acid based compound or a succinate based compound can be included as chelants. The term "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 (ALDA) , serine-N, N-diacetic acid (SEDA) , isoserine-N, N-diacetic acid (ISDA) , phenylalanine-N, N-diacetic acid (PHDA) , anthranilic acid-N, N-diacetic acid (ANDA) , sulfanilic acid-N, N-diacetic acid (SLDA) , taurine-N, N-diacetic acid (TUDA) , sulfomethyl-N, N-diacetic acid (SMDA) , ethylenediamine disuccinate (EDDS) , and alkali metal salts or ammonium salts thereof.
Other chelants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. 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.
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 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.
Water Conditioning Agents
The solid composition comprises at least one water conditioning agent. In an embodiment 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. In an embodiment 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.
In some embodiments, the least one water conditioning agent is included in the solid composition at an amount of at least about 1 wt-%to about 20 wt-%, about 2 wt-%to about 20 wt-%, about 2 wt-%to about 15 wt-%, about 2 wt-%to about 10 wt-%, or about 2 wt-%to about 6 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
A variety of such polycarboxylate homopolymers, copolymers and terpolymers are known and described in patent and other literature, and are available commercially. Exemplary polycarboxylates that may be utilized according to the invention include for example: homopolymers, copolymers and terpolymers of polyacrylates; polymethacrylates; polymaleates. Examples of suitable polymers include acrylic acid homopolymers, maleic acid homopolymers, methacrylic acid homopolymers, acrylic/maleic copolymers, maelic acid copolymers, acrylic/methacrylic copolymers, maleic acid terpolymers, hydrophobically modified acrylic acid copolymers and terpolymers, hydrophobically modified maleic acid copolymers and terpolymers, hydrophobically modified methacrylic acid copolymers and terpolymers. Suitable 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. Correspondingly, 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.
Other types of water conditioning agents include 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.
Surfactants
The solid composition comprises at least one nonionic surfactant.
In some embodiments, the least one nonionic surfactant is included in the solid composition at an amount of at least about 2 wt-%to about 40 wt-%, about 2 wt-%to about 30 wt-%, about 2 wt-%to about 25 wt-%, about 2 wt-%to about 20 wt-%, about 2 wt-%to about 15 wt-%, or about 2 wt-%to about 10 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
Exemplary nonionic surfactants (A-E) and polymer surfactants (F-J) are shown in Table 2.
TABLE 2
The at least one nonionic surfactant can include compounds of the general formula (I) , R
1- (A)
x- (B)
y1- (A)
z- (B)
y2-R
2 (I) , wherein R
1 and R
2 independently denote H or linear or branched, substituted or unsubstituted C1-C22 alkyl,
A denotes CH
2-CH
2-O,
B denotes CH
2-CHR
3-O, wherein R
3 denotes H or linear or branched, unsubstituted C1-C10 alkyl,
x is an integer in the range from 0 to 35,
y
1 is an integer in the range from 0 to 60,
y
2 is an integer in the range from 0 to 35,
z is an integer in the range from 0 to 35, and
wherein the sum of x+y
1+z+y
2 is at least 1.
Preferably the sum of x+y
1+z+y
2 is in the range of 1 to100, more preferably the sum of x+y
1+z+y
2 is in the range of 1 to 75 even more preferably the sum of x+y
1+z+y
2 is in the range of 2 to 75 and most preferably the sum of x+y
1+z+y
2 is in the range of 2 to 70. In preferred embodiments of the surfactant structures, the term “alkyl” refers to acyclic saturated aliphatic residues, including linear or branched alkyl residues. Furthermore, the alkyl residue is preferably unsubstituted and includes as in the case of C
1-C
22 alkyl 1 to 22 carbon atoms. As used herein, “branched” denotes a chain of atoms with one or more side chains attached to it. Branching occurs by the replacement of a substituent, e.g., a hydrogen atom, with a covalently bonded aliphatic moiety.
Representative examples of linear and branched, unsubstituted C
1-C
22 alkyl include, but are not limited to methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-hepta-decyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, isopropyl, isobutyl, iso-pentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoe-icosyl, isoheneicosyl, isodocosyl, 2-propyl heptyl, 2-ethyl hexyl and t-butyl.
The at least one nonionic surfactant of general formula (I) according to embodiments B, G and L are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating ethylene oxide (EO) units and a block of repeating propylene oxide (PO) unit interposed between first and second block of repeating ethylene units represented by formula (V) , HO- (CH
2CH
2O)
x (CH (CH
3) CH
2O)
y1 (CH
2CH
2O)
z-H (V) .
In some embodiments, the nonionic surfactant of general formula (I) according to embodiments B, G and L have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.
In some embodiments, the nonionic surfactant of general formula (I) according to embodiments C, H and M are the block copolymers of ethylene oxide and higher alkylene oxide functionalized/capped with fatty alcohols. Preferred higher alkylene oxides are propylene oxide, butylene oxide and pentylene oxide. The preferred ratio of ethylene oxide to the higher alkylene oxide units is 1: 2 to 5: 2.
In some embodiments, the nonionic surfactant of general formula (I) according to embodiments E, J and O are the block copolymers of propylene oxide and ethylene oxide wherein the copolymers include first and second blocks of repeating propylene oxide (PO) units and a block of repeating ethylene oxide (EO) unit interposed between first and second block of repeating propylene units as represented by formula (VI) , HO- (CH (CH
3) CH
2O)
y1- (CH
2CH
2O)
z- (CH (CH
3) CH
2O)
y2-H (VI) .
In some embodiments, the nonionic surfactant of general formula (I) according to embodiments E, J and O have a ratio of ethylene oxide (EO) units to propylene oxide (PO) units of from 1: 10 to 10: 1 and an average molecular weight from 500 to 10,000 g/mol.
In an embodiment, the at least one nonionic surfactant of the general formula (I) has a hydrophilic-lipophilic balance (HLB) value in the range of 2 to 17. In further embodiments, the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 11 when R
2 is H. In further embodiments, the nonionic surfactant of the general formula (I) has an HLB value in the range of 2 to 17 when R
2 is linear or branched, substituted or unsubstituted C
1-C
22 alkyl.
The HLB value represents the hydrophilic-lipophilic balance of the molecule. The lower the HLB value the more hydrophobic the material is, and vice versa. The HLB values can be calculated according to the method given in Griffin, J. Soc. Cosmetic Chemists, 5 (1954) 249-256. Griffith’s method for nonionic surfactants as described in 1954 is as follows: HLB = 20 X M
h/M, where M
h is the molecular mass of the hydrophilic portion of the molecule; and M is the molecular mass of the whole molecule. Only the EO part in the surfactants is regarded as hydrophilic, all other parts contribute only to the whole molecule.
Additional Surfactants
Still further additional useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety which in common practice is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Practically any hydrophobic compound having a hydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed with ethylene oxide, or its polyhydration adducts, or its mixtures with alkoxylenes such as propylene oxide to form a nonionic surface-active agent. The length of the hydrophilic polyoxyalkylene moiety which is condensed with any particular hydrophobic compound can be readily adjusted to yield a water dispersible or water soluble compound having the desired degree of balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:
Block polyoxypropylene-polyoxyethylene polymeric compounds based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound (1) . Examples of polymeric compounds made from a sequential propoxylation and ethoxylation of initiator are commercially available from BASF Corp. One class of compounds is difunctional (two reactive hydrogens) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10%by weight to about 80%by weight of the final molecule. Another class of compounds are tetra-flinctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from about 500 to about 7,000; and, the hydrophile, ethylene oxide, is added to constitute from about 10%by weight to about 80%by weight of the molecule.
Condensation products of one mole of alkyl phenol wherein the alkyl chain, of straight chain or branched chain configuration, or of single or dual alkyl constituent, contains from about 8 to about 18 carbon atoms with from about 3 to about 50 moles of ethylene oxide (2) . The alkyl group can, for example, be represented by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can be polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. Examples of commercial compounds of this chemistry are available on the market under the trade names
manufactured by Rhone-Poulenc and
manufactured by Union Carbide.
Condensation products of one mole of a saturated or unsaturated, straight or branched chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide (3) . The alcohol moiety can consist of mixtures of alcohols in the above delineated carbon range or it can consist of an alcohol having a specific number of carbon atoms within this range. Condensation products of one mole of saturated or unsaturated, straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide (4) . The acid moiety can consist of mixtures of acids in the above defined carbon atoms range or it can consist of an acid having a specific number of carbon atoms within the range. In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters formed by reaction with glycerides, glycerin, and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in this invention for specialized embodiments, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecule which can undergo further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances. Care must be exercised when adding these fatty ester or acylated carbohydrates to compositions of the present invention containing amylase and/or lipase enzymes because of potential incompatibility.
Examples of nonionic low foaming surfactants include:
Compounds from (1) which are modified, essentially reversed, by adding ethylene oxide to ethylene glycol to provide a hydrophile of designated molecular weight; and, then adding propylene oxide to obtain hydrophobic blocks on the outside (ends) of the molecule. The hydrophobic portion of the molecule weighs from about 1,000 to about 3, 100 with the central hydrophile including 10%by weight to about 80%by weight of the final molecule. The hydrophobic portion of the molecule weighs from about 2,100 to about 6,700 with the central hydrophile including 10%by weight to 80%by weight of the final molecule. Compounds from groups (1) , (2) , (3) and (4) which are modified by "capping" or "end blocking" the terminal hydroxy group or groups (of multi-functional moieties) to reduce foaming by reaction with a small hydrophobic molecule such as propylene oxide, butylene oxide, benzyl chloride; and, short chain fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms; and mixtures thereof. Also included are reactants such as thionyl chloride which convert terminal hydroxy groups to a chloride group. Such modifications to the terminal hydroxy group may lead to all-block, block-heteric, heteric-block or all-heteric nonionics.
Additional examples of effective low foaming nonionics include:
The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486 issued Sep. 8, 1959 to Brown et al. and represented by the formula
in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.
The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued Aug. 7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains where the weight of the terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight of the linking hydrophilic units each represent about one-third of the condensate.
The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178 issued May 7, 1968 to Lissant et al. having the general formula Z [ (OR)
nOH]
z wherein Z is alkoxylatable material, R is a radical derived from an alkylene oxide which can be ethylene and propylene and n is an integer from, for example, 10 to 2,000 or more and z is an integer determined by the number of reactive oxyalkylatable groups.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,677,700, issued May 4, 1954 to Jackson et al. corresponding to the formula Y (C
3H
6O)
n (C
2H
4O)
mH wherein Y is the residue of organic compound having from about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of at least about 6.4, as determined by hydroxyl number and m has a value such that the oxyethylene portion constitutes about 10%to about 90%by weight of the molecule.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No. 2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formula Y [ (C
3H
6O
n (C
2H
4O)
mH]
x wherein Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x reactive hydrogen atoms in which x has a value of at least about 2, n has a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900 and m has value such that the oxyethylene content of the molecule is from about 10%to about 90%by weight. Compounds falling within the scope of the definition for Y include, for example, propylene glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and the like. The oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of propylene oxide.
Additional conjugated polyoxyalkylene surface-active agents which are advantageously used in the compositions of this invention correspond to the formula: P [ (C
3H
6O)
n (C
2H
4O)
mH]
x wherein P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44 and m has a value such that the oxypropylene content of the molecule is from about 10%to about 90%by weight. In either case the oxypropylene chains may contain optionally, but advantageously, small amounts of ethylene oxide and the oxyethylene chains may contain also optionally, but advantageously, small amounts of propylene oxide.
Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R
2CON
R1Z in which: R1 is H, C
1-C
4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy group, or a mixture thereof; R
2 is a C
5-C
31 hydrocarbyl, which can be straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived from a reducing sugar in a reductive amination reaction; such as a glycityl moiety.
The alkyl ethoxylate condensation products of aliphatic alcohols with from about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
The ethoxylated C
6-C
18 fatty alcohols and C
6-C
18 mixed ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are water soluble. Suitable ethoxylated fatty alcohols include the C
6-C
18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50.
Suitable nonionic alkylpolysaccharide surfactants, particularly for use in the present compositions include those disclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside. ) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.
Fatty acid amide surfactants suitable for use the present compositions include those having the formula: R
6CON (R
7)
2 in which R
6 is an alkyl group containing from 7 to 21 carbon atoms and each R
7 is independently hydrogen, C
1-C
4 alkyl, C
1-C
4 hydroxyalkyl, or -- (C
2H
4O)
XH, where x is in the range of from 1 to 3.
A useful class of non-ionic surfactants includes the class defined as alkoxylated amines or, most particularly, alcohol alkoxylated/aminated/alkoxylated surfactants. These non-ionic surfactants may be at least in part represented by the general formulae: R
20-- (PO)
SN-- (EO)
tH, R
20-- (PO)
SN-- (EO)
tH (EO)
tH, and R
20--N (EO)
tH; in which R
20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of from 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10, preferably 2-5, and u is 1-10, preferably 2-5. Other variations on the scope of these compounds may be represented by the alternative formula: R
20-- (PO)
V--N [ (EO)
wH] [ (EO)
zH] in which R
20 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2) ) , and w and z are independently 1-10, preferably 2-5.
The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds generally employed in the practice of the present invention. A typical listing of nonionic classes, and species of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents and detergents" (Vol. I and II by Schwartz, Perry and Berch) .
Additional Functional Ingredients
The components of the solid composition can further be combined with various functional components suitable for uses disclosed herein, including metal safe alkaline detergents and rinse aids. In some embodiments, 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. 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 solid compositions. The functional ingredients provide desired properties and functionalities to the compositions. For the purpose of this application, the term "functional ingredient" includes a material that when dispersed or dissolved in a use and/or concentrate solution, such as an aqueous solution, provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the particular materials discussed are given by way of example only, and that a broad variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning. However, other embodiments may include functional ingredients for use in other applications.
In some embodiments, the 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.
According to embodiments of the disclosure, the various additional functional ingredients may be provided in a composition in the amount from about 0 wt-%and about 30 wt-%, from about 0 wt-%and about 25 wt-%, from about 0 wt-%and about 20 wt-%, from about 0.01 wt-%and about 30 wt-%, from about 0.1 wt-%and about 30 wt-%, from about 1 wt-%and about 30 wt-%, from about 1 wt-%and about 25 wt-%, from about 1 wt-%and about 20 wt-%, or from about 1 wt-%and about 15 wt-%. In addition, without being limited according to the disclosure, all ranges recited are inclusive of the numbers defining the range and include each integer within the defined range.
Acid Source
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. Preferably the acid has an aqueous solubility between 0.1 g/L and 1500 g/L at 20 ℃, more preferably between 0.25 g/L and 500 g/L at 20 ℃, most preferably between 0.25 and 100 g/L at 20 ℃. As used herein, the g/L description refers to the mass of acid added with sufficient aqueous medium (e.g., water) to form one liter of solution. Preferably the acid is a solid polycarboxylic acid. More preferably, 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.
In embodiments including a solid acid, 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-%.
Enzymes
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-%.
Amylases
Any amylase or mixture of amylases, 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) . For example, 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.
Cellulases
Any cellulase or mixture of cellulases, 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) . For example, the cellulase enzymes can be derived from a plant, an animal, or a microorganism such as a fungus or a bacterium. Preferred cellulase enzymes include, but are not limited to, those derived from Humicola insolens, Humicola strain DSM1800, or a cellulase 212-producing fungus belonging to the genus Aeromonas and those extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. The cellulase can be purified or a component of a microbial extract, and either wild type or variant (either chemical or recombinant) .
Lipases
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) . For example, 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) .
Proteases
Any protease or mixture of proteases, 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) . For example, 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. The 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.
Other Enzymes
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
Optionally additional hardening agents can be used in the solid compositions. Examples of 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 following patents disclose various combinations of solidification, binding and/or hardening agents that can be utilized in the solid compositions. The following U.S. patents are incorporated herein by reference: U.S. Pat. Nos. 7,153,820; 7,094,746; 7,087,569; 7,037,886; 6,831,054; 6,730,653; 6,660,707; 6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392; 6,156,715; 5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520; 4,680,134; RE32,763; and RE32818.
The composition may include a hardening agent in an amount in the range of up to about 30 wt-%. In some embodiments, 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-%.
METHODS OF MAKING SOLID COMPOSITIONS
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.
The use of pressed solids provides numerous benefits over conventional solid block or tablet compositions, which can require high pressure in a tablet press, or casting requiring the melting of a composition consuming significant amounts of energy, and/or extrusion requiring expensive equipment and advanced technical expertise. 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.
In a pressed solid process, a flowable solid, such as granular solids or other particle solids are combined under pressure to form the solid composition. 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, 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. In certain embodiments, 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. 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.
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. 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 other aspects, the solid compositions may be formed using a batch or continuous mixing system to combine ingredients. 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 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. Generally, 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.
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.
The methods can optionally include a curing step to produce the solid compositions. 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 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
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. Beneficially the methods provide metal protection for using of alkaline cleaning and rinsing compositions, without leaving white films or residues on treated metal surfaces. As a result, 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. Some non-limiting examples of dish machines include door machines or hood machines, conveyor machines, undercounter machines, glasswashers, flight machines, pot and pan machines, utensil washers, and consumer dish machines. The dish machines may be either single tank or multi-tank machines.
A door dish machine, also called a hood dish machine, refers to a commercial dish machine wherein the soiled dishes are placed on a rack and the rack is then moved into the dish machine. Door dish machines clean one or two racks at a time. In such machines, the rack is stationary and the wash and rinse arms move. A door machine includes two sets arms, a set of wash arms and a rinse arm, or a set of rinse arms.
Door machines may be a high temperature or low temperature machine. In a high temperature machine the dishes are sanitized by hot water. In a low temperature machine the dishes are sanitized by the chemical sanitizer. The door machine may either be a recirculation machine or a dump and fill machine. In a recirculation machine, the detergent solution is reused, or "recirculated" between wash cycles. The concentration of the detergent solution is adjusted between wash cycles so that an adequate concentration is maintained. In a dump and fill machine, the wash solution is not reused between wash cycles. New detergent solution is added before the next wash cycle.
In addition, 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. In a variety of these applications, cleaning compositions having a very high alkalinity are most desirable and efficacious, however the damage caused by corrosion of metal is undesirable. Moreover, the efficient drying of the surfaces is desirable.
In embodiments of using the solid alkaline metal protectant 2-in-1 detergent and rinse aid compositions, 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. In some embodiments employing the solid compositions, 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.
In an embodiment, the solid composition is housed within a dispenser to provide the use dilution into a warewashing machine (or other point of use) . In an embodiment, a dispenser may be employed to spray water (e.g. in a spray pattern from a nozzle) to form a use solution. For example, water may be sprayed toward an apparatus or other holding reservoir with the solid composition, wherein the water reacts with the solid composition to form the use solution. In certain embodiments of the methods, a use solution may be configured to drip downwardly due to gravity until the dissolved solution of the composition is dispensed for use. In an aspect, the use solution may be dispensed into a wash solution of a ware wash machine.
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. For example, the object can be wiped with, sprayed with, and/or immersed in the composition, or a use solution made from the composition. The composition can be sprayed, or wiped onto a surface; the composition can be caused to flow over the surface, or the surface can be dipped into the composition. Contacting can be manual or by machine. Preferred embodiments contact a use solution of the solid composition in a warewash machine.
In embodiments, a use solution of the 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. In additional embodiments, 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. For the purposes of this invention, the terms "dish" and "ware" are used in the broadest sense to refer to various types of articles used in the preparation, serving, consumption, and disposal of food stuffs including pots, pans, trays, pitchers, bowls, plates, saucers, cups, glasses, forks, knives, spoons, spatulas, and other glass, metal, ceramic, plastic composite articles commonly available in the institutional or household kitchen or dining room. In general, these types of articles can be referred to as food or beverage contacting articles because they have surfaces which are provided for contacting food and/or beverage. When used in these warewashing applications, the solid polymer surfactant systems provide effective sheeting action, low foaming properties and fast drying. In some aspects, 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.
In addition to having the desirable properties described above for metal protection without leaving residues or films on the surfaces, it may also be useful for the solid compositions to be biodegradable, environmentally friendly, and generally nontoxic. In some embodiments, the components including the rinse aid surfactant systems may be "food grade" .
EXAMPLES
Embodiments of the present disclosure are further defined in the following non-limiting Examples. It should be understood that these Examples, while indicating certain embodiments of the disclosure, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this disclosure, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the disclosure to adapt it to various usages and conditions. Thus, various modifications of the embodiments of the disclosure, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
In the following Examples, exemplary formulations according to the present application were prepared as described in Table 3 below.
EXAMPLE 1: METAL CORROSION TEST
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.
The exemplary compositions described in Table 3 were analyzed and compared to a non-silicated commercially available control formulation ( “Control” ) as shown in Table 4, and water.
TABLE 4
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, and 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.
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.
EXAMPLE 2: SOLID BLOCK WICKING TEST
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%, and 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.
As shown in FIGS. 2A-2B, 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.
EXAMPLE 3: CLEANING PERFORMANCE TEST
In this Example, two exemplary formulations as described in Table 3 were compared with the same non-silicated commercially available control formulation described in Table 4 ( “Control” ) , and water in a washing test. The exemplary formulations, P6 and P10 were tested at 500ppm concentration, while the Control was tested at 1500ppm concentration. Test strips were utilized to determine the cleaning performance of the formulas. These test strips contained blue stained protein and fat soils on cards. The strips were then placed in five different spots in a washing machine. The strips were then washed in one wash cycle and visually compared for soil removal. The test strips that have higher soil removal show minimal blue soil remaining and thus demonstrated improved washing performance. The test strips were further analyzed and quantified by determining the percentage of the soil removed based on the not washed test strips.
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.
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. These results clearly show that the exemplary formulations of P6, P10 and P13 provided significant improvement from the commercial formulation. The control formulation, at significantly higher concentrations than formulas P6, P10 and P13, performed only marginally better than purely water in the wash cycle.
EXAMPLE 4: RINSING AND DRYING TEST
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.
TABLE 5
These two formulas were tested by washing ceramic (ceramic 1 and 2) and melamine and measuring the resulting drying time. The test methodology included plates washed in door-type dish-machine with 65℃ water, 43 second washing and 82℃ water for an 11 second rinsing as one cycle. Chemical was automatically dosed in by dispenser with concentration sensor. For each type of plates, 4 plates were washed at the same time and drying time were visually recorded by a stopwatch. One cycle’s drying time was recorded as the average of 4 plates. At least 8 cycles’ data were collected and the average of them would be the drying time of this condition. The drying times of the ceramic and melamine after being washed by the exemplary formulation and the commercial formulation are shown in FIGS. 4A and 4B.
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.
As shown in these graphs, the formulations perform similarly. It is commonly known that average drying times of melamine are longer than ceramic or other washed dishes. Yet, the exemplary formula proved to dry the dishes similarly to the commercial formula, which includes silicone, without worse performance throughout a range of concentrations (400-1000ppm) .
It is to be understood that while the invention has been described in conjunction with the detailed description thereof, the foregoing description is intended to illustrate, and not limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments, advantages, and modifications are within the scope of the following claims. Any reference to accompanying drawings which form a part hereof, are shown, by way of illustration only. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure. All publications discussed and/or referenced herein are incorporated herein in their entirety.
The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilized for realizing the invention in diverse forms thereof.
Claims (22)
- A solid composition comprising: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; andat least one nonionic surfactant.
- The composition of claim 1, wherein the composition is substantially free of silicates or silicone-containing materials.
- The composition of any one of claims 1-2, wherein the chelant comprises an aminocarboxylate or an aminocarboxylic acid.
- The composition of any one of claims 1-3, wherein the water conditioning agent comprises a polyacrylate, polymethacrylate, and/or polymaleate homopolymer, copolymer or terpolymer.
- The composition of any one of claims 1-4, wherein the water conditioning agent comprises a first and a second water conditioning agent in a wt-ratio of about 0: 5: 1 to about 1: 0.5 of the first water conditioning agent that is a polycarboxylate or polycarboxylic acid to the second water conditioning agent that is a polyacrylate, polymethacrylate, and/or polymaleate homopolymer, copolymer or terpolymer.
- The composition of any one of claims 1-5, wherein the nonionic surfactant is an alcohol alkoxylate according to the following formulae:R 1-O- (EO) x3 (PO) y3-H (A)wherein R 1 is a straight-chain C 10-C 16 alkyl, wherein x 3 is from 5 to 8, and wherein y 3 is from 2 to 5;R 1-O- (EO) x4 (PO) y4-H (A2)wherein R 1 is a straight-chain C 10-C 16 alkyl, wherein x 4 is from 4 to 6, and wherein y 4 is from 3 to 5;R 2-O- (EO) x1-H (B)wherein R 2 is C 10-C 14 alkyl with an average of at least 2 branches per residue, andwherein x 1 is from 5 to 10;R 2-O- (EO) x2-H (C)wherein R 2 is C 10-C 14 alkyl with an average of at least 2 branches per residue, and wherein x 2 is from 2 to 4; and/ora surfactant polymer according to the following formulae:R 7-O- (PO) y 5 (EO) x 5 (PO) y 6-H (D)wherein R 7 is a branched C 8-C 16 Guerbet alcohol, x 5 is from 5 to 30, y 5 is from 1 to 4, and y 6 is from 10 to 20;R 6-O- (PO) y 4 (EO) x 4-H (E)wherein R 6 is a C 8-C 16 Guerbet alcohol, wherein x 4 is from 2 to 10, and wherein y 4 is from 1 to 2;wherein x is from 120-220, y is from 12 to 20, and z is from 12 to 20;wherein x is from 88 to 108, y is from 57 to 77, and z is from 88 to 108;wherein x is from 15 to 25, y is from 10 to 25, and z is from 15 to 25;R 4-O- (EO) x (XO) y-H (I)wherein R4 is C 13-C 15 alkyl, x is from 8 to 10, y is from 1 to 3, and XO is butylene oxide; and/orR 5-O- (EO) x (PO) y-H (J)wherein R5 is C 12-C 15 alkyl, x is from 3 to 5, and y is from 5 to 7.
- The composition of any one of claims 1-6, further comprising at least one additional functional ingredient.
- The composition of claim 7, wherein the at least one additional functional ingredient is an enzyme, additional chelant, and/or an acid.
- The composition of any one of claims 1-8, wherein the acid is a low solubility solid acid.
- The composition of any one of claims 1-9, wherein the solid is a pressed solid.
- The composition of any one of claims 1-10, wherein the alkali metal carbonate alkalinity source comprises from about 40 wt-%to about 90 wt-%of the composition, wherein the chelant comprises from about 2 wt-%to about 20 wt-%of the composition, wherein the at least one water conditioning agent comprises from about 2 wt-%to about 20 wt-%of the composition, and wherein the at least one nonionic surfactant comprises from about 2 wt-%to about 30 wt-%of the composition.
- The composition of any one of claims 1-10, wherein the alkali metal carbonate alkalinity source comprises from about 50 wt-%to about 90 wt-%of the composition, wherein the chelant comprises from about 4 wt-%to about 20 wt-%of the composition, wherein the at least one water conditioning agent comprises from about 2 wt-%to about 10 wt-%of the composition, and wherein the at least one nonionic surfactant comprises from about 2 wt-%to about 20 wt-%of the composition.
- The composition of any one of claims 1-10, wherein the alkali metal carbonate alkalinity source comprises from about 60 wt-%to about 85 wt-%of the composition, wherein the chelant comprises from about 6 wt-%to about 16 wt-%of the composition, wherein the at least one water conditioning agent comprises from about 2 wt-%to about 6 wt-%of the composition, and wherein the at least one nonionic surfactant comprises from about 2 wt-%to about 10 wt-%of the composition.
- A use solution comprising:the solid composition according to any one of claims 1-13 in a solution with an aqueous source, preferably water.
- A method of using a 2-in-1 detergent and rinse additive composition comprising:contacting the use solution according to claim 14 to an article or surface including a hard metal surface in need of cleaning and drying, and thereafterrinsing 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.
- The method of claim 15, where a use solution of the composition has a pH between about 9 and about 12.5, between about 9 and about 11, or between about 9 and about 10.5.
- The method of any one of claims 15-16, wherein the solid composition is housed within a dispenser to provide the use dilution into a warewashing machine.
- The method of claim 17, wherein the use solution is dispensed into a wash solution of a ware wash machine.
- The method of claim 18, wherein the ware wash machine is an institutional dish machine, a clean in place dish machine, or a consumer dish machine.
- The method of any one of claims 15-19, wherein a use solution concentration of from about 100 ppm to about 3000 ppm, and preferably 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 from about 350 ppm to about 1000 ppm.
- The method of any one of claims 15-20, wherein the hard metal surface is an alkaline sensitive metal surface.
- The method of claim 21, wherein the alkaline sensitive metal includes aluminum.
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