Detergent compositions containing phosphonate-stabilized enzymes

Abstract

To provide a detergent composition containing an enzyme, an alkaline source, and a phosphonate or amine phosphonate salt.SOLUTION: A use solution of a detergent composition containing phosphonate disclosed herein can retain its enzymatic activity for a long period of time. Specifically, it has been found that one particular type of phosphonate and another particular type of amine phosphonate salt stabilize an enzyme in the detergent composition. A solid detergent composition containing phosphonate or amine phosphonate salts disclosed herein can be more effective in removing dirt and makes it possible to save production and use costs.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 384,433, entitled "Enzyme Stability and Phosphonate Types," filed September 7, 2016, which is incorporated herein by reference in its entirety.

[0002] The present disclosure generally relates to the field of cleaning compositions. Specifically, solid detergent compositions containing an enzyme, a phosphonate, an alkaline source, and optionally other ingredients. The enzymes in these detergent compositions exhibit excellent stability after dissolving in the use solution of the composition. The enzyme stability allows the enzyme to function for a longer period of time, thus providing more effective soil removal / redeposition prevention. Conversely, the excellent enzyme stability allows the amount of enzyme and other ingredients to be reduced to increase the enzyme's effectiveness in the disclosed compositions, while still achieving similar cleaning results. [Background technology]

[0003] Detergency is defined as the ability to wet, emulsify, suspend, penetrate, and disperse soils. Conventional detergents used in the dishwashing and laundry industries include alkaline detergents. Alkaline detergent formulations using alkali metal carbonates and / or alkali metal hydroxides, intended for both commercial and consumer use, are known to provide effective detergency.

[0004] The enzyme is 20 世紀 Enzymes have been used in cleaning compositions since the early days of the invention. However, it wasn't until the mid-1960s that enzymes with both pH stability and soil reactivity for detergent applications became commercially available. Enzymes are known as effective chemicals for use with detergents and other cleaning agents to break down soils. Enzymes break down soils, making them more soluble and allowing surfactants to remove them from surfaces, providing improved cleaning of the substrate.

[0005] Specifically, enzymes can provide desirable activity for removing, for example, protein-based, carbohydrate-based, or triglyceride-based stains from substrates. As a result, enzymes have been used in a variety of cleaning applications to digest or decompose stains such as grease, oil (e.g., vegetable oil or animal fat), protein, and carbohydrate. For example, enzymes can be added as components of cleaning compositions for laundry, textiles, dishwashing, in-place cleaning, drains, floors, carpets, medical or dental instruments, meat cutting tools, hard surfaces, personal care, and the like. While enzyme-containing products have evolved from simple powders containing alkaline proteases to more complex granular compositions containing multiple enzymes and even liquid compositions, there remains a need for alternative cleaning applications using stabilized enzymes. Numerous mechanisms have been used to improve enzyme stabilization for storage in detergent compositions. However, improvements remain necessary to ensure that detergent composition use solutions retain their detergency and cleaning performance when exposed to the high temperatures and pH of actual cleaning applications for extended periods of time.

[0006] Therefore, it is an objective to develop detergent compositions containing enzymes and stabilizers that are capable of maintaining suitable enzyme stability for a much longer period of time under the high temperature and high pH conditions in which the use solutions are used.

[0007] It is a further object to develop multi-use solid detergent compositions that not only have storage, shelf, and dimensional stability, but also provide excellent enzyme stability under high temperature and high pH conditions within the solid compositions and in their use solutions, providing improved cleaning performance. Enzyme activity in these compositions or their use solutions is retained for extended periods under high temperature and high pH conditions.

[0008] It is an objective to develop methods for the use of stabilized enzymes either in the detergent composition itself and in the use solution for improved cleaning performance.

[0009] It is a further object to develop a method for stabilizing enzymes in solid detergent compositions and their use solutions.

[0010] Advantageously, such an objective overcomes a significant limitation of the state of the art of enzyme stability in detergent compositions, namely, that unstable enzymes significantly decrease in activity over time, including within short periods of 5 to 20 minutes, in the use solution of these detergent compositions.

[0011] A further object is to develop multi-use compositions and methods for using same to improve the protein removal and anti-redeposition properties of detergent compositions, particularly non-corrosive detergent compositions.

[0012] These and other objects, advantages, and features of the present disclosure will become apparent from the following specification, taken in conjunction with the claims set forth herein. Summary of the Invention

[0013] An advantage of the present disclosure is that the enzymes in the solid detergent composition can retain their activity for extended periods of time not only during storage of the solid composition but also in the use solution of the composition.

[0014] Surprisingly, it has been discovered that adding a specific type of phosphonate or its salt, or another specific type of amine phosphonate salt, to detergent compositions containing enzymes can maintain the enzyme activity in the use solution of the composition for a long period of time during the actual use of the composition for cleaning purposes.It has also been discovered surprisingly that the enzyme in the use solution of the detergent composition of the present disclosure has excellent stability.This discovery leads to a more effective composition due to the prolonged enzyme activity for removing soil.Advantageously, this improvement also allows the elimination or reduction of the use of enzymes, stabilizers, or some other ingredients that are commonly found in detergent compositions.

[0015] In one aspect, an enzyme, [ka] or a salt thereof, and an alkaline source, wherein the enzyme is a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; the alkaline source is a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; and R 10 and R 11 are independently hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivatives thereof, provided that R 10 and R 11 are both —CH2—PO(OH)2 groups.

[0016] In another aspect, there is provided a composition comprising an enzyme, an alkaline source, and an amine phosphonate salt, wherein the amine phosphonate salt is [ka] and an amine, wherein the enzyme is a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; and R 12 , R 13 , and R 14 is independently hydroxyl, methyl, a substituted alkyl, —PO(OH) 2 , —CH 2 COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof.

[0017] In yet another aspect, there is provided a solid detergent composition comprising an alkaline source, a phosphonate, and an enzyme, wherein the alkaline source comprises a metal carbonate, metal bicarbonate, metal silicate, or a mixture thereof; the enzyme is a protease, amylase, lipase, cellulase, peroxidase, gluconase, or a mixture thereof; and the phosphonate is [ka] or a salt thereof, and R 10 and R 11 are independently hydrogen, substituted carboxylic acid, phosphonate, ethanol, diglyco, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonate-methyl, with the proviso that R 10 and R 11 are both —CH—PO(OH) groups, and the components of the composition are mixed and used to form a solid detergent.

[0018] In another aspect, there is provided a solid detergent composition comprising an alkaline source, an enzyme, and an amine phosphonate salt, wherein the alkaline source comprises a metal carbonate, metal bicarbonate, metal silicate, or a mixture thereof; the enzyme is a protease, amylase, lipase, cellulose, peroxidase, gluconase, or a mixture thereof; and the amine phosphonate salt is selected from the group consisting of: [ka] and R is a product of a phosphonate and an amine represented by the formula 12、R13、 and R 14 are independently hydroxyl, methyl, —PO(OH)2, —CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof, and the components of the composition are mixed and used to produce a solid detergent.

[0019] In yet another aspect, there is provided a method of cleaning, sanitizing, and / or bleaching that includes forming a use solution of the compositions disclosed herein and contacting a surface or object in need of cleaning and sanitizing with the use solution.

[0020] In another aspect, a method for stabilizing an enzyme in a solid detergent composition is provided. The method comprises adding a hydroxybenzoate of formula (I) to the enzyme-containing detergent composition. [ka] or a salt thereof, or an amine phosphonate salt of R 10 and R 11 are independently hydrogen, substituted carboxylic acid, phosphonate, ethanol, diglycol, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonatemethyl, where R 10 and R 11 are both —CH—PO(OH) groups, and the amine phosphonate salt has the formula [ka] and an amine, 12 , R 13 , and R 14 are independently hydroxyl, methyl, —PO(OH) 2 , —CH 2 COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof.

[0021] While multiple embodiments are disclosed, still other embodiments of the present disclosure will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the examples, figures, drawings, and detailed description are to be regarded as illustrative in nature and not restrictive. [Brief explanation of the drawings]

[0022] [Figure 1A] Figure 1A shows the protease activity at 120°F (about 48.9°C) at different time points in use solutions of various base-formulated detergent compositions containing different phosphonates at different levels. Figure 1A shows the protease activity at a 0.3 wt% phosphonate level. [Figure 1B]Figure 1B shows the protease activity at 120°F in use solutions of various base-formulated detergent compositions containing different phosphonates at different levels at different time points. Figure 1B shows the protease activity at a 0.6 wt% phosphonate level. [Figure 1C] Figure 1C shows the protease activity at 120°F in use solutions of various base-formulated detergent compositions containing different phosphonates at different levels at different time points. Figure 1C shows the protease activity of elemental phosphorus at the 0.1 wt% level. [Figure 2A] Figure 2A shows the protease activity in use solutions of base or all ash formulated detergent compositions containing phosphonates with or without alkanolamines at different time points at 120° F. Figure 2B shows the protease activity with phosphonebutanetricarboxylic acid (PBTC) alone or together with alkanolamines in the base formulated detergent compositions. [Figure 2B] Figure 2B shows the protease activity in use solutions of base or all ash formulated detergent compositions containing phosphonates with or without alkanolamines at different time points at 120° F. Figure 2B shows the protease activity with 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) alone or with alkanolamines in the base formulated detergent compositions. [Figure 2C] Figure 2A shows the protease activity in the use solutions of base or all ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points at 120° F. Figure 2B shows the protease activity with PSO alone or together with alkanolamine in the base formulated detergent composition. [Figure 2D] Figure 2A shows the protease activity in use solutions of base or all ash detergent compositions containing phosphonates with or without alkanolamines at different time points at 120° F. Figure 2D, for example, shows the protease activity in all ash detergent compositions containing various phosphonates, with no bicarbonate in the detergent composition. [Figure 3A] Figure 3A shows amylase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 3A shows amylase activity at a 0.3 wt% level of phosphonate. [Figure 3B] Figure 3A shows amylase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 3B shows amylase activity at a 0.6 wt% level of phosphonate. [Figure 3C] Figure 3A shows amylase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 3B shows amylase activity at a 0.1 wt% elemental phosphorus level. [Figure 4A] Figure 4A shows amylase activity at 120°F in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 4B shows amylase activity with PBTC alone or together with alkanolamine in the base formulated detergent composition. [Figure 4B] Figure 4B shows amylase activity at 120°F in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 4C shows amylase activity with HEDP alone or with alkanolamine in base formulated detergent compositions. [Figure 4C] Figure 4C shows amylase activity at 120°F in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 4D shows amylase activity with PSO alone or together with alkanolamine in base formulated detergent compositions. [Figure 4D]Figure 4A shows the amylase activity in use solutions of base or all-ash formula detergent compositions containing phosphonates with or without alkanolamines at different time points at 120° F. Figure 4B shows the amylase activity in all-ash formula detergent compositions containing various phosphonates. [Figure 5A] Figure 5A shows lipase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 5A shows lipase activity at a 0.3 wt% level of phosphonate. [Figure 5B] Figure 5B shows lipase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 5B shows lipase activity at a 0.6 wt% level of phosphonate. [Figure 5C] Figure 5C shows lipase activity at 120°F in use solutions of various base-formulated detergent compositions containing different levels of phosphonate at different time points. Figure 5C shows lipase activity at a 0.1 wt% elemental phosphorus level. [Figure 6A] Figures 6A and 6B show lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6A shows lipase activity at 120°F with PBTC alone or together with alkanolamine in the base formulated detergent composition. [Figure 6B] Figure 6B shows lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6C shows lipase activity at 120°F with HEDP alone or with alkanolamine in base formulated detergent compositions. [Figure 6C]Figure 6A shows lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6B shows lipase activity at 120°F using PSO alone or with alkanolamine in a base formulated detergent composition. [Figure 6D] Figure 6A shows lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6B shows lipase activity at room temperature with PBTC alone or together with alkanolamine in the base formulated detergent composition. [Figure 6E] Figure 6B shows lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6C shows lipase activity at room temperature using HEDP in a base formulated detergent composition or with an alkanolamine. [Figure 6F] Figure 6F shows lipase activity at 120°F or at room temperature in use solutions of base or all-ash formulated detergent compositions containing phosphonate with or without alkanolamine at different time points. Figure 6F shows lipase activity at room temperature with PSO alone or together with alkanolamine in base formulated detergent compositions. [Figure 6G] Figure 6A shows the lipase activity in use solutions of base or all-ash formula detergent compositions containing phosphonates with or without alkanolamines at different time points at 120°F or at room temperature. Figure 6B shows the lipase activity in all-ash formula detergent compositions containing various phosphonates at 120°F.

[0023] Various embodiments of the present disclosure are described in detail with reference to examples, figures, and drawings, in which like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the present disclosure. The figures shown herein are presented for illustrative purposes of the present disclosure, not as limitations on the various embodiments according to the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0024] The present disclosure relates to detergent compositions containing enzymes that have excellent enzyme stability in their use solutions. The use solutions of such compositions retain their enzyme activity for extended periods of time. In particular, in the use solutions produced from the detergent compositions disclosed herein, the enzymes have such excellent stability that they can be effective in removing soils, proteins, and starches for extended periods of time.

[0025] The embodiments of the present disclosure are not limited to specific compositions and methods of use, which may vary and are understood by those skilled in the art. It should be further understood that all terminology used herein is merely for the purpose of describing specific embodiments and is not intended to be limiting in any manner or scope. For example, when used in this specification and the appended claims, the singular forms "a," "an," and "the" can include plural referents unless the context clearly indicates otherwise. Furthermore, all units, prefixes, and symbols can be expressed in their SI-recognized form.

[0026] Numerical ranges recited herein include the numbers within the defined range. Throughout this disclosure, various aspects of the disclosure are presented in range format. The description in range format should be understood to be merely for convenience and brevity, and should not be interpreted as an indefinite limitation on the scope of the disclosure. Thus, the description of a range should be considered to specifically disclose all possible subranges and individual numerical values ​​within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0027] In order to make the present disclosure easier to understand, certain terms are first defined.Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art in connection with the embodiments of the present disclosure.Many methods and materials similar to, modified or equivalent to those described herein can be used to practice the embodiments of the present disclosure without undue experimentation, and preferred materials and methods are described herein.In describing and claiming the embodiments of the present disclosure, the following terminology will be used in accordance with the definitions set forth below.

[0028] The term "about," as used herein, refers to variations in numerical quantities that may occur, for example, due to typical measuring and liquid handling procedures used in making concentrates or use solutions in the real world; inadvertent errors in those procedures; differences in the make, source, or purity of ingredients used to make the compositions or carry out the methods; etc. The term "about" also encompasses amounts that vary due to different equilibrium conditions for compositions resulting from a particular initial mixture. Whether modified by the term "about," the claims include the equivalent of the amount.

[0029] The terms "actives" or "percent actives" or "weight percent actives" or "actives concentration" are used interchangeably herein and refer to the concentration of the components involved in purification expressed as a percentage minus inactive ingredients such as water or salt.

[0030] As used herein, "substituted" refers to an organic group (e.g., an alkyl group) as defined below in which one or more bonds to hydrogen atoms contained therein have been replaced by bonds to non-hydrogen or non-carbon atoms. Substituents also include groups in which one or more carbon atom(s) or hydrogen atom(s) have been replaced by one or more bonds, including double or triple bonds, to heteroatoms. Thus, unless otherwise specified, a substituent is substituted with one or more substituents. A substituent may be substituted with 1, 2, 3, 4, 5, or 6 substituents.

[0031] Substituted ring groups include rings and ring systems in which a bond to a hydrogen atom is replaced with a bond to a carbon atom. Thus, substituted cycloalkyl, aryl, heterocyclyl, and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups, as defined herein.

[0032] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, and includes 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).

[0033] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to an alkyl group having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents 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, methyl ... The substituents may include nitro, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0034] In some embodiments, substituted alkyls can include heterocyclic groups. As used herein, the term "heterocyclic group" includes closed ring structures similar to carbocyclic groups in which one or more of the carbon atoms in the ring is an element other than carbon, such as nitrogen, sulfur, or oxygen. Heterocyclic groups can be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0035] An alkenyl group or alkene is a straight-chain, branched-chain, or cyclic alkyl group having from 2 to about 30 carbon atoms and further containing at least one double bond. In some embodiments, alkenyl groups have from 2 to about 10 carbon atoms, or typically from 2 to 10 carbon atoms. Alkenyl groups can be substituted or unsubstituted. Alkenyl groups can be substituted in the same manner as alkyl groups.

[0036] As used herein, the terms "alkylene," "cycloalkylene," and "alkenylene," alone or as part of another substituent, refer to a divalent radical derived from an alkyl, cycloalkyl, or alkenyl group, respectively, as exemplified by -CHCHCH-. For alkylene, cycloalkylene, and alkenylene groups, no orientation of the linking group is implied.

[0037] As used herein, the term "ester" refers to an ester of an -R 30 COOR 31 R refers to the group 30 R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 31 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0038] As used herein, the term "amine" (or "amino") refers to a group represented by -R 32 NR 33 R 34 R refers to the group 32 R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 33 and R 34is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0039] As used herein, the term "amine" also refers to an independent compound. When an amine is a compound, R 32’ NR 33’ R 34’ can be represented by the formula: 32’、 R 33’ and R 34 is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0040] As used herein, the term "alcohol" refers to an alcohol having an -R 35 Refers to the OH group. R 35 is absent, or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein.

[0041] As used herein, the term "carboxylic acid" refers to a group consisting of -R 36 Refers to the COOH group. 36 is absent, or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein.

[0042] As used herein, the term "ether" refers to an -R 37 OR 38 R refers to the group 37R is absent or a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein. 38 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0043] "Anti-redeposition agents" refer to compounds that help remain suspended in water instead of redepositing on the object being cleaned. Anti-redeposition agents are useful in the present disclosure to help reduce the redeposition of removed soils on the surface being cleaned.

[0044] As used herein, the term "cleaning" refers to performing, promoting, or assisting in the removal of stains, bleaching, reduction of microbial populations, and any combination thereof. As used herein, the term "microorganism" refers to any non-cellular or unicellular (including colonial) organism. Microorganisms include all prokaryotes. Microorganisms include bacteria (including cyanobacteria), spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, and some algae. As used herein, the term "microbe" is synonymous with microorganism.

[0045] As used herein, the term "disinfectant" refers to an agent that kills all vegetative cells, including most recognized pathogenic microorganisms, using the procedures set forth in the AOAC Use Dilution Methods, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 955.14 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2). As used herein, the term "high-level disinfection" or "high-level disinfectant" refers to a compound or composition that kills substantially all germs, except for high levels of bacterial spores, and is effective using a chemical germicide approved for marketing as a sterilant by the U.S. Food and Drug Administration. As used herein, the term "intermediate-level disinfection" or "intermediate-level disinfectant" refers to a compound or composition that kills mycobacteria, most viruses, and bacteria using a chemical germicide registered by the Environmental Protection Agency (EPA) as a tuberculocide. As used herein, the term "low-level disinfection" or "low-level disinfectant" refers to a compound or composition that kills some viruses and bacteria using a chemical germicide that is registered by the EPA as a hospital disinfectant.

[0046] As used herein, the phrase "food processing surface" refers to the surfaces of tools, machines, equipment, structures, buildings, etc. used as part of food processing, preparation, or preservation activities. Examples of food processing surfaces include surfaces of food processing or preparation equipment (e.g., slicing, canning, or conveying equipment including flumes), surfaces of food processing supplies (e.g., cookware, dishware, cleaning supplies, and bar glass), and surfaces of floors, walls, or fixtures of structures where food processing occurs. Food processing surfaces are found and used in food anti-spoilage air circulation systems, aseptic packaging sanitizers, food refrigerator and cooler sanitizers and disinfectants, dishwashing sanitizers, blancher sanitizers, food packaging materials, cutting board additives, third-sink sanitizers, beverage refrigerators and warmers, meat refrigerators or boilers, automatic dish sanitizers, sanitizing gels, cooling towers, food processing antimicrobial clothing sprays, and non-aqueous to low-aqueous food preparation lubricants, oils, and rinse additives.

[0047] As used herein, the phrase "food product" includes any food substance that may require treatment with an antimicrobial agent or composition and is edible with or without further cooking. Food products include meat (e.g., red meat and pork), seafood, poultry, agricultural products (e.g., fruits and vegetables), eggs, fertilized eggs, egg products, cooked foods, wheat, seeds, roots, tubers, leaves, stems, corn, flowers, sprouts, seasonings, or combinations thereof. The term "produce" refers to food products such as fruits and vegetables, which are typically sold uncooked and often unpackaged, and which may sometimes be eaten raw, as well as plants or plant-derived materials.

[0048] The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, panels, windows, plumbing fixtures, kitchen and bathroom fixtures, appliances, engines, circuit boards, and dishes. Hard surfaces can include, for example, healthcare surfaces and food processing surfaces.

[0049] As used herein, the phrase "healthcare surface" refers to surfaces of instruments, devices, carts, cages, furniture, structures, buildings, and the like used as part of a healthcare activity. Examples of healthcare surfaces include surfaces of medical or dental instruments, surfaces of medical or dental devices, surfaces of electronic equipment used to monitor patient health, and surfaces of floors, walls, or fixtures of structures where healthcare occurs. Healthcare surfaces are found in hospitals, surgical rooms, infirmary rooms, birthing rooms, funeral homes, and clinical diagnostic rooms. These surfaces may be representative of "hard surfaces" (walls, floors, bedpans, etc.), or textile surfaces, e.g., knitted, woven, and nonwoven surfaces (surgical garments, draperies, bed linens, bandages, etc.), or patient care equipment (respirators, diagnostic equipment, shunts, body scopes, wheelchairs, beds, etc.), or surgical and diagnostic equipment. Healthcare surfaces include items and surfaces used in animal healthcare.

[0050] As used herein, the term "instrument" refers to a variety of medical or dental instruments or devices that may benefit from cleaning with a composition according to the present disclosure.

[0051] The term "laundry" refers to items or articles to be cleaned in a washing machine. Generally, laundry refers to any item or article made from or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials may include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. Fibers may be treated or untreated. Exemplary treated fibers include those that have been flame-retardant treated. It should be understood that the term "linen" is often used to describe specific types of laundry items, including bed sheets, pillowcases, towels, table linens, tablecloths, bar mops, and uniforms. Additionally, the present disclosure provides compositions and methods for treating surfaces, including non-laundry items and hard surfaces such as dishes, particularly glasses, and other tableware.

[0052] As used herein, the phrases "medical instruments," "dental instruments," "medical devices," "dental devices," "medical equipment," or "dental equipment" refer to instruments, devices, tools, appliances, apparatus, and equipment used in medical or dental practice. Such instruments, devices, and equipment can be pasteurized, soaked, or washed, then heat sterilized, or can benefit from cleaning in the compositions of the present disclosure. These various instruments, devices, and equipment include, but are not limited to, diagnostic instruments, trays, pans, holders, racks, forceps, scissors, shears, saws (e.g., bone saws and their blades), hemostats, knives, chisels, rongeurs, files, nippers, drills, drill bits, rasps, burrs, spreaders, breakers, elevators, clamps, needle holders, carriers, clips, hooks, gouges, curettes, pitons, straighteners, punches, extractors, scoops, keratometers, spatulas, expressors, trocars, dilators, cages, glassware, tubing, catheters, cannulae, plugs, stents, scopes (e.g., endoscopes, stethoscopes, and arthroscopes), and related equipment, and the like, or combinations thereof.

[0053] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random, and alternating copolymers, terpolymers, and higher "x"-mers, further including derivatives, combinations, and blends thereof. Furthermore, unless otherwise specifically limited, the term "polymer" is intended to include all possible isomeric configurations of the molecule, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Furthermore, unless otherwise specifically limited, the term "polymer" is intended to include all possible geometric configurations of the molecule.

[0054] For purposes of this patent application, successful microbial reduction is achieved when the microbial population is reduced by at least about 50%, or significantly more than that achieved by washing with water. Greater reduction in microbial population provides greater levels of protection.

[0055] As used herein, the term "sanitizer" refers to an agent that reduces the number of bacterial contaminants to a safe level as determined by public health requirements. In one embodiment, a sanitizer for use in this disclosure will provide at least a 3-log reduction, and more preferably a 5-log reduction. These reductions can be evaluated using the procedures set forth in Germicidal and Detergent Sanitizing Action of Disinfectants, Official Methods of Analysis of the Association of Official Analytical Chemists, paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPA Guideline 91-2). According to this reference, a sanitizer must provide a 99.999% reduction (a 5-log reduction) against several test organisms within 30 seconds at room temperature, 25±2°C. Sanitizer and disinfectant standards may vary by application and region.

[0056] As used herein, the term "soil" or "stain" refers to non-polar, oily substances, which may or may not contain certain substances such as mineral clays, sand, natural minerals, carbon black, graphite, kaolin, environmental dust, etc.

[0057] As used in this disclosure, the term "sporicide" refers to a physical or chemical agent or process capable of causing a greater than 90% reduction (1 log reduction) in a Bacillus cereus or Bacillus subtili spore population within 10 seconds at 60° C. In certain embodiments, the sporicidal compositions of the present disclosure provide a greater than 99% reduction (2 log reduction), a greater than 99.99% reduction (4 log reduction), or a greater than 99.999% reduction (5 log reduction) in such population within 10 seconds at 60° C.

[0058] The distinction between antimicrobial "cidal" or "static" activity, definitions describing the degree of effectiveness, and official laboratory protocols for measuring this effectiveness are considerations for understanding the relevance of antimicrobial agents and compositions. Antimicrobial compositions can affect two types of microbial cell damage. The first is a lethal, irreversible action that results in complete microbial cell destruction or incapacitation. The second type of cell damage is reversible, so that organisms can reproduce again once the agent is removed. The former is called microbiocidal, and the latter is called microbistatic. Sanitizers and disinfectants are, by definition, agents that provide antimicrobial or microbicidal activity. In contrast, antiseptics are generally described as inhibitors or microbistatic compositions.

[0059] As used herein, the terms "substantially free" or "free" refer to a composition that is completely devoid of the component or has such a small amount of the component that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and must be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight, and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0060] The term "substantially similar cleaning performance" generally refers to what is generally achieved by a substitute cleaning product or system using the same degree of cleaning power (or at least not significantly less) or generally the same expenditure of effort (or at least not significantly less).

[0061] 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 "dishwashing" refers to the washing, cleaning, or rinsing of dishes. Ware also refers to items made of plastic. Types of plastics that can be cleaned with compositions according to the present disclosure include, but are not limited to, those containing polypropylene polymer (PP), polycarbonate polymer (PC), melamine formaldehyde resin or melamine resin (melamine), acrylonitrile-butadiene-styrene polymer (ABS), and polysulfone polymer (PS). Other exemplary plastics that can be cleaned using the compounds and compositions of the present disclosure include polyethylene terephthalate (PET) polystyrene polyamide.

[0062] As used herein, the term "water" includes food processing or transport water. Food processing or transport water includes produce transport water (e.g., found in flumes, pipe transport, cutters, slicers, blanchers, retort systems, washers, etc.), belt sprays for food transport lines, boot and hand wash soak pans, third sink rinse water, etc. Water can also include domestic and recreational water, such as pools, spas, recreational flumes and water slides, fountains, etc.

[0063] As used herein, the phrase "water-soluble" means that the material in the present composition is soluble in water. Generally, the material should be soluble at a concentration of about 0.1%, alternatively about 1%, alternatively about 5%, alternatively about 15% by weight in water at 25°C.

[0064] As used herein, "essentially similar compositions" refers to compositions in which everything else is the same except for the addition of a different amount of a first solid, or compositions in which the weight percent of alkali compound is within 10% of the reference composition 1. The compared blocks have identical shapes and dimensions.

[0065] The terms "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 multiplied by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "wt%," and the like.

[0066] 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 and compositions may include additional steps, components, or ingredients, provided that the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.

[0067] It should be noted that, as used herein and in the appended claims, the term "configured" describes a system, apparatus, or other structure that is constructed or configured to perform a particular task or conform to a particular configuration. The term "configured" may be used interchangeably with other similar phrases such as arranged and configured, constructed and arranged, adapted and configured, and adapted, built, manufactured, and arranged.

[0068] Detergent compositions and detergent products As used herein, the term "composition" refers to the chemical components of a product or article. The product or article may be in liquid, solid, or powder form, or a mixture thereof. The same or similar composition may result in a different product or article due to different processes, preparations, or amounts in which each component of the composition is combined in the product or article.

[0069] As used herein, the term "detergent composition" refers to the chemical components of a detergent product or detergent. Detergent products or detergents are typically used for cleaning purposes by themselves or by their use solutions. Detergents or detergent products can be in liquid, solid, powder form, or a mixture thereof. Detergent products or detergents can be supplied in one package or in separate packages. The same or similar detergent compositions may result in different detergent products due to different processes or amounts in which each component of the composition is combined in the detergent product. In this disclosure, the terms "detergent product" and "detergent" are used interchangeably.

[0070] Solid detergent As used herein, the term "solid" refers to a state of matter known to those skilled in the art. A solid can be crystalline, amorphous, or a mixture thereof. A solid can be a single compound or a mixture of compounds. A solid can be a mixture of two or more different solids. A solid can be a collection of particles, each having a size of a few, tens, or hundreds of micrometers or nanometers. A solid can be a powder of one or more compounds.

[0071] As used herein, a solid detergent or cleaning composition refers to a detergent or cleaning composition in a solid form such as a powder, flake, granule, pellet, tablet, lozenge, puck, briquette, brick, block, or another solid form known to those skilled in the art. While the term solid block is often referred to herein, it is understood that the solid composition can take a variety of forms. In a preferred embodiment, a compressed solid block is used. It should be understood that the term "solid detergent" refers to the state of the detergent composition under the expected storage and use conditions of the solid detergent composition. Generally, the detergent composition is expected to remain solid when provided at temperatures from room temperature up to about 120°F.

[0072] The solid detergent composition may be provided as a pressed solid block, a cast solid block, an extruded pellet or block, or a tablet, such that one or more solids are available in packages having sizes from about 1 gram to about 11,000 grams.

[0073] The solid detergent composition may be provided in the form of a unit dose. A unit dose refers to a solid detergent composition unit sized so that the entire unit is used in one wash cycle. When the solid detergent composition is provided as a unit dose, it is preferably provided as a pressed solid, a cast solid, an extruded pellet, or a tablet having a size of about 1 gram to about 50 grams. Alternatively, the pressed solid, the cast solid, the extruded pellet, or the tablet may have a size of 50 grams to 250 grams. The extruded solid, the cast solid, or the pressed solid may also have a weight of about 100 grams or more.

[0074] The solid detergent composition can also be provided in a multi-use (e.g., multi-use) solid form, such as a block or multiple pellets, which can be used repeatedly to generate an aqueous use solution of the detergent composition for multiple cycles or a predetermined number of dispensing cycles. The multi-use solid detergent composition can be used repeatedly to generate an aqueous detergent composition, e.g., a use solution, for multiple wash cycles. The multi-use solid detergent composition can have a mass of from about 1 kilogram to about 10 kilograms or more.

[0075] Typically, the solid detergent compositions disclosed herein dissolve rapidly and completely into a stable use solution upon contact with an aqueous solution. In some aspects of the present disclosure, the amount and type of anionic surfactant used in the solid detergent composition provides a desirable dissolution rate for a particular dispensing rate. A stable use solution does not contain any solids upon visual inspection.

[0076] The pressed solid detergent block is preferably made to provide stability so that the reactive components in the composition do not react with each other until the time of dilution and / or use.In some embodiments, the order of introducing the components to form the solid is not limited, since the amount of water introduced into the solid composition is minimal and / or not at all.However, in some embodiments, the pressed solid detergent block is made by using a binding system to minimize any damage to the coated granules that may be used.

[0077] Beneficially, the pressing process to create the compressed solid detergent block produces a compressed solid detergent block and prevents reaction or mixing of the components. In one aspect of the present disclosure, the solid detergent composition remains unreacted or unmixed until the point of use, e.g., dilution.

[0078] In the pressed solids process, flowable solids, such as granular solids or other particulate solids containing a binder, are combined under pressure. In the pressed solids process, the flowable solids of the composition are placed in a form (e.g., a mold or container). The method can include gently compressing the flowable solids in the form to produce a solid cleaning composition.

[0079] The method may further include a hardening step to produce a solid cleaning composition. As referred to herein, an unhardened composition comprising a flowable solid is compressed to provide sufficient surface contact between particles that make up the flowable solid so that the unhardened composition will solidify into a stable solid cleaning composition. A sufficient amount of particles (e.g., granules) in contact with each other provides effective particle bonding to create a stable solid composition. The inclusion of a hardening step may include allowing the compressed solid to harden for, for example, several hours or about one day (or more). In additional embodiments, the method may include vibrating the flowable solid in a mold or form, such as the method disclosed in U.S. Pat. No. 8,889,048, the entire contents of which are incorporated herein by reference.

[0080] The use of pressed solids offers numerous advantages over conventional solid block or tablet compositions, which require high pressure for tablet compression, or casting, which requires melting the composition, consuming significant amounts of energy, and / or extrusion, which requires expensive equipment and advanced technical knowledge. Pressed solids overcome the various limitations of other solid blocks and are therefore necessary for creating new pressed solid cleaning compositions. Furthermore, pressed solid blocks have a more consistent and attractive appearance than extruded ones, and thus pressed solid detergent blocks can be formed into solid blocks of unique shapes for identification and use control. They can retain their shape under conditions under which the blocks will be stored or handled. Generally, it is expected that the detergent composition will remain solid when provided at temperatures up to about 120°F.

[0081] In some situations, the method for making the pressed block reduces or removes water from the system before solidification. Preferably, the composition is formed using anhydrous components. In some other situations, the composition has a moisture content of less than about 20% by weight, less than about 15% by weight, less than about 12% by weight, less than 10% by weight, less than about 5% by weight, less than about 1% by weight, less than about 0.1% by weight, or less than about 0.05% by weight, and most preferably is water-free (e.g., dry). In one embodiment, the dry composition may be in the form of granules. In contrast, a cast or extruded solid detergent block may have about 20 to about 40% by weight of water. Therefore, due to the removal or reduction of water from the composition, pressed solid blocks are preferred, and ash hydration is not used as a solidification mechanism.

[0082] The particulate components of the present disclosure can be in the form of granules and / or flakes, but are preferably in the form of small, regular granules. The granules are then used to form a solid detergent block. The solidification process can last from a few seconds to several hours, depending on factors including, but not limited to, the size of the composition being formed or cast, the ingredients of the composition, and the temperature of the composition.

[0083] The solid detergent composition can be formed using a batch or continuous mixing system. To make an extruded block, the powder and liquid of the detergent composition are blended to form a mixture, then the blended mixture is forced through a mold to form a product, and then the product is allowed to harden over time into an extruded solid block. Using a single- or twin-screw extruder, one or more cleaning agents are combined and mixed under high shear to form a homogeneous mixture to produce the extruded block. To make a compressed solid block, the solid powder and / or other liquid components of the detergent composition are mixed to form a blended powder, then the blended powder is poured into a mold and compressed into a solid detergent block. Generally, the solid detergent block processed according to the method of the present disclosure is substantially homogeneous in terms of component distribution throughout its mass and is dimensionally stable.

[0084] In some embodiments, the solid detergent compositions of the present disclosure are provided as a pressed solid block having a mass of about 5 grams to about 10 kilograms. In certain embodiments, the pressed solid detergent block has a mass of about 1 to about 10 kilograms. In further embodiments, the block of solid detergent composition has a mass of about 5 kilograms to about 8 kilograms. In other embodiments, the block of solid detergent composition has a mass of about 5 grams to about 1 kilogram, or about 5 grams to about 500 grams.

[0085] In some embodiments, the compressed solid detergent blocks produced from the compositions of the present disclosure have a water content of less than about 20%, 15%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.7%, 0.5%, 0.3%, 0.1%, or 0.05% by weight. In some other embodiments, the compressed solid detergent blocks produced from the compositions of the present disclosure have a water content of about 0.1 to about 15%, about 0.1 to about 5%, about 0.1 to about 3%, about 1 to about 8%, about 5 to about 10%, about 5 to about 15%, or about 5 to about 15% by weight. In one aspect, the dry composition may be in the form of granules. In contrast, cast or extruded solid detergent blocks may have a water content of about 20 to about 40% by weight.

[0086] phosphonates The detergent compositions disclosed herein contain a specific type of phosphonate or a salt thereof, or an amine salt of another specific type of phosphonate. Applicants have unexpectedly discovered that these specific types of phosphonates or salts thereof disclosed herein stabilize enzymes in the detergent compositions.

[0087] As used herein, the term "phosphonate" refers to a group consisting of R 40’ refers to a separate compound having the formula PO(OH)2, where R 40’ is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl, or heterocyclyl group as defined herein.

[0088] As used herein, the term "phosphonate" also refers to -R 40 It can refer to PO(OH)2. 40 is a substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylalkylene, or heterocyclylene group as defined herein.

[0089] One type of phosphonate compound that stabilizes the enzyme(s) in the detergent composition has the formula [ka] wherein R 10 and R 11 are independently hydrogen, phosphonate, unsubstituted alkyl, or substituted alkyl, with the proviso that R 10 and R 11 are both —CH—PO(OH) groups. This type of phosphonate can be added to the detergent composition in its acid form or in its salt form after being neutralized with a base. Because the use solutions of the detergent compositions disclosed herein have a pH of about 8 to about 12, the two —OH groups of the phosphonate group are in their salt form, e.g., neutralized, when the phosphonate is in the use solution.

[0090] Another type of phosphonate compound for stabilizing enzyme(s) in detergent compositions is a compound represented by the formula [ka] and an amine phosphonate salt, which is the product of a phosphonate compound represented by 12 , R 13 and R 14 are independently hydroxyl, methyl, -PO(OH)2, -CH2COOH, substituted alkyl, phosphonate, ester thereof, salt thereof, or derivative thereof. The amine phosphonate salt is typically added to the detergent composition in the form of its salt, produced by reacting the phosphonate with an amine to neutralize all or part of the OH groups. The amine can be an alkanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The alkylamines may of course be mono-, di-, or tri-amines.

[0091] In some embodiments, the detergent compositions of the present disclosure comprise a compound of formula [ka] wherein R 10 and R 11 are independently hydrogen, unsubstituted alkyl, substituted alkyl, substituted carboxylic acid, phosphonate, ethanol, diglyco, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonate-methyl. In other embodiments, R 10 is hydrogen and R 11 is unsubstituted alkyl, substituted alkyl, substituted carboxylic acid, phosphonate, ethanol, diglyco, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonate-methyl. In some other embodiments, R 10 is hydrogen and R 11 is a substituted carboxylic acid, phosphonate, ethanol, diglyco, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonate-methyl.

[0092] As used herein, EO refers to -CH2CH2O-, e.g., an ethylene oxide group, and PO to a -CH2CH(CH3)O- group. (EO) n or (PO) n When is used, n is an integer from 1 to 30.

[0093] In some embodiments, R 11 is a —CH—PO(OH) group. In some other embodiments, R 11 is a -CH2-PO(OH)2 group, and R 10 isopropyl-2-(EO) nIn yet some other embodiments, the phosphonate is: [ka] aminomethylphosphonic acid, mixtures thereof, or salts thereof.

[0094] In some embodiments, the amine phosphonate salt has the formula [ka] wherein R 12 , R 13 , and R 14 is independently hydroxyl, methyl, —PO(OH), —CHCOOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof. 12 , R 13 , and R 14の One of them is hydroxyl, methyl, -PO(OH), -CHCOOH, an ester thereof, a salt thereof, or a derivative thereof. In some other embodiments, the phosphonate of the amine phosphonate salt is PO(OH)(C(CHCOOH)), phosphonebutane tricarboxylic acid (PBTC). In yet some other embodiments, the phosphonate of the amine phosphonate is C(CH)(OH)(PO(OH)), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP).

[0095] In some embodiments, the amine of the amine phosphonate salt is an alkanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The alkylamine may be a mono-, di-, or tri-amine.

[0096] In some embodiments, the detergent compositions disclosed herein comprise from about 0.1% to about 35% by weight, 0.1% to about 30% by weight, 0.1% to about 25% by weight, 0.1% to about 15% by weight, 0.1% to about 10% by weight, 0.1% to about 5% by weight, about 0.5% to about 5% by weight, about 0.1% to about 1% by weight, about 1% to about 10% by weight, 0.1% to about 1% by weight, about 1% to about 5% by weight, 5% to about 10% by weight, 10% to about 15% by weight, about 15% to about 20%, 20% to about 25%, 25% to about 30%, 30% to about 35%, about 0.1%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 32%, or about 35% by weight of the phosphonate, salt thereof, or amine phosphonate salt.

[0097] enzyme The disclosure provided herein relates to detergent compositions comprising enzymes. In some embodiments, the enzymes are provided in liquid or solid form and are mixed with other components of the detergent composition by spraying or mixing.

[0098] Enzymes that may be used in accordance with the present disclosure include those that provide desirable activity for the removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates; for cleaning, stain removal, and sanitizing presoaks, such as presoaks for medical and dental instruments, devices, and equipment; presoaks for tableware, cooking utensils, and tableware; or presoaks for meat-cutting equipment; for machine dishwashing; for laundry and textile cleaning and stain removal; for carpet cleaning and stain removal; for clean-in-place (CIP) and stain-in-place removal; for cleaning and stain removal of food processing surfaces and equipment; for drain cleaning, cleaning presoaks, and the like.

[0099] Although not limiting to the present disclosure, suitable enzymes for detergent compositions can act by degrading or altering one or more types of soil residues on an implement or device, thereby removing the soil or making the soil more removably by surfactants or other components of the cleaning composition. Both degrading and altering soil residues can improve detergency by reducing the physicochemical forces that bind the soil to the implement or device being cleaned, e.g., making the soil more water-soluble. For example, one or more proteases can cleave complex polymeric protein structures present in the soil residues into simpler, shorter-chain molecules that are themselves more easily desorbed from surfaces, solubilized, or removed by a detergent solution containing the protease.

[0100] Suitable enzymes include proteases, amylases, lipases, gluconases, cellulases, peroxidases, or mixtures thereof, of any suitable origin, such as vegetable, animal, bacterial, fungal, or yeast origin. The preferred selection is influenced by factors such as pH activity and / or stability optimum, thermostability, and stability to active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Preferably, the enzyme is a protease, lipase, amylase, or a combination thereof.

[0101] As used herein, "detersive enzyme" refers to an enzyme that cleans, stains, or has a beneficial effect on an instrument, device, or equipment, such as a medical or dental instrument, device, or equipment, or as a component of a solid detergent composition for laundry, textiles, dishwashing, clean-in-place, drains, carpets, butcher tools, hard surfaces, personal care, etc. Preferred detersive enzymes include hydrolases such as proteases, amylases, lipases, or combinations thereof. Preferred enzymes in solid detergent compositions for cleaning medical or dental devices or instruments include proteases, amylases, cellulases, lipases, or combinations thereof. Preferred enzymes in solid detergent compositions for food processing surfaces and equipment include proteases, lipases, amylases, gluconases, or combinations thereof. Preferred enzymes in solid detergent compositions for laundry or textiles include proteases, cellulases, lipases, peroxidases, or combinations thereof. Preferred enzymes in solid detergent compositions for carpets include proteases, amylases, or combinations thereof. Preferred enzymes in solid detergent compositions for meat cutting tools include proteases, lipases, or combinations thereof. Preferred enzymes in solid detergent compositions for hard surfaces include proteases, lipases, amylases, or combinations thereof. Preferred enzymes in solid detergent compositions for drains include proteases, lipases, amylases, or combinations thereof.

[0102] Enzymes are typically incorporated into solid detergent compositions according to the present disclosure in an amount sufficient to provide effective cleaning during a wash or presoak procedure. A cleaning-effective amount refers to an amount that produces a clean, sanitary, and preferably corrosion-free appearance on the cleaned material, particularly for medical or dental devices or instruments. A cleaning-effective amount can also refer to an amount that produces a cleaning, stain-removing, soil-removing, whitening, deodorizing, or freshness-improving effect on a substrate, such as a medical or dental device or instrument. Such cleaning effects can be achieved with as little as about 0.1% by weight of the enzyme in the detergent composition.

[0103] In the detergent compositions of the present disclosure, suitable cleaning can typically be achieved when an enzyme is also present, preferably at about 1 to about 35 wt. %, preferably about 2 to about 15 wt. %, preferably about 3 to about 10 wt. %, preferably about 4 to about 8 wt. %, preferably about 4, about 5, about 6, about 7, or about 8 wt. Higher enzyme levels are typically desired in highly concentrated cleaning or presoak formulations. Presoaks are preferably formulated for use at a dilution of about 1:500, or at a formulation concentration of about 2000 to about 4000 ppm, which brings the enzyme use concentration to about 20 to about 40 ppm.

[0104] Commercially available enzymes, such as alkaline proteases, are available in liquid or dry form, sold as crude aqueous solutions or in various purified, processed, and formulated forms, and generally contain from about 0.1% to about 80% by weight of active enzyme in combination with stabilizers, buffers, cofactors, impurities, and inert vehicles. The actual active enzyme content depends on the method of manufacture and is not critical, assuming the solid detergent composition has the desired enzymatic activity. The specific enzymes selected for use in the processes and products of the present disclosure depend on the end-use conditions, including the physical product form, use pH, use temperature, and the type of soil to be degraded or altered. Enzymes can be selected to provide optimal activity and stability for a given set of use conditions.

[0105] A valuable reference on enzymes is "Industrial Enzymes", Scott, D., in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, (editors Grayson, M. and EcKroth, D.), Vol. 9, pp. 173-224, John Wiley & Sons, New York, 1980.

[0106] In some other embodiments, the enzyme in the detergent composition is a single enzyme. In some other embodiments, the enzyme in the detergent composition is a mixture of two or more enzymes. In some other embodiments, the enzyme in the composition is a protease, amylase, lipase, hydrolase, cellulase, gluconase, peroxidase, mannanase, or a mixture thereof. In some other embodiments, the enzyme is a protease, amylase, lipase, cellulose, peroxidase, gluconase, or a mixture thereof. In some other embodiments, the enzyme in the detergent compositions disclosed herein is a protease, amylase, lipase, or a mixture thereof. In some other embodiments, the enzyme is a protease, amylase, or a mixture thereof. In some other embodiments, the enzyme is a protease, lipase, or a mixture thereof. In some other embodiments, the enzyme is an amylase, lipase, or a mixture thereof. In some other embodiments, the enzyme is a protease. In some other embodiments, the enzyme is an amylase. In yet some other embodiments, the enzyme is a lipase.

[0107] In some embodiments, the detergent compositions disclosed herein comprise from about 0.1% to about 35% by weight, 0.1% to about 30% by weight, 0.1% to about 25% by weight, 0.1% to about 15% by weight, 0.1% to about 10% by weight, 0.1% to about 5% by weight, about 0.5% to about 5% by weight, about 0.1% to about 1% by weight, about 1% to about 10% by weight, 0.1% to about 1% by weight, about 1% to about 5% by weight, 5% to about 10% by weight, 10 ... The amount of the enzyme may be about 15% by weight, about 15% by weight to about 20% by weight, 20% by weight to about 25% by weight, 25% by weight to about 30% by weight, 30% by weight to about 35% by weight, about 0.1% by weight, about 0.5% by weight, about 1% by weight, about 2% by weight, about 3% by weight, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 32% by weight, or about 35% by weight.

[0108] The detergent compositions of the present disclosure have further been surprisingly found to have significantly stabilized enzymes, particularly proteases, lipases, and / or amylases, protein digestion activity, and improved soil removal in their use solutions. The applicant has surprisingly discovered that by using a specific type of phosphonate alone or another specific amine phosphonate salt in the detergent composition, the enzymes in the use solution made from the detergent composition of the present disclosure remain active for much longer than those from a detergent composition that does not contain the phosphonate disclosed herein. As shown in this disclosure, in the use solution produced from the solid detergent of the present disclosure, both the protease and the lipase remain active for a very long period of time. The more stable the enzymes, the longer they remain effective in removing soil, protein, or starch (and fats, if lipase is included). As a result, the detergent compositions disclosed herein are also more effective.

[0109] The excellent stability of the enzymes in the detergent compositions of the present disclosure allows the compositions to use less enzyme and to avoid the use of other stabilizers or other ingredients commonly found in existing detergent compositions. Some stabilizers may be liquid and difficult to include in solid detergent compositions or may result in undesirable reactions with other ingredients. Some stabilizers raise health / safety / labeling concerns (e.g., undesirable GHS label icon warnings) for concentrated compositions. Minimal stabilizers add complexity to the formulation and take up "formulation space" for other functional ingredients. An additional advantage of using the disclosed disclosure is that the detergents disclosed herein can be produced using no or reduced amounts of other stabilizers.

[0110] Alkaline source Detergent compositions and methods according to the present disclosure include an effective amount of an alkaline source. The alkaline source includes one or more alkaline compounds. Generally, an effective amount of alkaline source should be considered to provide a use solution having a pH of at least about 8. A use solution having a pH of about 8 to about 10 may be considered mildly alkaline, and a pH greater than about 12 may be considered caustic. Generally, it is desirable to provide a use solution as a mildly alkaline cleaning composition, as this is considered safer than caustic-based use compositions.

[0111] The alkaline source may include an alkali metal carbonate, an alkali metal hydroxide, an alkali metal silicate, or a mixture thereof. Suitable metal carbonates that may be used include, for example, sodium or potassium carbonate, bicarbonate, sesquicarbonate, or a mixture thereof. Suitable alkali metal hydroxides that may be used include, for example, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Examples of useful alkali metal silicates include sodium or potassium silicate (having a ratio of MO:SiO of 2.4 to 5:1, where M represents the alkali metal), or metasilicates. The alkaline source may also include metal borates such as sodium or potassium borate.

[0112] Alkaline sources may also include ethanolamine, urea sulfate, amines, amine salts, and quaternary ammonium. The simplest cationic amines, amine salts, and quaternary ammonium compounds may be schematically depicted as follows: [ka] where R represents a long alkyl chain, R', R'', and R''' can be either a long alkyl chain or smaller alkyl or aryl groups or hydrogen, and X represents an anion.

[0113] The alkaline source may be added to the composition in solid form. For example, alkali metal hydroxides are commercially available as prilled solids or solids in the form of beads having mixed particle sizes ranging from 25 to about 12-100 US mesh. For example, alkali metal hydroxides may be added to the solid detergent composition in a variety of solid forms, including, for example, in the form of solid beads. Alkali metal hydroxides are commercially available.

[0114] The alkaline source is preferably in an amount that enhances substrate cleaning and improves the soil removal performance of the composition. Generally, it is expected that concentrates will contain the alkaline source in an amount of at least about 5%, at least about 10%, or at least about 15% by weight. The pressed solid detergent composition may contain from about 10% to about 95% by weight, preferably from about 15% to about 70%, from about 20% to about 60%, and even more preferably from about 70% to about 95% by weight of the alkaline source.

[0115] In some embodiments, the detergent compositions disclosed herein contain a metal carbonate, metal bicarbonate, metal silicate, or a mixture thereof as their alkaline source. In some other embodiments, the detergent compositions disclosed herein contain a metal carbonate, metal bicarbonate, or a mixture thereof as their alkaline source. In some embodiments, the alkaline source in the detergent compositions disclosed herein is an alkali metal carbonate, alkali metal bicarbonate solid, alkali metal silicate, or a mixture thereof. In some other embodiments, the alkaline source in the detergent compositions disclosed herein is an alkali metal carbonate, alkali metal bicarbonate, or a mixture thereof. In some other embodiments, the alkaline source in the detergent compositions disclosed herein is a mixture of an alkali metal carbonate and an alkali metal bicarbonate. In some other embodiments, the alkaline source in the detergent compositions disclosed herein is simply an alkali metal carbonate (e.g., all ash). In some embodiments, the alkaline source in the detergent compositions disclosed herein is sodium carbonate, sodium bicarbonate, sodium metal silicate, or a mixture thereof. In some embodiments, the alkaline source in the detergent compositions disclosed herein is sodium carbonate and sodium bicarbonate. In some embodiments, the alkaline source in the detergent compositions disclosed here is simply sodium carbonate.

[0116] In some embodiments, the detergent produced from the disclosed detergent composition or method has from about 1% to about 90%, 5% to about 85%, 15% to about 80%, 20% to about 75%, 25% to about 70%, 30% to about 65%, 35% to about 60%, 40% to about 55%, or 45% to about 50% by weight of the alkaline source. In some other embodiments, the detergent produced from the disclosed detergent composition or method has about 80% to about 90% by weight, about 70% to about 80% by weight, about 60% to about 70% by weight, about 50% to about 60% by weight, about 40% to about 50% by weight, about 30% to about 40% by weight, about 20% to about 30% by weight, about 10% to about 10% by weight, about 1% to about 10% by weight, or about 0.1% to about 1% by weight of the alkaline source. In some embodiments, the detergent produced from the disclosed detergent compositions or methods has about 90%, about 85%, about 80%, about 75%, about 70%, about 65%, about 60%, about 55%, about 50%, about 45%, about 40%, about 35%, about 30%, about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% by weight of the alkaline source. In some other embodiments, the detergent produced from the disclosed compositions and methods has about 10% to about 90% by weight, 20% to about 90% by weight, 30% to about 90% by weight, 40% to about 90% by weight, 50% to about 90% by weight, 60% to about 90% by weight, 70% to about 90% by weight, about 85% by weight, 75% by weight, about 65% by weight, about 55% by weight, about 45% by weight, about 35% by weight, about 25% by weight, about 15% by weight, or about 5% by weight of the alkaline source.

[0117] In some embodiments, the detergent composition comprises an alkaline source in an amount sufficient to provide a use composition with a pH of about 8 to about 12. In some other embodiments, the detergent composition comprises an alkaline source in an amount sufficient to provide a use composition with a pH of about 8 to about 11, about 8 to about 9, about 9 to about 12, about 9 to about 11, about 9 to about 10, about 8, about 9, about 10, about 11, about 12, about 8.5, about 9.5, about 10.5, or about 11.5.

[0118] In some embodiments, the detergent compositions disclosed here may include an additional alkaline compound such as an alkali metal sesquicarbonate, an alkali hydroxide, a metasilicate, a urea sulfate, an amine, an amine salt, a quaternary ammonia, a hydrate thereof, or a mixture of two or more thereof as an additional alkaline source.

[0119] In one aspect, an enzyme, [ka] or a salt thereof, and an alkaline source, wherein the enzyme is a protease, an amylase, a lipase, a cellulose, a peroxidase, a gluconase, or a mixture thereof; the alkaline source is a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; and R 10 is hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivative thereof, and R 11 is hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivatives thereof, provided that R 10 and R 11 and are both —CH—PO(OH) groups.

[0120] In some other embodiments, R 11 is a —CH—PO(OH) group. In yet some other embodiments, R 11 is a -CH2-PO(OH)2 group, and R 10 is substituted alkyl. In some embodiments, R 11 is a -CH2-PO(OH)2 group, and R 10 is a phosphonate, a phosphonate ester, or a derivative thereof.

[0121] In some embodiments, the phosphonate is [ka] aminomethylphosphonic acid, or mixtures thereof, where n is an integer from 1 to 30.

[0122] In some embodiments, the phosphonate is aminotrimethylene phosphonic acid (ATMP). In some other embodiments, the phosphonate is diglycolamine phosphonate (DGAP).

[0123] In some embodiments, the phosphonate is a fully neutralized salt of phosphonebutanetricarboxylic acid (PBTC) with an alkanolamine. In some other embodiments, the phosphonate is a fully neutralized salt of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) with an alkanolamine. The alkanolamine can be monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof.

[0124] In some embodiments, the alkaline source is a metal carbonate and a metal bicarbonate. In some other embodiments, the molar ratio of the metal carbonate to the metal bicarbonate is about 0.25:1 to about 1:0.25, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some other embodiments, the alkaline source is a metal carbonate (e.g., all ash). In some embodiments, the alkaline source is an alkali metal carbonate and an alkali metal bicarbonate. In some other embodiments, the molar ratio of the alkali metal carbonate to the alkali metal bicarbonate is about 0.25:1 to about 1:0.25, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some other embodiments, the alkaline source is an alkali metal carbonate (all ash).

[0125] In some embodiments, the enzyme is a protease, amylase, lipase, or mixture thereof. In some embodiments, the enzyme is a protease, amylase, or mixture thereof. In some embodiments, the enzyme is a protease, lipase, or mixture thereof. In some embodiments, the enzyme is a protease. In some other embodiments, the enzyme is an amylase, lipase, or mixture thereof. In some other embodiments, the enzyme is an amylase. In yet some other embodiments, the enzyme is a lipase.

[0126] In some embodiments, in a use solution of the composition, the enzyme retains at least 15% of its activity for at least 4 hours at 120° F. In some other embodiments, in a use solution of the composition, the enzyme retains at least 20% of its activity for at least 4 hours at 120° F. In some embodiments, in a use solution of the detergent composition, the enzyme retains at least 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of its activity for at least 240 minutes at 120° F.

[0127] In some embodiments, the composition comprises from about 0.1% to about 5%, 0.5% to about 3%, about 1% to about 1.5% by weight of an enzyme, from about 0.01% to about 2%, 0.05% to about 1.5%, or 0.1% to about 1% by weight of an enzyme. [ka] and about 50% to about 95%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, or about 80% to about 90% by weight of an alkaline source. In some of these embodiments, the phosphonate is aminotrimethylene phosphonic acid (ATMP). In some other of these embodiments, the phosphonate is diglycolamine phosphonate (DGAP). In some of these embodiments, the alkaline source is a mixture of alkali metal carbonate and alkali metal bicarbonate in a ratio of 0.25:1 to 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some other of these embodiments, the alkaline source is alkali metal carbonate (all ash).

[0128] In some embodiments, the composition comprises an enzyme, [ka] or salt thereof, an alkaline source, and an amine. In some embodiments, the amine comprises about 0.1% to about 35%, 0.1% to about 30%, 0.1% to about 25%, 0.1% to about 15%, 0.1% to about 10%, 0.1% to about 5%, about 0.5% to about 5%, about 0.1% to about 1%, about 1% to about 10%, 0.1% to about 1%, about 1% to about 5%, 5% to about 10%, or 10% to about 15% by weight of the composition. %, about 15% by weight to about 20% by weight, 20% by weight to about 25% by weight, 25% by weight to about 30% by weight, 30% by weight to about 35% by weight, about 0.1% by weight, about 0.5% by weight, about 1%, about 2% by weight, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 15%, about 20%, about 25%, about 30%, about 32%, or about 35% by weight, such as about 0.1 to 35% by weight.

[0129] In some other embodiments, the amine is an alkanolamine or a mixture thereof. In some other embodiments, the amine is monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The alkylamine may be a mono-, di-, or tri-amine, or a mixture thereof. In some embodiments, the composition has a molar ratio of phosphonate to amine of about 0.5:1 to 1:0.5.

[0130] In some embodiments, the composition comprises an enzyme, [ka] or a salt thereof, an alkaline source, and a metal hydroxide, tripolyphosphate, or a mixture thereof. In some embodiments, the composition comprises an enzyme, [ka] or a salt thereof, an alkaline source, an amine, and a metal hydroxide, tripolyphosphate, or a mixture thereof.

[0131] In some other embodiments, the composition comprises an enzyme, [ka] or salt thereof, an alkalinity source, a metal hydroxide, a tripolyphosphate, or mixtures thereof, and one or more additional functional ingredients including an oxidizer, a builder or water conditioner / water conditioning agent, a peroxyacid and its initializer, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant and / or chelating agent, a fragrance and / or dye, a rheology modifier or thickener, a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant, a hydrotrope or coupler, or a combination thereof.

[0132] In some other embodiments, the composition comprises an enzyme, [ka] or salts thereof, an alkalinity source, an amine, a metal hydroxide, a tripolyphosphate, or mixtures thereof, and one or more additional functional ingredients including an oxidizer, a builder or water conditioner / water conditioning agent, a peroxyacid and its initializer, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant and / or chelating agent, a fragrance and / or dye, a rheology modifier or thickener, a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant, a hydrotrope or coupler, or a combination thereof.

[0133] In some embodiments, the composition comprises from about 2% to about 15%, or from about 5% to 10% by weight of a water conditioning agent, hi some other embodiments, the composition comprises from about 0.1% to about 5%, from about 0.5% to about 4%, or from about 1% to about 3% by weight of a surfactant.

[0134] In another aspect, the disclosure provides a composition comprising an enzyme, an alkaline source, and an amine phosphonate salt, wherein the amine salt is [ka] and an amine, wherein the enzyme is a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; and R 12 is hydroxyl, methyl, -PO(OH)2, -CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof, and R 13 is hydroxyl, methyl, -PO(OH)2, -CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof, and R 14 is hydroxyl, methyl, —PO(OH) 2 , —CH 2 COOH, a substituted alkyl, a phosphonate, an ester thereof, or a derivative thereof.

[0135] In some other embodiments, R 12 , R 13 , and R 14の One of them is hydroxyl, methyl, -PO(OH)2, -CH2COOH, an ester thereof, a salt thereof, or a derivative thereof.

[0136] In some embodiments, the phosphonate of the amine phosphonate salt is PO(OH)(C(CHCOOH)), PBTC. In other embodiments, the phosphonate of the amine phosphonate salt is C(CH)(OH)(PO(OH)), HEDP.

[0137] In some embodiments, the amine of the amine phosphonate salt is an alkanolamine, or a mixture thereof. In other embodiments, the amine of the amine phosphonate salt is monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The amine phosphonate salt is an alkylamine or a mixture thereof. The alkylamine can, of course, be mono-, di-, or tri-amine. In some embodiments, the composition has a molar ratio of phosphonate to amine of about 0.5:1 to 1:0.5. In some embodiments, the amine phosphonate salt is only partially neutralized. In some other embodiments, the amine phosphonate salt is completely neutralized by the amine.

[0138] In some embodiments, the enzyme is a protease, amylase, lipase, or mixture thereof. In some other embodiments, the enzyme is a protease, amylase, or mixture thereof. In some embodiments, the enzyme is a protease, a lipase, or mixture thereof. In some other embodiments, the enzyme is a protease. In some other embodiments, the enzyme is an amylase, a lipase, or mixture thereof. In some other embodiments, the enzyme is an amylase. In yet some other embodiments, the enzyme is a lipase.

[0139] In some embodiments, the alkaline source of the composition is a metal carbonate and a metal bicarbonate. In some other embodiments, the molar ratio of the metal carbonate to the metal bicarbonate is about 0.5:1 to about 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some embodiments, the alkaline source is a metal carbonate. In some embodiments, the alkaline source of the composition is an alkali metal carbonate and an alkali metal bicarbonate. In some other embodiments, the molar ratio of the alkali metal carbonate to the alkali metal bicarbonate is about 0.5:1 to about 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some embodiments, the alkaline source is an alkali metal carbonate. In some embodiments, the alkaline source of the composition is sodium carbonate and sodium bicarbonate. In some other embodiments, the molar ratio of sodium carbonate to sodium bicarbonate is from about 0.5:1 to about 1:0.5, from 0.5:1 to 1:0.5, or from 0.75:1 to 1:0.75. In some embodiments, the alkaline source is sodium carbonate.

[0140] In some embodiments, the composition is about 0.1% to about 5%, 0.5% to about 3%, about 1% to about 1.5% by weight of an enzyme, about 0.01% to about 2%, 0.05% to about 1.5%, or 0.1% to about 1% by weight of an amine phosphonate salt, wherein the amine salt is [ka] and an amine, comprising about 50% to about 95%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, or about 80% to about 90% by weight of an alkaline source. In some of these embodiments, the phosphonate is a fully neutralized salt of phosphonebutanetricarboxylic acid (PBTC) with an alkanolamine. In other of these embodiments, the phosphonate is a fully neutralized salt of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) with an alkanolamine. The alkanolamine can be monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some of these embodiments, the alkaline source is a mixture of alkali metal carbonate and alkali metal bicarbonate in a ratio of 0.25:1 to 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In other of these embodiments, the alkaline source is alkali metal carbonate (all ash).

[0141] In some embodiments, in a use solution of the composition, the enzyme retains at least 15% of its activity for at least 40 minutes at 120° F. In some other embodiments, in a use solution of the detergent composition, the enzyme retains at least 20% of its activity for at least 4 hours at 120° F. In some embodiments, in a use solution of the detergent composition, the enzyme retains at least 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of its activity for at least 240 minutes at 120° F.

[0142] In some other embodiments, the amine phosphonate salt is from about 0.1% to about 35%, 0.1% to about 30%, 0.1% to about 25%, 0.1% to about 15%, 0.1% to about 10%, 0.1% to about 5%, about 0.5% to about 5%, about 0.1% to about 1%, about 1% to about 10%, 0.1% to about 1%, about 1% to about 5%, 5% to about 10%, or 10% by weight of the composition. about 15% by weight, about 15% by weight to about 20% by weight, 20% by weight to about 25% by weight, 25% by weight to about 30% by weight, 30% by weight to about 35% by weight, about 0.1% by weight, about 0.5% by weight, about 1%, about 2% by weight, about 3%, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 32% by weight, or about 35% by weight, such as about 0.1 to 35% by weight.

[0143] In some embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof. In some other embodiments, the composition further comprises one or more additional functional ingredients including an oxidizer, a builder or water conditioner / water conditioning agent, a peroxyacid and its initializer, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizing agent, a corrosion inhibitor, a sequestrant and / or chelating agent, a fragrance and / or dye, a rheology modifier or thickener, a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant, a hydrotrope or coupler, or a combination thereof.

[0144] In some embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof, and one or more additional functional ingredients. The additional functionalities can be oxidizers, builders or water conditioners / conditioners, peroxyacids and their initializers, chelating agents, threshold agents, crystal modifiers, disinfectants, defoamers, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, rinse aids, polymers, metal protecting agents, stabilizers, corrosion inhibitors, sequestrants and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, nonionic surfactants, cationic surfactants, or zwitterionic surfactants, hydrotropes or couplers, or combinations thereof.

[0145] In some embodiments, the composition comprises from about 2% to about 15%, or from about 5% to 10% by weight of a water conditioning agent, hi some other embodiments, the composition comprises from about 0.1% to about 5%, from about 0.5% to about 4%, or from about 1% to about 3% by weight of a surfactant.

[0146] In yet another aspect, the present disclosure provides a solid detergent composition comprising an alkaline source, a phosphonate, and an enzyme, wherein the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; the enzyme is a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; and the phosphonate is [ka] or a salt thereof, and R 10 is hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivative thereof, and R 11 is hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n-biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivatives thereof, provided that R 10 and R 11 are both —CH2—PO(OH)2 groups in the molecule, and the components of the composition are mixed and used to form a solid detergent.

[0147] In some embodiments, the solid detergent is produced by a casting process, an extrusion process, or a pressing process. In other embodiments, the solid detergent is produced by a pressing process. In some embodiments, the solid detergent is in block, tablet, or granular form. In some other embodiments, the solid detergent is a multi-use solid detergent.

[0148] In some embodiments, the solid detergent is dimensionally stable and has a growth exponent of less than 3% when heated at a temperature of 122° F. (50° C.). In some other embodiments, the solid detergent is dimensionally stable and has a growth exponent of less than 2% when heated at a temperature of 122° F.

[0149] In some other embodiments, R 11 is a —CH—PO(OH) group. In yet some other embodiments, R 11 is a -CH2-PO(OH)2 group, and R 10 is substituted alkyl. In some embodiments, R 11 is a -CH2-PO(OH)2 group, and R 10 is a phosphonate, a phosphonate ester, or a derivative thereof.

[0150] In some embodiments, the phosphonate is [ka] aminomethylphosphonic acid, or mixtures thereof, where n is an integer from 1 to 30.

[0151] In some embodiments, the alkaline source is a metal carbonate and a metal bicarbonate. In some other embodiments, the molar ratio of the metal carbonate to the metal bicarbonate is about 0.25:1 to about 1:0.25. In some embodiments, the alkaline source is a metal carbonate. In some embodiments, the alkaline source of the composition is an alkali metal carbonate and an alkali metal bicarbonate. In some other embodiments, the molar ratio of the alkali metal carbonate to the alkali metal bicarbonate is about 0.5:1 to about 1:0.5. In some embodiments, the alkaline source is an alkali metal carbonate. In some embodiments, the alkaline source of the composition is sodium carbonate and sodium bicarbonate. In some other embodiments, the molar ratio of the sodium carbonate to the sodium bicarbonate is about 0.5:1 to about 1:0.5. In some embodiments, the alkaline source is sodium carbonate.

[0152] In some embodiments, the enzyme is a protease, amylase, lipase, or mixture thereof. In some embodiments, the enzyme is a protease, amylase, or mixture thereof. In some embodiments, the enzyme is a protease, lipase, or mixture thereof. In some embodiments, the enzyme is a protease. In some other embodiments, the enzyme is an amylase, lipase, or mixture thereof. In some other embodiments, the enzyme is an amylase. In yet some other embodiments, the enzyme is a lipase.

[0153] In some embodiments, the composition comprises from about 0.1% to about 5%, 0.5% to about 3%, about 1% to about 1.5% by weight of an enzyme, from about 0.01% to about 2%, 0.05% to about 1.5%, or 0.1% to about 1% by weight of an enzyme. [ka] and about 50% to about 95%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, or about 80% to about 90% by weight of an alkaline source. In some of these embodiments, the phosphonate is aminotrimethylene phosphonic acid (ATMP). In some other of these embodiments, the phosphonate is diglycolamine phosphonate (DGAP). In some of these embodiments, the alkaline source is a mixture of alkali metal carbonate and alkali metal bicarbonate in a ratio of 0.25:1 to 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some other of these embodiments, the alkaline source is alkali metal carbonate (all ash).

[0154] In some embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 15% of its activity for at least 4 hours at 120° F. In some other embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 50% of its activity for at least 4 hours at 120° F. In some embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of its activity for at least 240 minutes at 120° F.

[0155] In some embodiments, the solid detergent composition further comprises an amine. In some embodiments, the amine comprises from about 0.1% to about 35%, 0.1% to about 30%, 0.1% to about 25%, 0.1% to about 15%, 0.1% to about 10%, 0.1% to about 5%, about 0.5% to about 5%, about 0.1% to about 1%, about 1% to about 10%, 0.1% to about 1%, about 1% to about 5%, 5% to about 10%, or 10% to about 15% by weight, about 15% by weight to about 20% by weight, 20% by weight to about 25% by weight, 25% by weight to about 30% by weight, 30% by weight to about 35% by weight, about 0.1% by weight, about 0.5% by weight, about 1%, about 2% by weight, about 3%, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 32% by weight, or about 35% by weight, about 0.1 to 35% by weight.

[0156] In some embodiments, the composition has a molar ratio of phosphonate to amine of about 0.5:1 to 1:0.5. In some other embodiments, the amine is monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The alkylamines may of course be mono-, di-, or tri-amines.

[0157] In some embodiments, the solid detergent composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof. In some other embodiments, the composition comprises one or more additional functional ingredients including an oxidizer, a builder or water conditioner / water conditioning agent, a peroxyacid and its initializer, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant and / or chelating agent, a fragrance and / or dye, a rheology modifier or thickener, a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant, a hydrotrope or coupler, and combinations thereof.

[0158] In some embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof, an amine, and one or more additional functional ingredients. In some other embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof, and an amine. In yet some other embodiments, the composition further comprises an amine and one or more additional functional ingredients. The additional ingredients can be oxidizers, builders or water conditioners / water conditioning agents, peroxyacids and their initializers, chelating agents, threshold agents, crystal modifiers, disinfectants, defoamers, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, rinse aids, polymers, metal protecting agents, stabilizers, corrosion inhibitors, sequestrants and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, nonionic surfactants, cationic surfactants, or zwitterionic surfactants, hydrotropes or couplers, and combinations thereof.

[0159] In some embodiments, the composition comprises from about 2% to about 15%, or from about 5% to 10% by weight of a water conditioning agent, hi some other embodiments, the composition comprises from about 0.1% to about 5%, from about 0.5% to about 4%, or from about 1% to about 3% by weight of a surfactant.

[0160] In another aspect, the disclosure provides a solid detergent composition comprising an alkaline source, an enzyme, and an amine phosphonate salt, wherein the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; the enzyme is a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; and the amine phosphonate salt is [ka] and R is a product of a phosphonate and an amine represented by the formula 12 is hydroxyl, methyl, -PO(OH)2, -CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof, and R 13 is hydroxyl, methyl, -PO(OH)2, -CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof, and R 14 is hydroxyl, methyl, —PO(OH)2, —CH2COOH, a substituted alkyl, a phosphonate, an ester thereof, or a derivative thereof, and the components of the composition are mixed and used to form a solid detergent.

[0161] In some embodiments, the solid detergent is produced by a casting process, an extrusion process, or a pressing process. In other embodiments, the solid detergent is produced by a pressing process. In some embodiments, the solid detergent is in block, tablet, or granular form. In some other embodiments, the solid detergent is a multi-use solid detergent.

[0162] In some embodiments, the solid detergent is dimensionally stable and has a growth exponent of less than 3% when heated at a temperature of 122° F. In some other embodiments, the solid detergent is dimensionally stable and has a growth exponent of less than 2% when heated at a temperature of 122° F.

[0163] In some other embodiments, R 12 , R 13 , and R 14のOne of them is hydroxyl, methyl, -PO(OH)2, -CH2COOH, an ester thereof, a salt thereof, or a derivative thereof.

[0164] In some embodiments, the phosphonate of the amine phosphonate salt is PO(OH)2(C(CH2COOH)3), PBTC. In other embodiments, the phosphonate of the amine phosphonate salt is C(CH3)(OH)(PO(OH)2), HEDP. In yet other embodiments, the amine of the amine phosphonate salt is an alkanolamine, monoethanolamine, diethanolamine, triethanolamine, ethanolamine, isopropylamine, or a mixture thereof. In some other embodiments, the amine of the amine phosphonate salt is C 2~6 The alkylamine may be a mono-, di-, or tri-amine, or a mixture thereof. In some embodiments, the composition has a molar ratio of phosphonate to amine of about 0.5:1 to 1:0.5.

[0165] In some embodiments, the enzyme is a protease, amylase, lipase, or mixture thereof. In some other embodiments, the enzyme is a protease, amylase, or mixture thereof. In some embodiments, the enzyme is a protease, a lipase, or mixture thereof. In some other embodiments, the enzyme is a protease. In some other embodiments, the enzyme is an amylase, a lipase, or mixture thereof. In some other embodiments, the enzyme is an amylase. In yet some other embodiments, the enzyme is a lipase.

[0166] In some embodiments, the alkaline source of the composition is a metal carbonate and a metal bicarbonate. In some other embodiments, the molar ratio of the metal carbonate to the metal bicarbonate is about 0.25:1 to about 1:0.25, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In some other embodiments, the alkaline source is a metal carbonate. In some embodiments, the alkaline source of the composition is an alkali metal carbonate and an alkali metal bicarbonate. In some other embodiments, the molar ratio of the alkali metal carbonate to the alkali metal bicarbonate is about 0.5:1 to about 1:0.5. In some embodiments, the alkaline source is an alkali metal carbonate. In some embodiments, the alkaline source of the composition is sodium carbonate and sodium bicarbonate. In some other embodiments, the molar ratio of sodium carbonate to sodium bicarbonate is about 0.5:1 to about 1:0.5. In some embodiments, the alkaline source is sodium carbonate.

[0167] In some embodiments, the composition is about 0.1% to about 5%, 0.5% to about 3%, about 1% to about 1.5% by weight of an enzyme, about 0.01% to about 2%, 0.05% to about 1.5%, or 0.1% to about 1% by weight of an amine phosphonate salt, wherein the amine salt is [ka] and an amine, comprising about 50% to about 95%, about 50% to about 90%, about 60% to about 90%, about 70% to about 90%, or about 80% to about 90% by weight of an alkaline source. In some of these embodiments, the phosphonate is a fully neutralized salt of phosphonebutanetricarboxylic acid (PBTC) with an alkanolamine. In other of these embodiments, the phosphonate is a fully neutralized salt of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) with an alkanolamine. The alkanolamine can be monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof.

[0168] In some of these embodiments, the alkaline source is a mixture of alkali metal carbonate and alkali metal bicarbonate in a ratio of 0.25:1 to 1:0.5, 0.5:1 to 1:0.5, or 0.75:1 to 1:0.75. In other of these embodiments, the alkaline source is alkali metal carbonate (all ash). In some embodiments, the amine phosphonate salt is only partially neutralized. In some other embodiments, the amine phosphonate salt is fully neutralized by the amine.

[0169] In some embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 15% of its activity for at least 4 hours at 120° F. In some other embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 50% of its activity for at least 4 hours at 120° F. In some embodiments, in a use solution of the solid detergent composition, the enzyme retains at least 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% of its activity for at least 240 minutes at 120° F.

[0170] In some other embodiments, the amine phosphonate salt is from about 0.1% to about 35%, 0.1% to about 30%, 0.1% to about 25%, 0.1% to about 15%, 0.1% to about 10%, 0.1% to about 5%, about 0.5% to about 5%, about 0.1% to about 1%, about 1% to about 10%, 0.1% to about 1%, about 1% to about 5%, 5% to about 10%, or 10% by weight of the composition. about 15% by weight, about 15% by weight to about 20% by weight, 20% by weight to about 25% by weight, 25% by weight to about 30% by weight, 30% by weight to about 35% by weight, about 0.1% by weight, about 0.5% by weight, about 1%, about 2% by weight, about 3%, about 4% by weight, about 5% by weight, about 6% by weight, about 7% by weight, about 8% by weight, about 9% by weight, about 10% by weight, about 15% by weight, about 20% by weight, about 25% by weight, about 30% by weight, about 32% by weight, or about 35% by weight, such as about 0.1 to 35% by weight.

[0171] In some embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof. In some other embodiments, the composition further comprises one or more additional functional ingredients including an oxidizer, a builder or water conditioner / water conditioning agent, a peroxyacid and its initializer, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant and / or chelating agent, a fragrance and / or dye, a rheology modifier or thickener, a nonionic surfactant, a cationic surfactant, or a zwitterionic surfactant, a hydrotrope or coupler, and combinations thereof.

[0172] In some embodiments, the composition further comprises a metal hydroxide, tripolyphosphate, or mixtures thereof, and one or more additional functional ingredients, which may be oxidizers, builders or water conditioners / conditioners, peroxyacids and their initializers, chelating agents, threshold agents, crystal modifiers, disinfectants, defoamers, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, rinse aids, polymers, metal protecting agents, stabilizers, corrosion inhibitors, sequestrants and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, nonionic surfactants, cationic surfactants, or zwitterionic surfactants, hydrotropes or couplers, and combinations thereof.

[0173] In some embodiments, the composition comprises from about 2% to about 15%, or from about 5% to 10% by weight of a water conditioning agent, hi some other embodiments, the composition comprises from about 0.1% to about 5%, from about 0.5% to about 4%, or from about 1% to about 3% by weight of a surfactant.

[0174] Additional Functional Ingredients In some embodiments, the compositions of the present disclosure contain additional ingredients, which may be in solid or liquid form and thus may be mixed with the other components of the compositions of the present disclosure.

[0175] Functional ingredients provide desired properties and functionality to detergent compositions. For purposes of this application, the term "functional ingredient" includes ingredients that, when dispersed or dissolved in a use solution, such as an aqueous solution, and / or a concentrated solution, provide beneficial properties in a particular use. Some specific examples of functional ingredients are discussed in more detail below, although the specific materials discussed are provided by way of example only, and a variety of other functional ingredients may be used. For example, many of the functional ingredients discussed below relate to materials used in cleaning applications. However, other embodiments may include functional ingredients for use in other applications.

[0176] Exemplary additional functional ingredients include builders or water conditioners / water conditioning agents, including, for example, detergent builders, chelating agents, threshold agents, crystal modifiers, hardening agents, bleaching agents, fillers, defoamers, anti-redeposition agents, stabilizers, dispersants, glass and metal corrosion inhibitors, fragrances and dyes, thickeners, etc. A further description of suitable additional functional ingredients is provided in U.S. Patent Application Serial No. 12 / 977,340, which is incorporated herein by reference in its entirety.

[0177] In some embodiments, the blocks produced from the disclosed methods, processes, or compositions further comprise additional functional ingredients including oxidizers, peroxyacids and their initializers, disinfectants, defoamers, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, threshold agents, crystal modifiers, phosphonates, binders, rinse aids, polymers, metal protecting agents, stabilizing agents, corrosion inhibitors, sequestrants and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, hydrotropes or couplers, and combinations thereof.

[0178] Anionic surfactants A method for adjusting the dispensing rate of a solid detergent block of a detergent composition according to the present disclosure, a process for producing a solid detergent block or a pressed solid composition at a predetermined dispensing rate, includes a first solid comprising an effective amount of one or more anionic surfactants.

[0179] Anionic surfactants are surface-active substances in which the hydrophobic charge is negative, or surfactants in which the hydrophobic section of the molecule does not carry a charge unless the pH is raised above neutral (e.g., carboxylic acid). Carboxylate, sulfonate, sulfate, and phosphate are polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium, and potassium impart water solubility, ammonium and substituted ammonium ions provide both water and oil solubility, and calcium, barium, and magnesium promote oil solubility. As those skilled in the art will appreciate, anions are preferred additives to heavy-duty detergent compositions because they are excellent detersive surfactants.

[0180] Anionic sulfate surfactants suitable for use in the present compositions include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C 17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polysaccharides such as sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as the sulfate or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 oxyethylene groups per molecule).

[0181] Anionic sulfonate surfactants suitable for use in the present compositions also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0182] Anionic carboxylate surfactants suitable for use in the present compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinic acids), ether carboxylic acids, and sulfonated fatty acids, such as sulfonated oleic acid. Such carboxylates include alkyl ethoxy carboxylates, alkylaryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates useful in the present compositions include those containing a carboxyl unit attached to a secondary carbon. The secondary carbon may be in a ring structure, as in, for example, p-octyl benzoic acid or alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants typically do not contain ether linkages, ester linkages, or hydroxyl groups. Furthermore, they typically lack a nitrogen atom in the head group (amphiphilic portion). Suitable secondary soap surfactants typically contain 11 to 13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acylamino acids (and salts) such as acylgluamates, acylpeptides, sarcosinates (e.g., N-acylsarcosinates), taurates (e.g., N-acyltaurates, and fatty acid amides of methyl tauride), and the like.

[0183] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: [ka] In the formula, R is C to C 22 alkyl group or [ka] where R 1 is C4~C 16 In some embodiments, R is an alkyl group, n is an integer from 1 to 20, m is an integer from 1 to 3, and X is a counterion such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10, and m is 1. In some embodiments, R is a C8 to C6 16 In some embodiments, R is C 12 ~C 14 is an alkyl group, n is 4, and m is 1.

[0184] In other embodiments, R is [ka] and R 1 C6~C 12 In still other embodiments, R 1 is a C9 alkyl group, n is 10, and m is 1.

[0185] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available in the acid form, which can be easily converted to the anionic or salt form. Commercially available carboxylates include Neodox 23-4, C 12~13 Carboxylate compounds include alkyl polyethoxy (4) carboxylic acids (Shell Chemical), and Emcol CNP-110, C alkylaryl polyethoxy (10) carboxylic acids (Witco Chemical). Carboxylate compounds are also available, for example, in the products Sandopan® DTC, C 13Alkylpolyethoxy(7)carboxylic acids are available from Clariant.

[0186] Nonionic surfactants Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic, alkylaromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety, typically ethylene oxide or its polyhydration products, polyethylene glycol. In fact, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydration adducts, or mixtures thereof with alkoxylenes such as propylene oxide, to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound with the desired degree of balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

[0187] Examples of initiator reactive hydrogen compounds include block polyoxypropylene-polyoxyethylene polymer compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine. Examples of polymer compounds made from sequential propoxylation and ethoxylation of the initiator are commercially available from BASF Corp. One class of compounds is difunctional (two reactive hydrogen) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobic material between hydrophilic groups, controlled in length to comprise about 10% to about 80% by weight of the final molecule. Another class of compounds is trifunctional block copolymers obtained 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; hydrophilic ethylene oxide is added so as to constitute about 10% to about 80% by weight of the molecule.

[0188] Condensation products of one mole of alkylphenol, in which the alkyl chain, straight or branched, or single or double alkyl members, contains from about 8 to about 18 carbon atoms, with from about 3 to about 50 moles of ethylene oxide. The alkyl group can be represented, for example, by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can also be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemistry are available under the trade names Igepal® manufactured by Rhone-Poulenc and Triton® manufactured by Union Carbide.

[0189] Condensation products of one mole of 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. The alcohol portion can consist of a mixture of alcohols within the carbon range described above, or it can consist of an alcohol having a specific number of carbon atoms within this range. Examples of similar commercial surfactants are available under the trade names Lutensol™ and Dehydol™ from BASF, Neodol™ from Shell Chemical Co., and Alfonic™ from Vista Chemical Co.

[0190] The condensation product of one mole of a 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. The acid portion may consist of a mixture of acids within the carbon atom range defined above, or may consist of an acid having a specific number of carbon atoms within this range. Examples of commercial compounds of this chemistry are available under the trade names Disponil or Agnique manufactured by BASF and Lipopeg™ manufactured by Lipo Chemicals, Inc.

[0191] In addition to ethoxylated carboxylic acids, commonly referred to as polyethylene glycol esters, glycerides, other alkanoic acid esters formed by the reaction of glycerin with polyhydric (saccharide or sorbitan / sorbitol) alcohols, have application in specific embodiments of the present disclosure, particularly indirect food additive applications. All of these ester moieties have one or more reactive hydrogen sites on their molecules that can be subjected to further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials. Care must be taken when adding these fatty esters or acylated carbohydrates to compositions of the present disclosure containing amylase and / or lipase enzymes due to potential incompatibilities.

[0192] Examples of nonionic low foaming surfactants are: These include compounds from (1) that have been modified, essentially inverted, by adding ethylene oxide to ethylene glycol to provide a hydrophile of a specified molecular weight, followed by the addition of propylene oxide to obtain a hydrophobic block on the outside (end) of the molecule. The hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 3,100, and the central hydrophile comprises 10% to about 80% by weight of the final molecule. These inverted Pluronics™ are manufactured by BASF Corporation under the trademark Pluronic™ R surfactants. Similarly, Tetronic™ R surfactants are manufactured by BASF Corporation by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule has a molecular weight of about 2,100 to about 6,700, and the central hydrophile comprises 10% to about 80% by weight of the final molecule.

[0193] Compounds from groups (1), (2), (3), and (4) that have been modified by "capping" or "end-blocking" the terminal hydroxy group(s) (of the polyfunctional moiety) to reduce foaming by reaction with hydrophobic small molecules such as propylene oxide, butylene oxide, benzyl chloride, and short-chain fatty acids, alcohols, or alkyl halides containing 1 to about 5 carbon atoms, and mixtures thereof. Also included are reactants such as thionyl chloride that convert the terminal hydroxy group to a chloride group. Such modifications to the terminal hydroxy group can result in all-block, block-heteric, heteric-block, or all-heteric nonionics.

[0194] 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. [ka] wherein 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.

[0195] The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548, issued Aug. 7, 1962 to Martin et al., have alternating hydrophilic oxyethylene and hydrophobic oxypropylene chains, with the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units, and the weight of the linking hydrophilic units each representing about one-third of the condensate.

[0196] General formula Z[(OR) n OH] z The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178, issued May 7, 1968 to Lissant et al., have the formula: wherein Z is an alkoxylatable material, R is a radical derived from alkylene oxide, which can be ethylene and propylene, n is an integer, for example, from 10 to 2,000 or more, and z is an integer determined by the number of reactive oxyalkylatable groups.

[0197] Formula Y(C3H6O) n (C2H4O) m Conjugated polyoxyalkylene compounds corresponding to H, where Y is the residue of an 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 the hydroxyl number, and m has a value such that the oxyethylene moieties constitute from about 10% to about 90% by weight of the molecule, are described in U.S. Pat. No. 2,677,700, issued May 4, 1954 to Jackson et al.

[0198] Formula Y[(C3H6O n (C2H4O) m H] xNo. 2,674,619 issued April 6, 1954 to Lundsted et al., describes a conjugated polyoxyalkylene compound having the formula: (wherein Y is the residue of an organic compound having about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, x having a value of at least about 2, n having a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900, and m having a value such that the oxyethylene content of the molecule is about 10% to about 90% by weight). Compounds falling within the definition for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chain optionally, but beneficially, contains a small amount of ethylene oxide, and the oxyethylene chain also optionally, but beneficially, contains a small amount of propylene oxide.

[0199] Additional conjugated polyoxyalkylene surfactants that may be beneficially used in the compositions of the present disclosure have the formula: P[(CHO) n (C2H4O) m H] x where P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, 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 optionally, but beneficially, contain small amounts of ethylene oxide, and the oxyethylene chains may also optionally, but beneficially, contain small amounts of propylene oxide.

[0200] Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions have the structural formula R2CON R1 Z, wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy group, or a mixture thereof; R2 is a C5-C 31Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z may be obtained from a reducing sugar in a reductive amination reaction, such as a glycityl moiety.

[0201] Alkyl ethoxylate condensation products of aliphatic alcohols with 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 be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

[0202] Ethoxylated C6~C 18 Fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols, especially those that are water soluble, are suitable surfactants for use in the present compositions. Suitable ethoxylated fatty alcohols are C6-C8 fatty acids having a degree of ethoxylation of 3 to 50. 18 Contains ethoxylated fatty alcohols.

[0203] Nonionic alkyl polysaccharide surfactants particularly suitable for use in the present compositions include those disclosed in U.S. Patent No. 4,565,647, issued January 21, 1986, to Llenado. These surfactants contain 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 reduced saccharide containing 5 or 6 carbon atoms may be used, e.g., glucose, galactose, and galactosyl moieties may be substituted for glucosyl moieties. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. position, producing glucose or galactose as opposed to glucoside or galactoside.) The intersaccharide bond may be, for example, between one position of an additional saccharide unit and the 2-, 3-, 4-, and / or 6-position on the preceding saccharide unit.

[0204] Fatty acid amide surfactants suitable for use in the present compositions include those having the formula: RCON(R) where R is an alkyl group containing 7 to 21 carbon atoms and each R is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(CHO). X H, and x is in the range of 1 to 3.

[0205] A useful class of nonionic surfactants includes the class defined as alkoxylated amine or, most specifically, alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants can be, at least in part, characterized by the general formula: 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, where R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations within these compounds include compounds of the alternative formula: R 20 --(PO) V --N[(EO) w H][(EO) z H], wherein R 20is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1 to 10, preferably 2 to 5. These compounds are commercially represented by the line of products sold by Huntsman Chemicals as nonionic surfactants. Preferred chemicals in this class include Surfonic™ PEA 25 amine alkoxylate. Preferred nonionic surfactants for the compositions of the present disclosure include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, and the like.

[0206] The article "Nonionic Surfactants," edited by Schick, MJ, Volume 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983, is an excellent reference for the variety of nonionic compounds commonly used in the practice of the present disclosure. A typical list of nonionic classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are given in "Surface Active Agents and Detergents," Volumes I and II, by Schwartz, Perry, and Berch.

[0207] Semi-polar nonionic surfactants Semi-polar nonionic surfactants are another class of nonionic surfactants useful in the compositions of the present disclosure. Generally, semi-polar nonionics are high-foaming agents and foam stabilizers, which can limit their application in CIP systems. However, in the compositional embodiments of the present disclosure designed for high-foam cleaning methods, semi-polar nonionics have immediate practical utility. Semi-polar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0208] Amine oxides have the general formula: [ka] where the arrow is a conventional representation of a semipolar bond; R 1 , R 2 , and R 3 R may be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Generally, for the amine oxide of interest, R 1 is an alkyl radical of about 8 to about 24 carbon atoms, and R 2 and R 3 is alkyl or hydroxyalkyl of 1 to 3 carbon atoms, or a mixture thereof; R 2 and R 3 may be bonded to each other, for example, through an oxygen or nitrogen atom, to form a ring structure, and R 4 is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, and n ranges from 0 to about 20.

[0209] Useful water-soluble amine oxide surfactants are selected from coconut or tallow alkyl di-(lower alkyl)amine oxides, specific examples of which include dodecyl dimethylamine oxide, tridecyl dimethylamine oxide, etradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, octadecyl dimethylaine oxide, dodecyl dipropylamine oxide, tetradecyl Dipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0210] Useful semi-polar nonionic surfactants also include water-soluble phosphine oxides having the following structure: [ka] where the arrow is a conventional representation of a semipolar bond; R 1 is an alkyl, alkenyl, or hydroxyalkyl moiety ranging in chain length from 10 to about 24 carbon atoms; R 2 and R 3 are each alkyl moieties independently selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[0211] Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.

[0212] Semi-polar nonionic surfactants useful herein also include water-soluble sulfoxide compounds having the following structure: [ka] where the arrow is a conventional representation of a semipolar bond; R 1 is an alkyl or hydroxyalkyl moiety of from about 8 to about 28 carbon atoms, 0 to about 5 ether linkages, and 0 to about 2 hydroxyl substituents; R 2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

[0213] Useful examples of these sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

[0214] Semi-polar nonionic surfactants for use in the compositions of the present disclosure include dimethylamine oxides such as lauryl dimethylamine oxide, myristyl dimethylamine oxide, cetyl dimethylamine oxide, and combinations thereof. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(lower alkyl)amine oxides, specific examples of which include octyl dimethylamine oxide, nonyl dimethylamine oxide, decyl dimethylamine oxide, undecyl dimethylamine oxide, dodecyl dimethylamine oxide, iso-dodecyl dimethylamine oxide, tridecyl dimethylamine oxide, tetradecyl dimethylamine oxide, pentadecyl dimethylamine oxide, hexadecyl dimethylamine oxide, heptadecyl dimethylamine oxide, oc ... The amine oxide is selected from decyl dimethylamine oxide, dodecyl dipropylamine oxide, tetradecyl dipropylamine oxide, hexadecyl dipropylamine oxide, tetradecyl dibutylamine oxide, octadecyl dibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0215] Suitable nonionic surfactants suitable for use with the compositions of the present disclosure include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, or mixtures thereof, or the like. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers such as Pluronic and reverse Pluronic surfactants, alcohol alkoxylates such as Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6), and capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11, or mixtures thereof, or the like.

[0216] cationic surfactants A surfactant is classified as cationic if the charge on the hydrotrope portion of the molecule is positive. Hydrotropes do not carry a charge unless the pH is lowered to near-neutral or below, but surfactants that are then cationic (e.g., alkylamines) are also included in this group. In theory, cationic surfactants can be synthesized from any combination of elements containing the "onium" structure RnX+Y-- and can include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the field of cationic surfactants is dominated by nitrogen-containing compounds, likely because synthetic routes to nitrogenous cationic surfactants are simple and easy, providing high product yields, which makes nitrogenous cationic surfactants less expensive.

[0217] Cationic surfactants preferably include, and more preferably refer to, compounds containing at least one long carbon-chain hydrophobic group and at least one positively charged nitrogen. The long carbon-chain group may be directly attached to the nitrogen atom by simple substitution, or more preferably, indirectly attached through a bridging functional group(s) in so-called interrupted alkylamines and amidoamines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more easily dissolved in water by co-surfactant mixtures, and / or water-soluble. To increase water solubility, additional primary, secondary, or tertiary amino groups can be introduced, or the amino nitrogen can be quaternized with a low-molecular-weight alkyl group. Furthermore, the nitrogen can be part of a branched or linear moiety with various degrees of unsaturation, or part of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants can contain complex bonds with two or more cationic nitrogen atoms.

[0218] Surfactant compounds classified as amine oxides, amphoterics, and zwitterions are themselves typically cationic in solutions at near-neutral to acidic pH, overlapping with the classification of surfactants. Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solutions and like cationic surfactants in acidic solutions.

[0219] The simplest cationic amines, amine salts and quaternary ammonium compounds can be depicted schematically as follows: [ka] wherein R represents an alkyl chain, R', R'', and R''' can be either an alkyl chain or an aryl group, or hydrogen, and X represents an anion. Amine salts and quaternary ammonium compounds are preferred for practical use in the present disclosure due to their high water solubility.

[0220] The majority of commercially available cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art and are described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104(2) 86-96 (1989). The first class includes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourth class includes quaternaries, such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, and tetraalkylammonium salts. Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties may include detergency in compositions below neutral pH, antimicrobial efficacy, thickening or gelling in conjunction with other agents, and the like.

[0221] Cationic surfactants useful in the compositions of the present disclosure include those having the formula R 1 m R 2 x Y L Z, wherein each R 1 is optionally substituted with up to three phenyl or hydroxy groups and up to four of the following structures: [ka] or an organic group containing a straight or branched alkyl or alkenyl group optionally interrupted by an isomer or mixture of these structures, which contains about 8 to 22 carbon atoms. 1 The group may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, there is no more than one R 1 The group has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3. Each R 2 is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, and there is not more than one R 2is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled with hydrogen.

[0222] Y may be, but is not limited to, [ka] or a group containing a mixture thereof. Preferably, L is 1 or 2, and the Y group, when L is 2, is an R group having 1 to about 22 carbon atoms and two free carbon single bonds. 1 and R 2 Z is a water-soluble anion such as a halide, sulfate, methylsulfate, hydroxide, or nitrate, with chloride, bromide, iodide, sulfate, or methylsulfate being preferred in numbers that provide electroneutrality of the cationic component.

[0223] amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In a few surfactants, sulfonates, sulfates, phosphonates, or phosphates provide the negative charge.

[0224] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary amines and aliphatic tertiary amines, in which the aliphatic radical can be straight-chain or branched, and one of the aliphatic substituents contains about 8 to 18 carbon atoms, and the other contains an anionic water-solubilizing group, such as carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are subdivided into two major classes known to those skilled in the art and are described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104(2)69-71 (1989), the entire contents of which are incorporated herein by reference. The first class includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkylamino acids and their salts. Some amphoteric surfactants may be considered to fall into both classes.

[0225] Amphoteric surfactants can be synthesized by methods known to those skilled in the art.For example, 2-alkylhydroxyethyl imidazoline is synthesized by condensation and ring closure of long-chain carboxylic acid (or derivative) with dialkylethylenediamine.Commercial amphoteric surfactants are derivatized by sequential hydrolysis and ring opening of imidazoline ring by alkylation with, for example, chloroacetic acid or ethyl acetate.During alkylation, one or two carboxy-alkyl groups react to form tertiary amine and ether bond, and different alkylating agents produce different tertiary amines.

[0226] Long chain imidazole derivatives having application in the present disclosure generally have the following general formula: [ka] Neutral pH Zwitterions Amphoteric sulfonates [ka] wherein R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation to neutralize the charge of the anion, typically sodium. Commercially known imidazoline-derived amphoterics that can be used in the present compositions include, for example, cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. Amphocarboxylic acids can be produced from fatty imidazolines in which the dicarboxylic acid functional group of the amphodicarboxylic acid is acetoacetic acid and / or dipropionic acid.

[0227] The carboxymethylated compounds (glycinates) described hereinabove are often called betaines, which are a special class of amphoteric surfactants discussed herein below in the section entitled Zwitterionic Surfactants.

[0228] Long-chain N-alkyl amino acids are easily prepared by the reaction RNH2, where R = C8-C 18 These are aliphatic amines with straight-chain or branched alkyl and halogenated carboxylic acids. Alkylation of the primary amino group of an amino acid results in secondary and tertiary amines. The alkyl substituent may have additional amino groups that provide two or more reactive nitrogen centers. Most commercially available N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercial N-alkylamino acid ampholytes having application in the present disclosure include alkyl beta-aminodipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In one embodiment, R can be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

[0229] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include, as part of their structure, an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety such as glycine, or a combination thereof, and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkyl amphodicarboxylic acids. These amphoteric surfactants include C 12 -Alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -Alkyl-C(O)-N(H)-CH2-CH2-N + The surfactant may include a chemical structure represented as (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is one suitable amphoteric surfactant and is commercially available under the trade name Miranol™ FBS from Rhodia Inc., Cranbury, NJ. Another suitable coconut-derived amphoteric surfactant, having the chemical name disodium cocoamphodiacetate, is sold under the trade name Mirataine™ JCHA, also from Rhodia Inc., Cranbury, NJ.

[0230] A typical listing of amphoteric classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued December 30, 1975, to Laughlin and Heuring. Further examples are given in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry, and Berch). Each of these references is incorporated herein by reference in its entirety.

[0231] Zwitterionic surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can contain an anionic charge. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, heterocyclic secondary and tertiary amines, or quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants contain a positively charged quaternary ammonium, or in some cases a sulfonium or phosphonium ion, a negatively charged carboxyl group, and an alkyl group. Zwitterions generally contain cationic and anionic groups that are ionized to approximately equal degrees in the isoelectric region of the molecule, which can generate strong "inner salt" attractions between the positive and negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radical may be straight-chain or branched, one of the aliphatic substituents containing 8 to 18 carbon atoms, and one containing an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0232] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula for these compounds is: [ka] where R 1 contains an alkyl, alkenyl, or hydroxyalkyl radical of 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety, Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms, and R 2 is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms, x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R 3is an alkylene or hydroxyalkylene or hydroxyalkylene of 1 to 4 carbon atoms, and Z is a radical selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate, and phosphate groups.

[0233] Examples of zwitterionic surfactants having the above structure include 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate, 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate, 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate, 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate, 3-(N,N-dimethyl-N- Examples of suitable detergent surfactants include S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-propane-1-sulfonate, 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in the detergent surfactants may be straight or branched chain and saturated or unsaturated.

[0234] Zwitterionic surfactants suitable for use in the present compositions include betaines of the general structure: [ka]

[0235] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH, nor do they exhibit reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C 12~14 Acylamidopropyl betaine, C 8~14 Acylamidohexyldiethylbetaine, 4-C 14~16 Acylmethylamidodiethylammonio-1-carboxybutane, C 16~18 Acylamide dimethyl betaine, C 12~16 Acylamidopentanediethyl betaine, and C 12~16 Acylmethylamidodimethylbetaine is an example.

[0236] Sultaines useful in the present disclosure include those of the formula (R(R 1 )2N + R 2 SO 3- and wherein R is a C to C 18 is a hydrocarbyl group, and each R 1 are typically independently C1-C3 alkyl, e.g., methyl, and R 2 is a C1-C6 hydrocarbyl group, for example a C1-C3 alkylene or hydroxyalkylene group.

[0237] A typical listing of zwitterionic classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued December 30, 1975, to Laughlin and Heuring. Further examples are given in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry, and Berch). Each of these references is incorporated herein in its entirety.

[0238] Antifoaming agents Antifoaming agent can also be included in dishwashing compositions to reduce foam stability.Examples of antifoaming agent include but are not limited to: ethylene oxide / propylene block copolymers, such as those available under the name of Pluronic N-3; silicone compounds, such as polydimethylsiloxane, polydimethylsiloxane, and silica dispersed in functionalized polydimethylsiloxane, such as those available under the name of Abil B9952; fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, and alkyl phosphate esters, such as monostearyl phosphate.Discussions about antifoaming agent can be found, for example, in U.S. Patent No. 3,048,548 to Martin et al., U.S. Patent No. 3,334,147 to Brunelle et al., and U.S. Patent No. 3,442,242 to Rue et al., the disclosures of which are incorporated herein by reference. When the concentrate includes an antifoaming agent, the antifoaming agent may be provided in an amount of from about 0.0001% to about 10% by weight, from about 0.001% to about 5% by weight, or from about 0.01% to about 1.0% by weight.

[0239] Concentrates and Use Solutions for Methods of Use The detergent compositions provided in the blocks are concentrated compositions. Generally, a concentrate refers to a composition that is intended to be diluted with water to provide a use solution that contacts an object to provide the desired cleaning, rinsing, etc.

[0240] Use solutions can be prepared from concentrates by diluting the concentrate with water at a dilution ratio that provides a use solution with the desired cleaning properties. The water used to dilute the concentrate to form the use composition may be referred to as dilution water or diluent and may vary from location to location. Typical dilution factors are approximately 1 to approximately 10,000, but will depend on factors such as water hardness and the amount of soil to be removed. Concentrates can be diluted at a concentrate-to-water ratio of about 1:10 to about 1:10,000. Specifically, concentrates are diluted at a concentrate-to-water ratio of about 1:100 to about 1:5,000. More specifically, concentrates can be diluted at a concentrate-to-water ratio of about 1:250 to about 1:2,000.

[0241] In one embodiment of the present disclosure, a use solution of the detergent composition has from about 10 ppm to about 6000 ppm of the alkaline source. In a preferred embodiment of the present disclosure, a use solution of the detergent composition has from about 500 ppm to about 4000 ppm of the alkaline source. In an even more preferred embodiment of the present disclosure, a use solution of the detergent composition has from 2500 ppm to about 3500 ppm of the alkaline source. Additionally, although not intended to be limited in accordance with the present disclosure, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0242] In one aspect of the present disclosure, the detergent composition preferably provides effective cleaning at a low use dilution, e.g., requires less volume to effectively clean. In one aspect, the detergent composition may be diluted in water prior to use at a dilution range of about 1 / 16 ounces per gallon to about 2 ounces per gallon or more. Detergent compositions that require less volume to achieve the same or better cleaning efficacy and provide hardness scale control and / or other benefits at a low use dilution are desirable.

[0243] In some embodiments, the detergent composition is contacted with a diluent, such as water, to form a concentrate and / or use solution for various use applications.

[0244] In some aspects, the present disclosure provides a method for removing stains from a surface, e.g., a hard surface, and / or for bleaching the surface. In some embodiments, the method includes contacting a use solution of a detergent composition with the surface and removing the composition from the surface after an amount of time sufficient to facilitate stain removal and / or bleaching. The contacting step can continue for any suitable time. In some embodiments, the contacting step continues for at least 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 10 minutes, 30 minutes, 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, 1 day, 3 days, 1 week, or more. The detergent composition can be contacted with the surface (or target for stain removal and / or bleaching) in any suitable manner. In some embodiments, the detergent composition is applied by means of spraying, foaming, immersion, or the like.

[0245] The methods can be used to achieve any suitable soil removal (e.g., cleaning), disinfection, sanitizing, bleaching, and / or reduction of microbial populations in and / or on a surface or target. In some embodiments, the methods can be used to reduce microbial populations by at least 1 log10. In other embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 2 log10. In yet other embodiments, the methods of the present invention can be used to reduce microbial populations in and / or on a target or treated target composition by at least 3 log10.

[0246] In some embodiments, the method further comprises rinsing the surface. In some embodiments, the method further comprises mechanical application of force, agitation, and / or pressure to aid in the removal of stains and / or bleaching the surface.

[0247] The disclosed method can be used to remove various stains from and / or bleach various surfaces. For example, suitable surfaces for cleaning using the disclosed method include, but are not limited to, walls, floors, utensils, dishes, tableware, pots and pans, heat exchange coils, ovens, fryers, smokehouses, sewer drains, etc.

[0248] In some embodiments, the method of the present disclosure is followed by only a rinse step. In other embodiments, the method of the present disclosure is followed by a conventional CIP method suitable for the surface to be cleaned. In still other embodiments, the method of the present disclosure is followed by a CIP method such as those described in U.S. Patent Nos. 8,398,781 and 8,114,222, entitled "Methods for Cleaning Industrial Equipment with Pre-treatment," both of which are incorporated by reference in their entireties.

[0249] How to use In another aspect, disclosed herein is a method of cleaning, disinfecting, and / or bleaching that includes forming a use solution of the disclosed composition that includes an alkaline source, an enzyme, and certain types of phosphonate or amine phosphonate salts.

[0250] In yet another aspect, disclosed herein is a method of cleaning, sanitizing, and / or bleaching that includes forming a use solution of the disclosed composition, which includes an alkaline source, an enzyme, and certain types of phosphonate or amine phosphonate salts, and contacting a surface or object in need of cleaning and sanitizing with the use solution.

[0251] In some embodiments, a use solution of the disclosed detergent compositions retains at least 15% of its enzyme activity 240 minutes after its production, hi some other embodiments, a use solution of the disclosed detergent compositions retains at least 20% of its enzyme activity 120 minutes after its production.

[0252] In yet another aspect, the present disclosure is a method for stabilizing an enzyme in a solid detergent. The method comprises: [ka] or a salt thereof, or an amine phosphonate salt of formula R 10 and R 11 are independently hydrogen, substituted carboxylic acid, phosphonate, ethanol, diglycol, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, or phosphonatemethyl, and the amine phosphonate salt is represented by the formula [ka] and an amine, 12 , R 13 , and R 14 are independently hydroxyl, methyl, —PO(OH) 2 , —CH 2 COOH, a substituted alkyl, a phosphonate, an ester thereof, a salt thereof, or a derivative thereof.

[0253] All publications and patent applications in this specification are indicative of the level of those skilled in the art to which this disclosure pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. [Example]

[0254] Embodiments of the present disclosure are further defined in the following non-limiting examples. It should be understood that these examples, while illustrating certain embodiments of the present disclosure, are given by way of illustration only. From the above discussion and these examples, those skilled in the art can ascertain the essential features of the present disclosure and can make various changes and modifications to the embodiments of the present disclosure to adapt them to various uses and conditions without departing from the spirit and scope thereof. Thus, various modifications of the embodiments of the present 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.

[0255] In the examples, the following materials are used: Bio-terge® AS-90-90% Active C 14 ~C 16 Alpha olefin sulfonate (AOS); Ufaryl DL90C-90%C 10 ~C 13 Activated Linear Alkylbenzene Sulfonate (LAS), drum-dried powder; Belclene 200-50% active 500-100MW polymaleic acid; Acusol™ 445N - 45% active polyacrylic acid (4500-10000 MW); Acusol™ 445ND - 45% active polyacrylic acid (4500-10,000 MW), spray dried; Acusol™ 820—a hydrophobically modified alkali-soluble acrylic polymer emulsifier (HASE) with very high aqueous thickening and stabilizing effects; Acusol™ 929—46% active polyacrylic acid (approximately 10,000–15,000 MW); Heavy ash-sodium carbonate; Light ash - sodium carbonate; Sodium bicarbonate, granules; PEG8000 - polyethylene glycol with an average molecular weight of 8,000; Powdered bicarbonate - powdered sodium bicarbonate; CMC-7LT - carboxymethyl cellulose; LAE24-7-Linear alcohol ethoxylate (7 moles EO); ATMP-aminotri(methylenephosphonic acid); AMPA-aminomethylphosphonic acid; PBTC-phosphonebutanetricarboxylic acid, Bayhibit AM; STPP - sodium tripolyphosphate; HEDP-1-hydroxyethylidene-1,1-diphosphonic acid, Dequest2010; DGAP-diglycolamine phosphonate, scale inhibitor 2588; MEAP-monoethanolamine phosphonate, scale inhibitor 2670; PAPEMP - Polyaminopolyether methylene phosphonic acid, Kemguard 8010; PSO-phosphinosuccinic acid mixture from Nalco, Nalco TX15712SQ.

[0256] Example 1 Enzyme activity in detergents with different phosphonate levels was tested at 4000 ppm at 5 grains per gallon (GPG) of water at 120°F at various time points collected within 4 hours after use solutions were generated from the detergent compositions. Samples were collected at different time points during the test, immediately frozen in an acetone / dry ice bath, and stored at -80°C before assessing enzyme activity. For use in such assays, t=0 minutes was used as the reference point for 100% enzyme activity.

[0257] The enzyme activity (% retention) in the formulations was assayed to simulate presoak conditions in a beaker using chemical, temperature, and pH conditions associated with manual dishwashing or presoak applications. Enzyme activity is an indicator of the stability of the enzyme in the detergent, specifically in the aqueous use solution in the sump (under high pH, ​​temperature, and dilution conditions).

[0258] The protease assay analysis was performed as follows: For the assay, the detergent compositions were used to generate the aqueous use solutions evaluated herein. The components in the detergent compositions tested are listed in Table 1.

[0259] Enzyme activity under presoak or manual dishwashing conditions was quantitatively monitored using a standard protease assay. Samples were prepared under benchtop conditions, whereby a use solution from the detergent composition or detergent was obtained and maintained at presoak or manual dishwashing temperature in a stirred water bath. After the time course for assessing enzyme stability began, aliquots were taken at various time points and flash-frozen. A time = 0 sample was prepared for each series by dissolving the detergent formulation at room temperature, mixing thoroughly, and flash-frozen. Samples were thawed and diluted, if necessary, with an assay buffer typically used in protease assays. Glycine buffer, pH 9.0, was used herein. The assay monitored the direct reaction of proteases on small, commercially available peptidyl substrates, as product release provided a correlation with active enzyme content. Product was detected using a plate reader with a measurable dynamic range (upper limit of instrument transmittance > 3.5). Enzyme activity levels were evaluated against a calibration curve using the average values ​​of replicates used to map protease stability under presoak or manual dishwashing conditions. Enzyme retention at each time point was calculated as % enzyme activity relative to the time = 0 sample.

[0260] The lipase and amylase assays were performed similarly, but with different substrates and buffers. For lipase activity, the substrate was p-nitrophenyl valerate, and for amylase, the substrate was ethylidene phosphate (EPS). The buffer used was TRIS (tris(hydroxymethyl)aminomethane) buffer at pH 8.0 for the lipase assay, and HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) buffer at pH 8.0 for the amylase assay.

[0261] The phosphonates evaluated and their concentration levels are listed in Table 2. The phosphonate structures and their overall effect on enzyme activity were evaluated using the following: Table 3-1 and Table 3-2 The relative enzyme activity over time in use solutions of the tested detergent compositions containing different phosphonates at different concentrations is listed in Tables 4A-4E, 5A-5E, and 6A-6F. [Table 1] [Table 2] [Table 3-1] [Table 3-2] [Table 4A-1] [Table 4A-2] [Table 4B-1] [Table 4B-2] [Table 4C-1] [Table 4C-2] [Table 4D-1] [Table 4D-2] [Table 4E] [Table 5A-1] Table 5A-2 Table 5B-1 Table 5B-2 Table 5C-1

Table 5C-2

Table 6C-2

[0262] The protease, amylase, and lipase activities at different time points in use solutions of various detergent compositions containing phosphonates are plotted in Figures 1A-6G, respectively. The data in Tables 4A-4E and Figures 1A-2C show that base-formulated proteases are more stable in detergent compositions containing ATMP, DGAP, PAPEMP, and MEAP, with the use solutions retaining at least 50% protease activity even 4 hours after formation. AMPA also improves protease stability, but to a lesser extent. These phosphonates share common structural features with NR'R"-PO(OH). On the other hand, detergent compositions containing no phosphonates, or other types of phosphonates such as PBTC and HEDP, exhibit very short enzyme activity windows, and use solutions lose more than 70% of their enzyme activity after only 20 minutes of formation. However, for at least some other phosphonates, such as PBTC and HEDP, which share common structural features with CR'R"R"'-PO(OH), when the phosphonate is neutralized with an amine such as triethanolamine, detergent compositions containing the amine salts of such phosphonates exhibit much improved enzyme activity over corresponding detergent compositions in which the phosphonate is not neutralized with an amine. Figure 2D shows that proteases in whole ash formulas are more stable in use solutions of detergent compositions containing ATMP or DGAP than in use solutions of the same detergent compositions containing PBTC or HEDP without the amine(s).

[0263] The data in Tables 5A-5E and Figures 3A-4C show that amylase activity in the base formula is also affected differently by different types of phosphonates in a manner similar to protease activity, although the effect of phosphonates on amylase activity is less pronounced than that on protease activity. However, Figure 4D shows that amylase in the whole ash formula is more stable in use solutions of detergent compositions containing ATMP or DGAP than in use solutions of the same detergent compositions containing PBTC or HEDP without the amine(s).

[0264] The data in Tables 6A-6F and Figures 5A-6F show that lipase is also more stable in detergent compositions containing ATMP, DGAP, PAPEMP, and MEAP, with use solutions retaining at least about 15% lipase activity even 4 hours after generation. However, Figure 6G shows that lipase in the whole ash formula is more stable in use solutions of detergent compositions containing ATMP or DGAP than in use solutions of the same detergent compositions containing PBTC or HEDP without the amine(s).

[0265] Applicants have unexpectedly discovered that several phosphonates, some of which are commonly used in detergent compositions, actually destabilize proteases, amylases, or lipases, as shown in Figures 1A-6G.

[0266] Phosphonates are used in many consumer or high-intensity detergents as scale inhibitors, sequestering agents, or scale preventatives to enhance the performance of other active ingredients in hard water applications, but their general ability as enzyme stabilizers in detergent compositions has not been recognized or investigated, let alone the specific types of phosphonates disclosed herein. Applicant has unexpectedly discovered that these two specific types of phosphonates, alone or in the form of their amine salts, can stabilize enzymes in detergent compositions after the use solution is formed and during cleaning applications. This discovery has led to increased effectiveness of detergent compositions and new methods for creating or formulating new detergent compositions that are more efficient and cost-effective at removing soils.

[0267] The invention being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as departures from the spirit and scope of the disclosure, and all such modifications are intended to be included within the scope of the following claims.

[0268] The above specification provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the disclosure, the invention resides in the claims hereinafter appended. Examples of embodiments of the present invention are listed below. [1] enzyme, [ka] or a salt thereof, and an alkaline source, the enzyme comprises a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; the alkaline source is a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; In the formula, R 10 and R 11 are independently hydrogen, substituted alkyl, 2-(EO) n -Biphosphonateamine-ethyl, 2-(PO) n -biphosphonateamine-isopropyl, phosphonate, phosphonate ester, or derivatives thereof, However, R 10 and R 11 are both -CH 2 -PO(OH) 2 A composition which is a group. [2] R 11 But -CH 2 -PO(OH) 2 Item 2. The composition according to item 1, wherein the compound is a group. [3] R 11 But -CH 2 -PO(OH) 2 is a group, and R 10 Item 10. The composition of claim 1, wherein is a substituted alkyl. [4] R 11 But -CH 2 -PO(OH) 2 is a group, and R 10 is a phosphonate, a phosphonate ester, or a derivative thereof. [5] The phosphonate is

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[10] 10. The composition according to any one of items 1 to 9, wherein the enzyme is about 0.1 to 35% by weight of the composition.

[11] 11. The composition according to any one of items 1 to 10, wherein the alkaline source is about 0.1 to 90% by weight of the composition.

[12] 12. The composition according to any one of items 1 to 11, wherein a use solution of the composition has a pH of about 8 to about 12.

[13] 13. The composition of any one of items 1 to 12, wherein in a use solution of the composition, the enzyme retains at least 15% of its activity at 120°F (about 48.9°C) for at least 4 hours.

[14] 13. The composition of any one of items 1 to 12, wherein in a use solution of the composition, the enzyme retains at least 20% of its activity at 120°F (about 48.9°C) for at least 4 hours.

[15] 15. The composition according to any one of items 1 to 14, further comprising an amine.

[16] 16. The composition according to item 15, wherein the amine is about 0.1 to 35% by weight of the composition.

[17] Item 16. The composition according to item 15, wherein the molar ratio of the phosphonate to the amine is about 0.5:1 to 1:0.5.

[18] 18. The composition according to any one of items 15 to 17, wherein the amine is an alkanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof.

[19] 19. The composition of any one of items 1 to 18, wherein the composition further comprises a metal hydroxide, tripolyphosphate, or a mixture thereof.

[20] 20. The composition of any one of the preceding claims, further comprising one or more of additional functional ingredients comprising an oxidizer, a builder, a water conditioner, a water conditioning agent, a peroxyacid, an initializer for a peroxyacid, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant, a chelating agent, a fragrance, a dye, a rheology modifier, a thickener, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant, a hydrotrope, a coupler, or any combination thereof.

[21] 1. A composition comprising an enzyme, an alkaline source, and an amine phosphonate salt, The amine phosphonate salt is

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[22] R 12 、R 13 , and R 14 One of the groups is hydroxyl, methyl, -PO(OH) 2 , -CH 2 22. The composition according to item 21, wherein the compound is COOH, an ester thereof, a salt thereof, or a derivative thereof.

[23] The phosphonate is PO(OH) 2 (C(CH 2 COOH) 3 22. The composition according to item 21, wherein the PBTC is PBTC.

[24] The phosphonate is C(CH 3 )(OH)(PO(OH) 2 ) 2 22. The composition according to item 21, wherein the composition is HEDP.

[25] 25. The composition according to any one of items 21 to 24, wherein the amine is monoethanolamine, diethanolamine, triethanolamine, isopropylamine, or a mixture thereof.

[26] 26. The composition according to any one of items 21 to 25, wherein the enzyme comprises a protease, an amylase, a lipase, or a mixture thereof.

[27] 27. The composition of any one of items 21 to 26, wherein the alkaline source comprises a metal carbonate, a metal bicarbonate, or a mixture thereof.

[28] 28. The composition according to item 27, wherein the molar ratio of the metal carbonate to the metal bicarbonate is from about 0.25:1 to about 1:0.25.

[29] 29. The composition according to any one of items 21 to 28, wherein a use solution of the composition has a pH of about 8 to about 12.

[30] 30. The composition of any one of items 21 to 29, wherein in a use solution of the composition, the enzyme retains at least 15% of its activity at 120°F (about 48.9°C) for at least 40 minutes.

[31] 31. The composition according to any one of items 21 to 30, wherein the amine comprises about 0.1 to 35% by weight of the composition.

[32] 32. The composition according to any one of items 21 to 31, wherein the phosphonate comprises about 0.1 to 35% by weight of the composition.

[33] 33. The composition according to any one of items 21 to 32, wherein the enzyme constitutes about 0.1 to 35% by weight of the composition.

[34] 34. The composition according to any one of items 21 to 33, wherein the alkaline source constitutes about 0.1 to 90% by weight of the composition.

[35] 35. The composition of any one of items 21 to 34, wherein the composition further comprises a metal hydroxide, tripolyphosphate, or a mixture thereof.

[36] 36. The composition of any one of items 21 to 35, wherein the composition further comprises one or more of an oxidizing agent, peroxyacid, initializer for peroxyacid, chelating agent, threshold agent, crystal modifier, disinfectant, defoamer, anti-redeposition agent, bleaching agent, solubility modifier, dispersant, rinse aid, polymer, metal protecting agent, stabilizing agent, corrosion inhibitor, sequestrant, chelating agent, fragrance, dye, rheology modifier, thickener, nonionic surfactant, cationic surfactant, zwitterionic surfactant, hydrotrope, coupler, or any combination thereof.

[37] 1. A solid detergent composition comprising an alkaline source, a phosphonate, and an enzyme, the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or a mixture thereof; the enzyme comprises a protease, an amylase, a lipase, a cellulase, a peroxidase, a gluconase, or a mixture thereof; The phosphonate is

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[38] Item 38. The solid detergent composition of item 37, wherein the solid detergent is produced by a casting process, an extrusion process, or a pressing process.

[39] Item 39. The solid detergent composition according to item 37 or 38, wherein the solid detergent is in the form of a block, a tablet, or a granule.

[40] 40. The solid detergent composition according to any one of items 37 to 39, wherein the solid detergent is a multi-use solid detergent.

[41] R 11 But -CH 2 -PO(OH) 2 41. The solid detergent composition according to any one of items 37 to 40, wherein the solid detergent composition is a group.

[42] R 11 But -CH 2 -PO(OH) 2 is a group, and R 10 However, ethanolyl, diglyco, substituted alkyl, isopropyl-2-(EO) n -biphosphonate amine, or methyl-phosphonate.

[43] The phosphonate is

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[44] 44. The solid detergent composition of any one of items 37 to 43, wherein the alkaline source comprises a metal carbonate and a metal bicarbonate.

[45] Item 45. The solid detergent composition according to item 44, wherein the molar ratio of the metal carbonate to the metal bicarbonate is from about 0.25:1 to about 1:0.25.

[46] 46. ​​The solid detergent composition of any one of items 37 to 45, wherein the enzyme comprises a protease, an amylase, a lipase, or a mixture thereof.

[47] 47. The solid detergent composition of any one of items 37 to 46, further comprising an amine or a salt thereof.

[48] 48. The solid detergent composition of claim 47, wherein the amine is fully neutralized.

[49] 49. The solid detergent composition of item 47 or 48, wherein the amine comprises an alkanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropylamine, a salt thereof, or any mixture thereof.

[50] 50. The solid detergent composition of any one of items 37 to 49, further comprising a metal hydroxide, tripolyphosphate, or a mixture thereof.

[51] 51. The solid detergent composition of any one of items 37 to 50, further comprising one or more of an oxidizer, a builder, a water conditioner, a water conditioning agent, a peroxyacid, an initializer for a peroxyacid, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizing agent, a corrosion inhibitor, a sequestering agent, a chelating agent, a fragrance, a dye, a rheology modifier, a thickener, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant, a hydrotrope, a coupler, or any combination thereof.

[52] 52. The solid detergent composition of any one of items 37 to 51, wherein a use solution of the composition has a pH of from about 8 to about 12.

[53] 53. The solid detergent composition of any one of items 37-52, wherein, in a use solution of the composition, the enzyme retains at least 15% of its activity at 120°F (about 48.9°C) for at least 4 hours.

[54] 54. The solid detergent composition of any one of items 37 to 53, wherein the phosphonate comprises about 0.1 to 35% by weight of the composition.

[55] 55. The solid detergent composition of any one of items 37 to 54, wherein the enzyme comprises about 0.1 to 35% by weight of the composition.

[56] 56. The solid detergent composition of any one of items 37 to 55, wherein the alkaline source comprises about 0.1 to 90% by weight of the composition.

[57] 57. The solid detergent composition of any one of items 37 to 56, wherein the solid detergent is dimensionally stable and has a growth exponent of less than 3% when heated to a temperature of 122°F (50°C).

[58] 1. A solid detergent composition comprising an alkaline source, an amine phosphonate salt, and an enzyme, the alkaline source comprises a metal carbonate, a metal bicarbonate, a metal silicate, or any mixture thereof; the enzyme comprises a protease, an amylase, a lipase, or a mixture thereof; The amine phosphonate salt is

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[59] Item 59. The solid composition of item 58, wherein the solid detergent is produced by a casting process, an extrusion process, or a pressing process, the solid detergent is in the form of a solid block, tablet, or granule, and the solid is a multi-use solid detergent.

[60] 1. A method for cleaning, disinfecting, and / or bleaching, said method comprising: Producing a use solution of the composition according to any one of items 1 to 59; contacting a surface or object in need of cleaning and disinfection with said use solution.

[61] 1. A method for stabilizing an enzyme in a solid detergent, the method comprising: formula

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Claims

1. 0.1% to 35% by weight of an enzyme, including a protease; 0.1% to 10% by weight of a phosphonate selected from aminotrimethylene phosphonic acid (ATMP), diglycolamine phosphonate (DGAP), monoethanolamine phosphonate (MEAP), polyaminopolyether methylene phosphonic acid (PAPEMP), or combinations thereof; 1. A solid detergent composition comprising 50% to 90% by weight of an alkaline source, a use solution of the composition having a pH of 8 to 12; the alkali source comprises an alkali metal carbonate and an alkali metal bicarbonate, and the molar ratio of the alkali metal carbonate to the alkali metal bicarbonate is 0.75:1 to 1:0.75; A composition wherein, in a use solution of said composition, said enzyme retains at least 50% of its activity for at least 4 hours at 120°F (about 48.9°C).

2. The phosphonate is 【Chemistry 1】 or a mixture thereof, wherein n is an integer from 1 to 30.

3. The composition of claim 1 or 2, wherein the composition further comprises an amine, and the amine is 0.1 to 35% by weight of the composition.

4. 4. The composition of claim 3, wherein the molar ratio of said phosphonate to said amine is from 0.5:1 to 1:0.

5.

5. 5. The composition of any one of claims 1-4, further comprising one or more additional functional ingredients including an oxidizer, a builder, a water conditioner, a water conditioning agent, a peroxyacid, an initializer for a peroxyacid, a chelating agent, a threshold agent, a crystal modifier, a disinfectant, a defoamer, an anti-redeposition agent, a bleaching agent, a solubility modifier, a dispersant, a rinse aid, a polymer, a metal protecting agent, a stabilizer, a corrosion inhibitor, a sequestrant, a chelating agent, a fragrance, a dye, a rheology modifier, a thickener, a nonionic surfactant, a cationic surfactant, a zwitterionic surfactant, a hydrotrope, a coupler, or any combination thereof.

6. 6. The composition of any one of claims 1 to 5, wherein the solid detergent composition is produced by a casting process, an extrusion process, or a pressing process, wherein the solid detergent composition is a solid block, tablet, or granule, and wherein the solid detergent composition is provided in a multi-use solid form.

7. 1. A method for cleaning, disinfecting, and / or bleaching, said method comprising: Producing a use solution of the composition of any one of claims 1 to 6; contacting a surface or object in need of cleaning and disinfection with said use solution.

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