Hardness additives for improved edge hardening and block detergents containing hardness additives

Abstract

Disclosed are solid detergent compositions designed to maintain the integrity of the solid throughout the production of the pressed solid, during mechanical conveying, and during ejection from the mold. The inclusion of a hardness additive composition comprising a synergistic ratio of a polycarboxylic acid polymer chelating agent to an aminocarboxylate chelating agent provides a solid detergent composition with unexpected instant block hardness without a curing step. Also provided are methods of making and solid detergent compositions that have cleaning performance at least substantially similar to that of solid detergent compositions that do not include the hardness additive composition.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority under 35 U.S.C. § 119 to Provisional Application No. 62 / 811,656, filed February 28, 2019, which is incorporated herein by reference in its entirety.

[0002] The present invention relates to a solid detergent composition designed to maintain the integrity of the solid during mechanical conveying and ejection from the mold through the production of pressed solids. The solid detergent composition provides a solid with unexpected instant block hardness exceeding that of solid compositions without a curing step as a result of a hardness additive composition employing a dispersant polymer therein. The hardness additive composition contains a synergistic ratio of dispersant polymer, i.e., a polycarboxylic acid polymer chelant to an aminocarboxylate chelant. Methods of making the solid detergent composition and the solid detergent composition are also provided. [Background technology]

[0003] Conventional solid compositions, including solid detergents, can be made by a variety of solidification techniques. These include casting a molten composition, extruding and forming blocks or tablets at high pressure in a tablet press. Each of these methods of making solids has significant limitations. For example, expensive tablet presses can only apply high pressure to form tablet or pack-sized solids. Tablet presses are not suitable for making solid blocks. Casting requires melting the composition to form a liquid. Melting consumes energy and can destroy certain desirable ingredients in some cleaning products. Extrusion requires expensive equipment and advanced technical know-how.

[0004] There remains a need for additional methods for making solid compositions, and for compositions that can be made by these methods.

[0005] It is therefore an object of the claimed compositions to formulate hardness additive compositions with dispersant polymers suitable for use in a variety of compositions, including solid detergent compositions, to provide improved solid block hardness / rigidity.

[0006] A further objective of the present composition and hardness additive composition is to provide block hardness / rigidity immediately upon completion of block pressing, i.e., without the need for a curing step for solidification.

[0007] Yet another object of the present composition and hardness additive composition is to reduce or eliminate chips, gauges, brittle edges, and other structural weaknesses in pressed solids that result in product loss from the solids.

[0008] Other objects, advantages, and features of the detergent compositions disclosed herein and their uses will become apparent from the following specification taken in conjunction with the accompanying drawings. Summary of the Invention [Problem to be solved by the invention]

[0009] An advantage of the hardness additive compositions disclosed herein, and solid compositions containing same, and their uses, is the improved hardness of the solid composition, which does not have brittle or weak edges that would cause loss of solid material. [Means for solving the problem]

[0010] In one aspect, provided herein is a solid hardness additive composition comprising: from about 5% to about 40% by weight of the composition of at least one polycarboxylic acid polymer chelating agent comprising a polyacrylate or polyacrylic acid polymer or homopolymer; and from about 60% to about 95% by weight of the composition of at least one aminocarboxylate chelating agent comprising one or more of ethylenediamine-N,N-tetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), and glutamic acid N,N-diacetic acid (GLDA), wherein the polycarboxylic acid polymer chelating agent to the polyacrylate or polyacrylic acid polymer or homopolymer is from about 5% to about 40% by weight of the composition. The ratio of polymers has one of the following ratios: (A) the ratio of polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) or its salt in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt is about 0.3:1 to about 0.9:1, (B) the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or its salt is about 0.06:1 to about 0.12:1, and / or (C) the ratio of polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt is about 0.2:1 to about 0.5:1.

[0011] In other embodiments, a solid detergent composition includes a solid hardness additive composition, an alkaline source, and at least one nonionic surfactant, wherein the polycarboxylic acid polymer chelating agent of the hardness additive composition comprises less than about 4%, preferably about 2% or less, by weight of the composition.

[0012] In another aspect, provided herein is a method of making a solid composition comprising combining a hardness additive composition with an alkalinity source, at least one surfactant, and at least one additional functional ingredient, mixing to form a uniform mixture, and pressing in a mold to form a solid composition, wherein the solid is a block that has edge hardness upon pressing and removal from the mold.

[0013] While multiple embodiments are disclosed, still other embodiments of the detergent compositions disclosed herein will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the detergent compositions disclosed herein. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not restrictive. [Brief explanation of the drawings]

[0014] [Figure 1] 1 shows a box plot of total loose powder lost over three press solids tests comparing a control formulation (without hardness additive composition) to formulations containing the hardness additive composition, demonstrating the improvement in immediate block edge hardness. [Figure 2] 1 shows a box plot of total loose powder lost in press solids production for formulations containing hardness additive compositions compared to negative control formulations. [Figure 3] 1 shows a box plot of total loose powder lost over four press solids tests demonstrating improvement in immediate block edge hardness for control formulations (with (positive control) and without (negative control) hardness additive composition) compared to formulations containing the hardness additive composition. [Figure 4] 1 shows a box plot comparison of scrap rates for produced pressed solids containing a hardness additive composition ("New") compared to a formulation without the hardness additive composition ("Original").

[0015] Various embodiments of the detergent compositions disclosed herein will be described in detail with reference to the drawings, in which like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the compositions and methods disclosed herein, and their uses. The figures shown herein do not limit the various embodiments according to the detergent compositions disclosed herein, but are shown for illustrative purposes of the detergent compositions disclosed herein. DETAILED DESCRIPTION OF THE INVENTION

[0016] The embodiments of the detergent compositions, hardness additive compositions, and methods for making and using them disclosed herein are not limited to specific detergent compositions, which may vary and are understood by those skilled in the art, and may include, for example, additive systems for various compositions, including soft or sticky solids that require instant hardening. It should be further understood that all terminology used herein is solely 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" may include plural referents unless the context clearly dictates otherwise. Furthermore, all units, prefixes, and symbols may be indicated in their SI-recognized form.

[0017] The numerical ranges recited herein include the numbers within the defined range. Throughout this disclosure, various aspects or embodiments of the compositions or methods disclosed herein are presented in range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as a rigid limitation on the scope of the invention. Thus, the description of a range should be considered to specifically disclose all possible subranges and individual numerical values ​​within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0018] In order to make the detergent composition and hardness additive composition disclosed herein and their use more easily understandable, 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 to which the present invention relates.Many methods and materials similar, modified, or equivalent to those described herein can be used to implement the present invention without undue experimentation, and preferred materials and methods are described herein.In describing and claiming the present invention, the following terminology is used in accordance with the definitions set forth below.

[0019] 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 differ 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.

[0020] The terms "actives" or "percent actives" or "percent actives by weight" or "actives concentration" are used interchangeably herein and refer to the concentration of ingredients involved in cleaning expressed as a percentage minus inactive ingredients such as water or salt.

[0021] 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.), cycloalkyl 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).

[0022] 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.

[0023] 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 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.

[0024] As used herein, the term "cleaning" refers to methods used to promote or aid in the removal of soils.

[0025] The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, panels, windows, plumbing fixtures, kitchen and bathroom furniture, appliances, engines, circuit boards, and dishes. Hard surfaces can include, for example, healthcare surfaces and food processing surfaces.

[0026] 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 order "x"-mers, and further includes 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.

[0027] As used herein, the term "scrap rate" refers to the number or amount of solid composition that is not suitable for use. It is desirable to achieve a scrap rate of less than about 5%, preferably less than about 3%, and most preferably about 0% by using the hardness additive composition. For commercial or large-scale production of solid block compositions, the scrap rate can be calculated based on the total number of defective and therefore unusable blocks. For example, if 316,000 kg of solid composition were produced in one year, this would correspond to 105,334 blocks, and a 5% scrap rate would correspond to <5,267 defective blocks, and a more preferred 3% scrap rate would correspond to <3,160 defective blocks. For purposes of calculating the scrap rate under experimental conditions, such as the examples described herein, the scrap rate is defined in terms of the total amount of loose powder lost from the solid block composition, which represents the scrap rate in commercial production.

[0028] As used herein, the term "soil" refers to polar or non-polar organic or inorganic materials, including but not limited to carbohydrates, proteins, fats, oils, etc. These materials may exist in their organic state or may be complexed with metals to form inorganic complexes.

[0029] As used herein, the terms "substantially free," "free," "substantially free of," 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 should 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.

[0030] The term "substantially similar cleaning performance" refers to that generally achieved by a substitute cleaning product or system that generally uses the same degree of cleanliness (or at least not significantly less), or generally the same effort expenditure (or at least not significantly less), or both. As referred to herein, a solid detergent composition that includes a hardness additive composition provides a solid detergent with substantially similar cleaning performance as a solid detergent composition that does not include the hardness additive composition.

[0031] 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.

[0032] The methods, hardness additive compositions, and detergent compositions disclosed herein can comprise, consist essentially of, or consist of the components and ingredients of the hardness additive compositions and / or detergent compositions disclosed herein, as well as other ingredients not described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients so long as the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods and compositions.

[0033] Hardness additive composition The hardness additive composition is suitable for various solid compositions, including solid detergent compositions, for example, to improve the hardness, i.e., block edge rigidity, of the solid composition immediately after pressing. Advantageously, the hardness additive composition is useful when added to various solid compositions, such as solid detergent compositions, solid formulations that have a sticky consistency and benefit from enhanced hardening, caustic formulations, manual detergents, laundry detergents, and the like. As an added benefit, the composition does not require a hardening step for solidification to increase the strength or hardness of the solid, including the edges, which are known to be the weakest and most brittle parts of pressed solids. This immediate improvement in hardness upon pressing of the solid composition is an unexpected advance in the formulation of various alkaline compositions that can be formed into solids by pressing.

[0034] Without being limited to a particular mechanism of action for improving the hardness of the solid composition, the hardness additive composition provides a ratio of a dispersant polymer, i.e., a polycarboxylic acid polymer chelating agent, as a block hardening additive to an aminocarboxylate chelating agent for water hardness inhibition, which combination synergistically hardens the composition. It is unexpected that a particular combination of chelating agents provides improved solid hardness. Chelants are molecules that can coordinate (i.e., bind) metal ions commonly found in natural waters to prevent them from interfering with the action of other detergent ingredients in the cleaning composition. However, when the hardness additive composition is included in a solid composition, it is used in a unique ratio of polycarboxylic acid polymer chelating agent to aminocarboxylate chelating agent, and further, the polycarboxylic acid polymer chelating agent (e.g., Acusol polymer) may be combined in the solid composition at a weight ratio of less than about 4% by weight, and preferably about 2% by weight. These are lower concentrations than conventional use of polycarboxylic acid polymers for chelating.

[0035] Exemplary ranges of hardness additive compositions, as weight percentages of the composition, are set forth in Table 1. In various embodiments, the hardness additive composition is provided as a premix with at least two or at least three components provided. In one embodiment, the hardness additive composition provided as a premix of a solid composition is a liquid premix. [Table 1]

[0036] In some embodiments, the ratio of polycarboxylic acid polymer chelating agent to aminocarboxylate chelating agent provides synergistically improved hardening of the block. In one embodiment, the ratio of polycarboxylic acid polymer chelating agent to aminocarboxylate, preferably methylglycine diacetic acid (MGDA) or its salt, is at least about 0.06:1, at least about 0.1:1, at least about 0.12:1, at least about 0.48:1, or any ratio therebetween, including, for example, from about 0.06:1 to about 0.48:1, or from about 0.06:1 to about 0.12:1. In further embodiments, the ratio of polycarboxylic acid polymer chelating agent to aminocarboxylate, preferably glutamic acid N,N-diacetic acid (GLDA) or its salt in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt, is at least about 0.3:1 to about 1:1, or from about 0.3:1 to about 0.9:1. In yet another embodiment, the ratio of polycarboxylic acid polymer chelating agent to aminocarboxylate, preferably ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt, is from about 0.2:1 to about 0.5:1. Additionally, without being limited by the detergent compositions disclosed herein, all recited ratio ranges are inclusive of the numbers defining that range and include each integer within that defined ratio range.

[0037] In a preferred embodiment, the ratio of polycarboxylic acid polymer chelating agent to polyacrylate or polyacrylic acid polymer satisfies at least one of the following ratios and / or at least two of the following ratios: (A) the ratio of polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) or its salt in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt is from about 0.3:1 to about 0.9:1; (B) the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetate (MGDA) or its salt is from about 0.06:1 to about 0.48:1, or from about 0.06:1 to about 0.12:1; and (C) the ratio of polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or its salt is from 0.2:1 to about 0.5:1. In yet another preferred embodiment, the ratio of polycarboxylic acid polymer chelating agent to polyacrylate or polyacrylic acid polymer satisfies all three of the aforementioned ratios.

[0038] In some embodiments, in addition to the ratio of polycarboxylic acid polymer chelating agent to polyacrylate or polyacrylic acid polymer, there is a preferred total amount of premix containing a hardness additive added to the solid composition. In preferred embodiments, less than about 15 wt.% of the hardness additive composition premix is ​​added to the solid composition, preferably less than about 14 wt.%, preferably less than about 13 wt.%, preferably less than about 12 wt.%, preferably less than about 11 wt.%, preferably less than about 10 wt.%, or most preferably less than about 9 wt.% of the hardness additive composition premix is ​​added to the solid composition.

[0039] Solid detergent composition The hardness additive composition is suitable for inclusion in a variety of solid compositions, including detergent compositions such as alkali metal alkaline detergents for cleaning a variety of industrial and consumer surfaces. Exemplary ranges of detergent compositions are shown in Tables 2A-2B, expressed as weight percentages of the solid detergent composition. In Table 2A, the hardness additive composition may be provided as a premix, i.e., a liquid premix. One or more additional premixes, such as a liquid premix of surfactants, may be included in the formulation. [Table 2A] [Table 2B]

[0040] The detergent compositions disclosed herein may be solid concentrate compositions. A "solid" composition refers to a composition in the form of a solid, such as a powder, particle, aggregate, flake, granule, pellet, tablet, lozenge, puck, briquette, brick, solid block, unit dose, or another solid form known to those skilled in the art. The term "solid" 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 in solid form when exposed to elevated temperatures of 100°F, 112°F, and preferably 120°F. Pressed solids can take any form, including blocks. When referring to pressed solids, it means that the hardened composition will not visibly flow and will substantially retain its shape under moderate stress, pressure, or simple gravity. For example, the solid will maintain the shape of the mold when removed from the mold. The degree of hardness of the solid composition can range, but it is desirable that pressed solids containing the hardness additive composition have a relatively dense and hard molten solid block hardness similar to concrete.

[0041] Detergent compositions containing the hardness additive composition benefit from the absence of chips and gauges in the solid block. As an added benefit, the solid block does not exhibit brittle edges and can advantageously withstand physical stresses from the pressing, conveying, and packaging systems used.

[0042] The detergent compositions disclosed herein can be made available as concentrates (or as multiple concentrates that are diluted and combined) before or at the time of use to provide use solutions for application on various surfaces, i.e., hard surfaces. The advantage of providing concentrates for later combination or dilution is that they reduce shipping and storage costs, as they are cheaper to ship and store than use solutions and are more sustainable because less packaging is used.

[0043] Polycarboxylic acid polymer chelating agent The hardness additive composition (and solid compositions using same) includes at least one polycarboxylic acid polymer chelating agent, which is a dispersant polymer in the hardness additive composition. These chelating agents are also known as water treatment polymers. The polycarboxylic acid polymer chelating agent is a phosphorus-free chelating agent. Polycarboxylates include chelating polymers having pendant carboxylate (—CO2—) groups, such as polyacrylic acid homopolymer, polymaleic acid homopolymer, maleic acid / olefin copolymer, sulfonated copolymer or terpolymer, acrylic / maleic acid copolymer or terpolymer, polymethacrylic acid homopolymer, polymethacrylic acid copolymer or terpolymer, acrylic acid-methacrylic acid copolymer, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymer, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymer, and combinations thereof. For a further discussion of chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 5, pp. 339-366 and Vol. 23, pp. 319-320, the disclosures of which are incorporated herein by reference. These materials can also function as crystal modifiers when used at substoichiometric levels.

[0044] Polycarboxylic acid polymer chelating agents can include polyacrylic acid homopolymers and polymaleic acid homopolymers, as well as polymers modified with fatty acid end groups. Exemplary polyacrylic acid homopolymers include those having a molecular weight of about 500 to 100,000 g / mol, or about 1,000 to 50,000 g / mol, or about 1,000 to 25,000 g / mol. Exemplary suitable commercially available polyacrylic acid polymers include Acusol 445N (fully neutralized homopolymer of acrylic acid), Acusol 448, and Acusol 944, available from Dow Chemical.

[0045] In additional embodiments, acrylic acid homopolymers and / or mixtures of polymers containing acrylate monomers may be used.

[0046] In one embodiment, the hardness additive composition disclosed herein comprises from about 5% to about 40% by weight of a polycarboxylic acid polymer chelating agent, from about 10% to about 35% by weight of a polycarboxylic acid polymer chelating agent, from about 10% to about 30% by weight of a polycarboxylic acid polymer chelating agent, and preferably from about 10% to about 25% by weight of a polycarboxylic acid polymer chelating agent. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0047] In yet another embodiment, the solid detergent composition containing the hardness additive composition comprises from about 0.1% to about 5% by weight of the polycarboxylic acid polymer chelating agent, from about 0.5% to about 5% by weight of the polycarboxylic acid polymer chelating agent, from about 1% to about 5% by weight of the polycarboxylic acid polymer chelating agent, from about 1% to about 4% by weight of the polycarboxylic acid polymer chelating agent, or from about 1% to about 2% by weight of the polycarboxylic acid polymer chelating agent. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0048] Aminocarboxylate Chelators The hardness additive composition (and solid compositions employing same) comprises at least one aminocarboxylate (or aminocarboxylic acid) chelating agent. In preferred embodiments, the aminocarboxylate comprises an aminocarboxylic acid material that contains little or no NTA, or the detergent compositions disclosed herein are NTA-free. Exemplary aminocarboxylates include, for example, N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) (also referred to herein as ethylenediamine-N,N-tetraacetic acid, 2,2',2",2'"-(ethane-1,2-diyldinitrilo)tetraacetic acid), methylglycine diacetic acid (MGDA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), glutamic acid N,N-diacetic acid (GLDA), diethylenetriaminepentaacetic acid (DTPA), iminodisuccinic acid (IDS), ethylenediaminedisuccinic acid (EDDS), 3-hydroxy-2,2-iminodisuccinic acid (HIDS), hydroxyethyliminodiacetic acid (HEIDA), and other similar acids having an amino group with a carboxylic acid substituent. In one embodiment, the aminocarboxylate is ethylenediaminetetraacetic acid (EDTA).

[0049] In a preferred embodiment, the aminocarboxylate comprises, consists of, or consists essentially of ethylenediamine-N,N-tetraacetic acid, methylglycine diacetic acid, and glutamic acid N,N-diacetic acid.

[0050] In various embodiments, the hardness additive compositions and solid detergent compositions employ chelating agents that are substantially free of NTA-containing compounds, making the compositions more environmentally acceptable.

[0051] In one embodiment, the hardness additive composition disclosed herein comprises from about 60% to about 95% by weight of the aminocarboxylate chelating agent, from about 65% to about 90% by weight of the aminocarboxylate chelating agent, from about 70% to about 90% by weight of the aminocarboxylate chelating agent, and preferably from about 75% to about 90% by weight of the aminocarboxylate chelating agent. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0052] In yet another embodiment, the solid detergent composition containing the hardness additive composition comprises from about 5% to about 45% by weight of the aminocarboxylate chelating agent, from about 5% to about 40% by weight of the aminocarboxylate chelating agent, from about 5% to about 35% by weight of the aminocarboxylate chelating agent, from about 5% to about 30% by weight of the aminocarboxylate chelating agent, or from about 5% to about 25% by weight of the aminocarboxylate chelating agent. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0053] Alkaline source In one embodiment, the detergent compositions disclosed herein include an alkaline source. In one embodiment, the alkaline source is preferably an alkali metal hydroxide and / or alkali metal carbonate. Suitable alkali metal hydroxides and carbonates include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide. In another embodiment, the alkali metal carbonates and alkali metal hydroxides are further understood to include bicarbonates and sesquicarbonates. It should also be understood that, according to the detergent compositions disclosed herein, any "ash-based" or "alkali metal carbonate" includes all alkali metal carbonates, bicarbonates, and / or sesquicarbonates. In a preferred embodiment, the alkaline source is an alkali metal carbonate. In some other preferred embodiments, the alkaline source is an alkali metal carbonate free of unreacted alkali metal hydroxide. In even more preferred embodiments, the alkaline cleaning composition does not include an organic alkaline source.

[0054] The alkaline source is provided in an amount sufficient to provide a use solution of the detergent compositions disclosed herein having a pH of at least about 8, at least about 9, at least about 10, at least about 11, or at least about 12. The pH range of the use solution is preferably from about 8.0 to about 13.0, more preferably from about 10 to 12.5.

[0055] In one embodiment, the detergent composition comprises from about 20% to about 90% by weight of the alkaline source, from about 20% to about 80% by weight of the alkaline source, from about 30% to about 80% by weight of the alkaline source, from about 40% to about 80% by weight of the alkaline source, from about 40% to about 75% by weight of the alkaline source, and preferably from about 50% to about 80% by weight of the alkaline source. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0056] Additional Functional Ingredients The components of the claimed detergent compositions can be further combined with various functional components suitable for use in warewashing and other applications using alkaline detergents or cleaning compositions. In some embodiments, the claimed detergent compositions, including the hardness additive composition (including the polycarboxylic acid polymer chelating agent and the aminocarboxylate chelating agent), alkalinity source, nonionic surfactant, and any additional chelating agent / builder, comprise a majority or substantially all of the total weight of the detergent composition. For example, in some embodiments, little or no additional functional ingredients are disposed therein.

[0057] In other embodiments, additional functional ingredients may be included in the claimed detergent compositions. The functional ingredient provides the composition with desired properties and functionality. For purposes of this application, the term "functional ingredient" includes materials 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 materials are discussed in more detail below, although the specific materials discussed are provided merely as examples, and a variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning, particularly warewashing applications. However, other embodiments may include functional ingredients for use in other applications.

[0058] In a preferred embodiment, the detergent composition does not contain the chelating agent NTA. In a further preferred embodiment, the detergent composition does not contain silicate. In yet another preferred embodiment, the detergent composition does not contain phosphate and / or phosphonate. In yet another preferred embodiment, the detergent composition does not contain silicate, NTA, phosphate and / or phosphonate.

[0059] The compositions may also include additional anti-foaming agents, anti-redeposition agents, bleaching agents, solubility modifiers, dispersants, rinse aids, metal protectants (etch prevention), enzymes, stabilizers, corrosion inhibitors, metal catalysts, additional sequestering and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, hydrotropes, or color formers, buffers, solvents, and the like.

[0060] Antifoaming agents The detergent compositions disclosed herein may optionally contain an antifoaming agent. The antifoaming agent is preferably a nonionic surfactant. In a preferred embodiment, the antifoaming agent is a nonionic alkoxylated surfactant. In another preferred embodiment, the antifoaming agent is represented by the formula RO-(PO) 0-5 (EO) 1-30 (PO) 1-30 , or RO-(PO) 1-30 (EO) 1-30 (PO) 1-30 wherein R is C 8-18 Linear or branched alkyl groups, EO = ethylene oxide, PO = propylene oxide. Exemplary suitable alkoxylated surfactants include ethylene oxide / propylene block copolymers (EO / PO copolymers) such as those available under the names Pluronic or Plurafac®, capped EO / PO copolymers, partially capped EO / PO copolymers, fully capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof, and the like.

[0061] Other antifoaming agents include silicone compounds such as silica dispersed in polydimethylsiloxane, polydimethylsiloxane, and functionalized polydimethylsiloxane, such as that available under the name Abil B9952, fatty amides, hydrocarbon waxes, fatty acids, fatty acid esters, fatty alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene glycol esters, alkyl phosphate esters such as monostearyl phosphate, etc. Discussions of antifoaming agents 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 for all purposes.

[0062] 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 alkali oxide moiety, typically ethylene oxide or its polyhydrated product, polyethylene glycol. Specifically, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydrated additives, 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 balance between hydrophilic and hydrophobic properties. According to the present invention, the nonionic surfactant useful in the composition is a low-foaming nonionic surfactant. Examples of nonionic low-foaming surfactants useful in the present invention include the following:

[0063] Block polyoxypropylene-polyoxyethylene polymer compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Examples of polymer compounds made from sequential propoxylation and ethoxylation of the initiator are commercially available under the tradenames Pluronic® and Tetronico from BASF Corp. Pluronic® compounds are 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 1,000 to 4,000. Ethylene oxide is then added to sandwich the hydrophobic material between hydrophilic groups, with the length controlled to comprise about 10% to about 80% by weight of the final molecule. Tetronic® compounds are tetrafunctional block copolymers obtained by the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from 500 to 7,000, and the hydrophilic ethylene oxide comprises 10% to 80% by weight of the molecule.

[0064] Condensation products of one mole of alkylphenol, in which the alkyl chain, linear or branched, or single or double alkyl moiety, contains 8 to 18 carbon atoms, with 3 to 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 be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercially available compounds of this chemistry are available on the market under the trade names Igepal®, manufactured by Rhone-Poulenc, and Triton®, manufactured by Dow.

[0065] The condensation product of one mole of a saturated or unsaturated, straight- or branched-chain alcohol having 6 to 24 carbon atoms with 3 to 50 moles of ethylene oxide. The alcohol portion can consist of a mixture of alcohols within the carbon range described above, or can consist of an alcohol having a specific number of carbon atoms within this range. Examples of similar commercially available surfactants are available under the trade names Neodol® manufactured by Shell Chemical Co. and Alfonic® manufactured by Vista Chemical Co.

[0066] The condensation product of one mole of a saturated or unsaturated, straight- or branched-chain carboxylic acid having 8 to 18 carbon atoms with 6 to 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 commercially available compounds of this chemistry are available on the market under the trade names Nopalcol®, manufactured by Henkel Corporation, and Lipopeg®, manufactured by Lipo Chemicals, Inc.

[0067] The following structure: RO-(PO) 0-5 (EO) 1-30 (PO) 1-30 wherein R is a C8-18 linear or branched alkyl group, EO=ethylene oxide, and PO=propylene oxide.

[0068] Compounds from (1) modified, essentially inverted, by adding ethylene oxide to ethylene glycol to provide a hydrophile of a specified molecular weight; then adding propylene oxide to obtain a hydrophobic block on the outside (end) of the molecule. The hydrophobic portion of the molecule has a molecular weight between 1,000 and 3,100, and the central hydrophile comprises 10% to 80% by weight of the final molecule. These inverted Pluronics® are manufactured by BASF Corporation under the trade name Pluronic® R surfactants.

[0069] An alkoxylated diamine produced by the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The hydrophobic portion of the molecule has a molecular weight of 250 to 6,700, with the central hydrophile comprising 0.1% to 50% by weight of the final molecule. Commercially available examples of this chemistry are available from BASF Corporation under the trade name Tetronic™ surfactants.

[0070] An alkoxylated diamine produced by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of the molecule has a molecular weight of 250 to 6,700, with the central hydrophile comprising 0.1% to 50% by weight of the final molecule. Commercially available examples of this chemistry are available from BASF Corporation under the trade name Tetronic® surfactants.

[0071] Disclosed herein are compounds modified by "capping" or "end-blocking" the terminal hydroxy groups (of polyfunctional moieties) to reduce foaming from reactions of hydrophobic small molecules, such as propylene oxide, butylene oxide, or benzyl chloride, with short-chain fatty acids containing 1 to 5 carbon atoms, alcohols, or alkyl halides, and mixtures thereof. Also included are reactants, such as thionyl chloride, that convert the terminal hydroxy groups to chloride groups. Such modifications to the terminal hydroxy groups can result in all-block, block-hetero, hetero-block, or all-hetero nonionic materials.

[0072] The polyoxyalkylene surfactants advantageously used in the compositions of the present invention have the formula: P[(C3H6O) n (C2H4O) m H] xwhere P is the residue of an organic compound having 8 to 18 carbon atoms and containing x reactive hydrogen atoms, where x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least 44, and m has a value such that the oxypropylene content of the molecule is 10% to 90% by weight. In either case, the oxypropylene chains may optionally, but advantageously, contain small amounts of ethylene oxide, and the oxyethylene chains may optionally, but advantageously, contain small amounts of propylene oxide.

[0073] Alkoxylated amine, or most specifically alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants are at least partially represented by the following general formula: R 20 --(PO) s N-(EO) t H, R20--(PO) s N-(EO) t H(EO) t H, and R 20 --N(EO) t H, In the formula, R 20 is an alkyl, alkenyl, or other aliphatic group of 8 to 20, preferably 12 to 14 carbon atoms, or an alkyl-aryl group; 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 in the scope of these compounds are represented by the alternative formula: R 20 --(PO) v --N[(EO) w H][(EO) z H] where 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.

[0074] In one embodiment, the detergent composition comprises from about 0% to about 15% by weight of antifoaming agent, from about 0.5% to about 10% by weight of antifoaming agent, from about 0.5% to about 5% by weight of antifoaming agent, and preferably from about 0.5% to about 3%, about 1%, about 3%, about 5%, or about 10% by weight of antifoaming agent. Additionally, without being limited by the detergent compositions disclosed herein, all recited ranges are inclusive of the numbers defining the range and include each integer within the defined range.

[0075] phosphonates In some embodiments, the claimed detergent compositions may comprise a phosphonate. Examples of phosphonates include phosphinosuccinic acid oligomers (PSO), as described in U.S. Patents 8,871,699 and 9,255,242; 2-phosphinobutane-1,2,4-tricarboxylic acid (PBTC); 1-hydroxyethane-1,1-diphosphonic acid, CHC(OH)[PO(OH)]; aminotri(methylenephosphonic acid), N[CHPO(OH)]; aminotri(methylenephosphonic acid); phosphonate), sodium salt (ATMP), N[CH2PO(ONa)2]3; 2-hydroxyethyliminobis(methylenephosphonic acid), HOCH2CH2N[CH2PO(OH)2]2; diethylenetriaminepenta(methylenephosphonic acid), (HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2; diethylenetriaminepenta(methylenephosphonate), sodium salt (DTPMP), CH (28-x) N3Na x O 15 P5(x=7); Hexamethylenediamine(tetramethylenephosphonate), potassium salt, C10 H (28-x) N2K x O 12 Examples of suitable phosphonates include, but are not limited to, P4 (x=6); bis(hexamethylene)triamine (pentamethylene phosphonic acid), (HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2; monoethanolamine phosphonate (MEAP); diglycolamine phosphonate (DGAP) and phosphoric acid, H3PO3. Preferred phosphonates are PBTC, HEDP, ATMP, and DTPMP. Preferably, the phosphonate or alkali phosphonate, or the combination of the phosphonate and alkali source, is neutralized before being added to the mixture, so that upon addition of the phosphonate, little or no heat or gas is generated by the neutralization reaction. However, in one embodiment, the claimed detergent composition does not contain phosphorus.

[0076] Suitable amounts of phosphonate included in the detergent compositions disclosed herein include from about 0% to about 25% by weight of the detergent composition, from about 0.1% to about 20%, from about 0% to about 15%, from about 0% to about 10%, from about 0% to about 5%, from about 0.5% to about 10%, from about 0.5% to about 5%, or from about 0.5% to about 15% by weight of the detergent composition.

[0077] surfactants In some embodiments, the detergent compositions disclosed herein comprise a surfactant. In some other embodiments, the detergent compositions disclosed herein comprise a nonionic anti-foam surfactant or agent. In some other embodiments, the detergent compositions disclosed herein comprise an additional surfactant along with the nonionic anti-foam surfactant or agent. Surfactants suitable for use with the detergent compositions disclosed herein include, but are not limited to, additional nonionic surfactants, anionic surfactants, cationic surfactants, and zwitterionic surfactants. In yet some other embodiments, the detergent compositions disclosed herein do not comprise any additional surfactant other than one or more nonionic anti-foam surfactants or agents.

[0078] In some embodiments, the detergent compositions disclosed herein comprise, in addition to the nonionic antifoam surfactant or agent, about 0% to about 50% by weight of additional surfactant, about 0% to about 25% by weight, about 0% to about 15% by weight, about 0% to about 10% by weight, or about 0% to about 5% by weight, about 0% by weight, about 0.5% by weight, about 1% by weight, about 3% by weight, about 5% by weight, about 10% by weight, or about 15% by weight of additional surfactant.

[0079] Anionic surfactants Surface-active substances classified as anionic surfactants because the hydrophobic group is negatively charged, or surfactants in which the hydrophobic portion of the molecule does not carry a charge unless the pH is raised above neutral (e.g., carboxylic acids), are also useful in the detergent compositions disclosed herein. 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 solubility and oil solubility, and calcium, barium, and magnesium promote oil solubility. As will be understood by those skilled in the art, anionic surfactants are excellent detersive surfactants and are therefore preferred additions to heavy-duty detergent compositions.

[0080] Anionic sulfate surfactants suitable for use in the claimed detergent 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 17These include alkylpolysaccharide sulfates such as acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as the sulfates or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 oxyethylene groups per molecule).

[0081] Anionic sulfonate surfactants suitable for use in the claimed detergent compositions also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0082] Anionic carboxylate surfactants suitable for use in the claimed detergent compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleic acid, and the like. 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 connected to a secondary carbon. The secondary carbon may be in a ring structure, such as in p-octyl benzoic acid or alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants generally do not contain ether or ester bonds or hydroxyl groups. Furthermore, they generally lack a nitrogen atom in the head group (amphiphilic portion). Suitable secondary soap surfactants generally contain 11 to 13 total carbon atoms, although more carbon atoms may be present, e.g., up to 16. Suitable carboxylates also include acylamino acids (and salts), such as, for example, acyl glutamates, acyl peptides, sarcosinates (e.g., N-acylsarcosinates), taurates (e.g., N-acyltaurates and fatty acid amides of methyl tauride).

[0083] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH2CH2O) n (CH2) m -CO2X (3) where R is C-C 22 is an alkyl group, or [ka] , R 1 is C4-C 16is 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-C 16 In some embodiments, R is a C 12 -C 14 It is an alkyl group, n is 4, and m is 1.

[0084] In other embodiments, R is [ka] and R 1 is C6-C 12 In still other embodiments, R 1 is a C9 alkyl group, n is 10, and m is 1.

[0085] 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, such as the product Sandopan® DTC, C alkyl polyethoxy (4) carboxylic acid (Shell Chemical), and Emcol CNP-110, C alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical). 13 Alkylpolyethoxy(7)carboxylic acids are also available from Clariant.

[0086] Cationic surfactants Cationic Quaternary Surfactants / Quaternary Alkylamine Alkoxylates Cationic quaternary surfactants are materials based on a nitrogen-centered cationic moiety that have a net positive charge. Suitable cationic surfactants contain a quaternary ammonium group. Suitable cationic surfactants are particularly those of the general formula: N (+) R 1 R 2 R 3 R 4 X (-) wherein R 1 , R 2 , R 3 , and R 4 are each independently an alkyl group, an aliphatic group, an aromatic group, an alkoxy group, a polyoxyalkylene group, an alkylamide group, a hydroxyalkyl group, an aryl group, or H + ions, each having 1 to 22 carbon atoms, and a group R 1 , R 2 , R 3 , and R 4 and X(-) represents an anion, such as a halogen, acetate, phosphate, nitrate, or alkyl sulfate, preferably chloride, provided that at least one of the groups has at least 8 atoms. The aliphatic group may also contain bridging groups or other groups, such as additional amino groups in addition to the carbon and hydrogen atoms.

[0087] Specific cationic active ingredients include, for example, but are not limited to, alkyldimethylbenzylammonium chloride (ADBAC), alkyldimethylethylbenzylammonium chloride, dialkyldimethylammonium chloride, benzethonium chloride, N,N-bis-(3-aminopropyl)dodecylamine, chlorhexidine gluconate, organic and / or organic salts of chlorhexidene gluconate, PHMB (polyhexamethylene biguanide), salts of biguanides, substituted biguanide derivatives, organic salts of quaternary ammonium-containing compounds or inorganic salts of quaternary ammonium-containing compounds, or mixtures thereof.

[0088] 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 can be directly attached to the nitrogen atom by simple substitution, or more preferably, indirectly attached through a bridging functional group 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.

[0089] Surfactant compounds classified as amine oxides, amphoterics, and zwitterions are themselves generally 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.

[0090] The simplest cationic amines, amine salts and quaternary ammonium compounds are depicted schematically 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. Amine salts and quaternary ammonium compounds are preferred for practical use in the present invention due to their high degree of water solubility.

[0091] Preferred cationic quaternary ammonium compounds are: [ka] where R represents a C8-C18 alkyl or alkenyl, and R 1 and R 2 is a C1-C4 alkyl group, n is 10 to 25, and x is an anion selected from a halide or methyl sulfate.

[0092] The majority of large-scale commercial cationic surfactants are known to those skilled in the art and can be subdivided into four major classes and additional subgroups, as 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 gel formation in conjunction with other agents, and the like.

[0093] Cationic surfactants useful in the detergent compositions claimed herein are those of the formula R 1 m R 2 x YLZ (wherein each R 1 is an organic group containing a linear or branched alkyl or alkenyl group optionally substituted with up to three phenyl or hydroxy groups and optionally interrupted with up to four of the following structures: [ka] or isomers or mixtures of these structures containing 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 2 is 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.

[0094] Y is as follows: [ka] or a group containing a mixture thereof, but is not limited thereto.

[0095] Preferably, L is 1 or 2, and when L is 2, the Y group is an R group having 1 to 22 carbon atoms and two free carbon single bonds. 1 and R 2 Z is a water-soluble anion such as sulfate, methylsulfate, hydroxide, or nitrate, with sulfate or methylsulfate being particularly preferred in a number that confers electroneutrality to the cationic component.

[0096] Suitable concentrations of cationic quaternary surfactants in the claimed detergent compositions can be from about 0% to about 10% by weight of the claimed detergent compositions.

[0097] amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups.These ionic entities can be either anionic or cationic groups as 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 some surfactants, sulfonate, sulfate, phosphonate, or phosphate provide negative charge.

[0098] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical can be straight-chain or branched, one of the aliphatic substituents contains approximately 8 to 18 carbon atoms, and one contains an anionic water-solubilizing group, such as carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are known to those skilled in the art and are subdivided into two main classes, as 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 can be considered to fit into both classes.

[0099] 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.Commercially available amphoteric surfactants are derivatized by subsequent hydrolysis and alkylation to open the imidazoline ring, for example, using 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.

[0100] Long chain imidazole derivatives having use in the present invention generally have the following general formula: [ka] Neutral pH Zwitterions Amphoteric sulfonates [ka] In the formula, R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation, typically sodium, to neutralize the charge of the anion. Commercially known imidazoline-derived amphoteric compounds that can be used in the present composition include, for example, cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. Amphocarboxylic acids can be generated from aliphatic imidazolines, where the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0101] The carboxymethylated compounds (glycinates) described herein above are often referred to as betaines. Betaines are a special class of amphoteric compounds described herein below in the section entitled Zwitterionic Surfactants.

[0102] Long-chain N-alkyl amino acids are readily prepared by the reaction RNH2, where R = C8-C 18These are aliphatic amines with straight-chain or branched alkyl or 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 multiple 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 that have application in the present invention 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.

[0103] 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 from Rhodia Inc., Cranbury, NJ under the trade name Miranol™ FBS. 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.

[0104] A typical list of amphoteric classes and species of these surfactants is described in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are described 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.

[0105] Zwitterionic surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and may 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 sometimes sulfonium or phosphonium ion, a negatively charged carboxyl group, and an alkyl group. Zwitterionic compounds generally contain cationic and anionic groups that ionize to approximately the same degree in the isoelectric region of the molecule, which can create a strong "inner salt" attraction 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 radicals can be straight-chain or branched, and in which one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0106] Betaine and sultaine surfactants are examples of zwitterionic surfactants for use herein. The general formula for these compounds is: [ka] In the formula, R 1comprises 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; R 2 is an alkyl group or a monohydroxyalkyl group containing 1 to 3 carbon atoms, x is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen atom or a phosphorus atom, and R 3 is an alkylene or hydroxyalkylene or hydroxyalkylene of 1 to 4 carbon atoms, and Z is a radical selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfate group, a phosphonate group, and a phosphate group.

[0107] 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 such detergent surfactants may be straight-chained or branched, saturated or unsaturated.

[0108] Zwitterionic surfactants suitable for use in the present compositions include betaines of the following general structure: [ka] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH or exhibit reduced water solubility in these isoelectric ranges. 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.

[0109] Sultaines useful in the present invention have the formula (R(R 1 )2N + R 2 SO 3- where R is C6-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.

[0110] A typical listing of zwitterionic classes and species of these surfactants is found in U.S. Patent No. 3,929,678, issued December 30, 1975, to Laughlin and Heuring. Further examples are found 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.

[0111] enzyme The detergent compositions disclosed herein can further comprise enzymes that remove soil, prevent redeposition, and additionally promote foam reduction in the use solution of the cleaning composition. The purpose of the enzyme is to break down sticky soils, such as starch or proteinaceous materials, that are typically found on soiled surfaces and are removed by the detergent composition into the wash water source. The enzymes remove soil from the substrate and prevent soil redeposition on the substrate surface. The enzymes provide additional cleaning and detergent benefits, such as antifoaming.

[0112] Exemplary types of enzymes that can be incorporated into detergent compositions or detergent use solutions include amylases, proteases, lipases, cellulases, cutinases, gluconases, peroxidases, and / or mixtures thereof. The detergent compositions disclosed herein may use multiple enzymes from any suitable source, such as plant, animal, bacterial, fungal, or yeast sources. However, according to preferred embodiments of the detergent compositions disclosed herein, the enzyme is a protease. As used herein, the term "protease" or "proteinase" refers to an enzyme that catalyzes the hydrolysis of peptide bonds.

[0113] As those skilled in the art will recognize, enzymes are designed to work on specific types of soils. For example, according to one embodiment of the present invention, protease enzymes may be used in warewashing applications because they are effective in high-temperature warewashing machines and for reducing protein-based soils. Protease enzymes are particularly useful for cleaning protein-containing soils, such as blood, skin scale, mucus, grass, and food (e.g., eggs, milk, spinach, meat residues, tomato sauce). Protease enzymes can cleave macromolecular protein linkages of amino acid residues, converting the substrate into smaller fragments that are easily soluble or dispersible in aqueous solutions. Proteases are often referred to as detersive enzymes due to their ability to destroy soils through a chemical reaction known as hydrolysis. Protease enzymes can be obtained, for example, from Bacillus subtilis, Bacillus licheniformis, and Streptomyces griseus. Protease enzymes are also commercially available as serine endoproteases. Examples of commercially available protease enzymes are available under the following trade names: Esperase, Purafect, Purafect L, Purafect Ox, Everlase, Liquanase, Savinase, Prime L, Prosperase, and Blap.

[0114] For the detergent compositions disclosed herein, enzymes can vary based on the particular cleaning application and the type of soil requiring cleaning. For example, the temperature of a particular cleaning application will influence the enzymes selected for the detergent compositions disclosed herein. For example, warewashing applications clean substrates at temperatures above about 60°C, or above about 70°C, or about 65-80°C, and enzymes such as proteases are desirable due to their ability to retain enzymatic activity at such high temperatures.

[0115] The enzymes for the detergent compositions disclosed herein may be independent entities and / or may be incorporated into detergent compositions.In addition, enzymes may be incorporated into various delayed or controlled release formulations.For example, solid molded detergent compositions may be prepared without the application of heat.As those skilled in the art will understand, enzymes tend to be denatured by the application of heat, and therefore, the use of enzymes in the claimed detergent compositions requires a method of forming detergent compositions that does not rely on heat as a step in the forming process, such as solidification.

[0116] Enzymes may also be commercially available in solid (i.e., packs, powders, etc.) or liquid formulations. Commercially available enzymes are generally combined with stabilizers, buffers, cofactors, and inert media. The actual active enzyme content will depend on the method of preparation, which is well known to those skilled in the art, and such method of preparation is not critical to the present invention.

[0117] Alternatively, the enzymes may be provided separately from the claimed detergent compositions for a particular use, for example, added directly to the washing liquor or wash water of a dishwasher.

[0118] Further description of enzymes suitable for use in the detergent compositions disclosed herein is disclosed in, for example, U.S. Pat. Nos. 7,670,549, 7,723,281, 7,670,549, 7,553,806, 7,491,362, 6,638,902, 6,624,132, and 6,197,739, and U.S. Patent Publication Nos. 2012 / 0046211 and 2004 / 0072714, each of which is incorporated by reference herein in its entirety. Additionally, the reference "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, is incorporated herein in its entirety.

[0119] In preferred embodiments, the enzymes provided in the detergent compositions disclosed herein are in an amount from about 0.01% to about 40%, from about 0.01% to about 30%, from about 0.01% to about 10%, from about 0.1% to about 5%, and preferably from about 0.5% to about 2% by weight of the detergent composition.

[0120] How to make / improve solid block hardness The solid compositions disclosed herein can be formed by combining the components in the weight percentages and ratios disclosed herein. The detergent compositions disclosed herein can be provided as solids, and a use solution is formed during the warewashing process (or other use application).

[0121] The solid detergent compositions disclosed herein can be formed using a hardness additive composition that can be provided as a premix, or individual components of the hardness additive composition can be mixed separately with additional components of the detergent composition and mixed during manufacture. The method includes mixing the hardness additive composition with the detergent composition components to form a homogeneous mixture. The method further includes pressing the mixture into a mold to form a solid composition.

[0122] The method for producing the solid can be carried out using a batch or continuous mixing system. In an exemplary embodiment, a single- or twin-screw extruder is used to combine and mix the components together, optionally with high shear, to form a homogeneous mixture. The solid detergent composition processed according to the method of the present invention is substantially homogeneous in terms of the distribution of ingredients throughout its mass and is dimensionally stable.

[0123] Specifically, in the forming process, liquid and solid components are introduced into a final mixing system and mixed sequentially until the components form a substantially homogeneous semi-solid mixture with the components distributed throughout its mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 5 seconds, at least approximately 15 seconds, at least approximately 30 seconds, or more. The mixture is then ejected from the mixing system into a pressing mold. The solid is removed from the mold, unexpectedly providing a fast-setting solid, such as a solid block with no brittle edges and requiring no curing step. In one embodiment, the solid is not cured.

[0124] A variety of pressures can be used to form the solid composition. For example, in some embodiments, the method of making the solid can use pressures on the solid of up to about 90,000 psi, up to about 80,000 psi, up to about 70,000 psi, or up to about 60,000 psi.

[0125] The instantaneous hardening of the pressed solid beneficially helps maintain its physical integrity through the mechanical transport system, including ejection from the press mold. The solid can be packaged immediately upon ejection or removal from the press mold. In exemplary embodiments, the formed solid begins to instantly harden into a solid form within a few seconds to approximately one minute. The solid does not exhibit brittle edges, large or small chips, and / or gag or chunks that would break apart due to breakage during the mechanical transport system of the press. This beneficially enables a continuous processing or production system that does not require the hardening of the solid block, which is typically required to remove the solid block from the transport system (often requiring additional time before packaging).

[0126] The resulting solid detergent composition can take any form, including, but not limited to, a pressed solid block. The solid can be formed into a variety of shapes based on the selection of the desired mold. The weight and size of the solid can vary, as will be understood by those skilled in the art, including from approximately 50 grams to approximately 250 grams, approximately 100 grams or more, or from approximately 1 to approximately 10 kilograms. In some embodiments, the solid composition can be dissolved, for example, in an aqueous or other medium, to produce a concentrated solution and / or a use solution. This solution can be directed to a reservoir for subsequent use and / or dilution, or can be applied directly to the point of use.

[0127] All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention 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]

[0128] Embodiments of the solid detergent compositions, hardness additive compositions, and methods for making the same disclosed herein are further defined in the following non-limiting examples. Although these examples illustrate specific embodiments of the detergent compositions, hardness additive compositions, and methods for making the same disclosed herein, it should be understood that they 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 embodiments and can make various changes and modifications to the embodiments of the detergent compositions disclosed herein to adapt them to various uses and conditions without departing from the spirit and scope thereof. Thus, in addition to those shown and described herein, various modifications of the embodiments disclosed 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.

[0129] A variety of solid detergent compositions were evaluated, as shown in Table 3 of the Examples. The various components used in Table 3 refer to both generic and trade names, including: Ash - sodium carbonate, Trilon M-methylglycine-N,N-diacetic acid sodium salt (MGDA), 78% active; EDTA - Ethylenediamine-N,N-tetraacetic acid, 99% active, GLDA-N,N-dicarboxymethylglutamic acid tetrasodium salt, Acusol 445 - polyacrylic acid available from DOW Chemical; Acusol 944 - acrylic acid homopolymer available from DOW Chemical; Enzymes - protease enzymes. [Table 3A] [Table 3B]

[0130] Example 1 The edge hardness of the blocks was evaluated according to the following procedure.

[0131] 1. Remove the pressed blocks from the conveyor line within two minutes of them being ejected from the press.

[0132] 2. Insert the pressed block into a plastic container that can collect all the loose powder that falls from the block. The bottom of the block needs to be in contact with the plastic container.

[0133] 3. Grasp the top 1 / 4 of the block with both hands (using chemical resistant gloves). Rock the block back and forth 6 times to loosen any powder on the edges of the block.

[0134] 4. Immediately after rocking the block, rotate the block clockwise twice and counterclockwise twice around the complete bottom edge of the block.

[0135] 5. The final step in removing the loose powder is to use your available hands to brush off any remaining loose powder that has not fallen into the plastic container. In this final step, do not forcefully brush the powder off the block; instead, remove the loose particles.

[0136] 6. Take the remaining powder in the plastic container, weigh it, and record the amount.

[0137] 7. Repeat this method with at least five blocks from every batch. For long, complete production batches, take five blocks from the beginning, middle, and end of the batch.

[0138] These methods aim to quantify the loss of mass (in grams) from the weak bottom edge of the pressed block composition. The threshold for acceptable loose powder loss is determined on a scale based on commercial production of the product. For example, for a 3000 gram solid block, less than about 0.7 grams of lost loose powder is required. A minimal amount of block mass loss (measured by total weight of loose powder) is desired. In one embodiment, from a manufacturing perspective, the goal is to obtain at least about a 95%, or preferably a 97%, yield from production (representing a loss or "scrap rate" of 5% or 3%, respectively).

[0139] The initial production of the P0 formulation (a control without the hardness additive composition) resulted in significantly higher scrap rates and failed to achieve a 97% production yield. The evaluation is intended to identify compositions containing the hardness additive composition that offer improvements over the P0 (control) in terms of total loose powder loss. Based on the boxplot, the desired threshold for powder mass loss is less than 3.54 grams (indicating a 25% scrap rate), preferably less than 1.82 grams (indicating a 5% scrap rate or less), and most preferably less than 1.08 grams. For a 3000 gram solid block composition, measurements between 1.82 grams and 2.75 grams result in a scrap rate of less than about 5%, while measurements below 1.36 grams result in a scrap rate of approximately 0%. Those skilled in the art can calculate the desired scrap rate based on different sizes (i.e., total block weights) of solid compositions using the hardness additive composition.

[0140] An evaluation of total loose powder from P0 (a control block containing no hardness additive composition) was conducted compared to P1 and P7 formulations. Results are shown in Figure 1, which displays a boxplot showing total loose powder from three evaluations; the first evaluation included 12–13 days of curing of the block (providing the block with an additional 12–13 days of curing); the second and third evaluations did not include curing; instead, edge hardness evaluations were conducted immediately after the block was removed from the press mold. The first data set, evaluating formulation P0 (a control containing no hardness additive composition) even after 12–13 days of curing, demonstrated powder loss from the block above the acceptable threshold. Composition P7 demonstrated a loss of approximately <1.82 grams, and P1 demonstrated a loss of approximately <2.75 grams, illustrating that the hardness additive composition in the formulation improves edge hardness immediately after pressing (without a curing period).

[0141] Example 2 Edge hardness of additional blocks of formulation P0 compared to P1, P2, P3, and P4 was performed according to the formulations in Table 3 and the method described in Example 1. As shown in Figure 2, the negative control P0 still failed to exhibit sufficient block hardness, as measured by total loose powder mass loss. Improved block hardness was exhibited by formulations P1, P2, P3, and P4, demonstrating a reduction in total loose powder mass loss. Each of these formulations demonstrated a loss of approximately <2.75 grams, illustrating that the hardness additive composition in the formulations improves edge hardness immediately after pressing (without a curing period).

[0142] Example 3 Edge hardness of additional blocks of formulations P1, P2, P3, P4, P7, P8 (positive control), and P9 (positive control) was performed according to the formulations in Table 3 and the method described in Example 1. Testing was performed for P8 and P0 in a separate location (same setup and methodology) from the remaining tests. As illustrated in Figure 3, in addition to the block mass weight loss (grams), the overall percentage of pressed blocks deemed defective due to insufficient curing immediately after pressing caused powder loss due to brittle edges of the blocks. As shown, the threshold set forth in Example 1 as commercially acceptable is having no more than 5% block defects overall, preferably 0% defects.

[0143] Figure 3 shows that the P0 negative control formulation resulted in pressed solids with unacceptable levels of loose powder mass loss, including rejection rates of at least 25% or at least 50%. The P0 formulation failed to harden (unlike Example 1 and Figure 1), indicating that the immediate block hardness of the P0 negative control was inferior to the hardened block strength. This further demonstrates that block hardness immediately after pressing a solid is a more difficult requirement to meet. The deformation of the P7 formulation was the result of removing 1% Trilon M from P1, which resulted in a wetter formulation. Figure 3 also shows the improved block hardness compared to P0 for the various evaluated formulations P1, P2, P3, P4, and P7. The positive controls P8, P9, P10, which do not contain any hardening additive composition, also performed well and provided immediate hardness, which is believed to be a result of the P8 and P9 formulations not containing Acusol 445, and P10 containing Acusol 448, resulting in the P8 formulation having increased phosphate in the formulation and P9 being a silicated formulation.

[0144] Figure 4 shows an overall comparison of all evaluated formulations containing the hardness additive composition ("New") compared to formulations without the hardness additive composition ("Original") based on scrap rates during the production process. As shown, a statistically significant improvement in immediate block hardness is observed with the hardness additive composition. For improved solid compositions containing the hardness additive composition, a scrap rate of less than about 5% is the desired commercial result. As referred to herein, scrap rate refers to the commercial production threshold of the number of blocks per 100 that do not meet commercially acceptable standards; for example, blocks having any chunks of the formulation missing after ejection from the press die, or for a 3000 gram solid block, having less than about 0.7 grams of lost loose powder within the shrink wrap and chunks greater than 1 inch in diameter. As shown, a significant reduction in scrap rate is observed for the new formulations containing the hardness additive composition.

[0145] The invention being thus described, it will be apparent that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims. 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 invention, the invention resides in the claims.

[0146] The features disclosed in the foregoing description, or in the following claims, or the accompanying drawings, whether presented in a particular form or in terms of means for performing a disclosed function, or a method or process for achieving a disclosed result, may be utilized, separately or in any combination of such features, as appropriate, to realize the invention in diverse forms thereof. Examples of embodiments of the present invention are listed in the following items [1] to

[19] . [1] 1. A hardness additive composition comprising: about 5% to about 40% by weight of the composition of at least one polycarboxylic acid polymeric chelating agent comprising a polyacrylate or polyacrylic acid polymer or homopolymer; from about 60% to about 95% by weight of the composition of at least one aminocarboxylic acid chelating agent comprising one or more of ethylenediamine-N,N-tetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), and glutamic acid N,N-diacetic acid (GLDA); The ratio of polycarboxylic acid polymer chelating agent to polyacrylate or polyacrylic acid polymer is in the following ratio: (A) the ratio of polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) or a salt thereof in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is from about 0.3:1 to about 0.9:1; (B) the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or a salt thereof is from about 0.06:1 to about 0.12:1; and / or (C) a hardness additive composition having a ratio of polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof of about 0.2:1 to about 0.5:1. [2] 2. The composition of claim 1, wherein the aminocarboxylate chelating agent comprises ethylenediamine-N,N-tetraacetic acid, methylglycine diacetic acid, and glutamic acid N,N-diacetic acid. [3] 3. The composition of claim 2, wherein the ratio of polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) or a salt thereof in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is from about 0.3:1 to about 0.9:1. [4] 3. The composition of claim 2, wherein the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or a salt thereof is from about 0.06:1 to about 0.12:1. [5] 3. The composition according to item 2, wherein the ratio of polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is from 0.2:1 to about 0.5:1. [6] The ratio of polycarboxylic acid polymer chelating agent to polyacrylate or polyacrylic acid polymer is in the following ratio: (A) the ratio of polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) or a salt thereof in combination with ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is from about 0.3:1 to about 0.9:1; (B) the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or a salt thereof is from about 0.06:1 to about 0.12:1; and / or (C) the ratio of polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is from about 0.2:1 to about 0.5:1. [7] 7. The composition of any one of items 1 to 6, wherein the polycarboxylic acid polymer chelating agent is present in an amount of about 10% to about 30% by weight of the composition, and the aminocarboxylate chelating agent is present in an amount of about 70% to about 90% by weight of the composition. [8] The hardness additive composition according to any one of items 1 to 7, an alkaline source; and at least one nonionic surfactant, A detergent composition wherein the polycarboxylic acid polymer chelating agent of the hardness additive composition comprises less than about 4%, preferably about 2% or less by weight of the composition. [9] 9. The detergent composition of claim 8, wherein the alkaline source is an alkali metal carbonate.

[10] 10. The detergent composition according to item 8 or 9, wherein the nonionic surfactant comprises an alcohol ethoxylate and / or an ethylene oxide / propylene block copolymer.

[11] 11. The detergent composition according to any one of items 8 to 10, further comprising an additional chelating agent.

[12] 12. The detergent composition according to any one of items 8 to 11, wherein the composition comprises about 15% by weight to about 50% by weight of the hardness additive composition, about 20% by weight to about 90% by weight of the alkali metal alkalinity source, about 1% by weight to about 25% by weight of the nonionic surfactant, and about 1% by weight to about 20% by weight of the additional functional ingredient.

[13] 13. The detergent composition according to any one of items 8 to 12, further comprising at least one enzyme.

[14] 14. The detergent composition according to any one of items 8 to 13, wherein the composition does not contain silicates, NTAs, phosphates, and / or phosphonates.

[15] 1. A method for improving solid block hardness, said method comprising: combining the hardness additive composition according to any one of items 1 to 7 with an alkalinity source, at least one surfactant, and at least one additional functional ingredient; mixing to form a uniform mixture; and pressing the composition in a mold to form a solid composition. The method wherein the solid is a block that has edge hardness upon pressing and removal from the mold.

[16] 16. The method of claim 15, wherein the method does not include hardening the solid block.

[17] 17. The method according to item 15 or 16, further comprising packaging the solid block immediately after pressing and removing it from the mold.

[18] Item 18. The method of item 17, wherein the packaging comprises shrink wrapping.

[19] 19. The method according to any one of items 15 to 18, wherein the scrap rate of the solid block production is less than about 5%, or preferably less than about 3%.

Claims

1. 1. A hardness additive composition for adjusting the hardness of a pressed solid block composition comprising an alkali metal carbonate and a nonionic surfactant, said hardness additive composition comprising: 5% to 40% by weight of the composition of at least one polycarboxylic acid polymeric chelating agent comprising a homopolymer of polyacrylic acid; and 60% to 95% by weight of the composition of an aminocarboxylic acid chelating agent comprising ethylenediamine-N,N-tetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), and glutamic acid N,N-diacetic acid (GLDA); The weight ratio of the polycarboxylic acid polymer chelating agent to the aminocarboxylic acid chelating agent is the following ratio: (A) the weight ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or a salt thereof is from 0.06:1 to 0.12:1; and (B) the weight ratio of the polycarboxylic acid polymer chelating agent to ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof is 0.2:1 to 0.5:

1.

2. 10. The composition of claim 1, wherein the polycarboxylic acid polymer chelating agent comprises from 10% to 30% by weight of the composition and the aminocarboxylic acid chelating agent comprises from 70% to 90% by weight of the composition.

3. The hardness additive composition according to claim 1 or 2; an alkaline source; and at least one nonionic surfactant, the polycarboxylic acid polymer chelating agent of the hardness additive composition comprises less than 4% by weight of the composition; A detergent composition, wherein the composition is in the form of a pressed solid block.

4. 4. The detergent composition of claim 3, wherein the alkaline source is an alkali metal carbonate.

5. 5. A detergent composition according to claim 3 or 4, wherein the nonionic surfactant comprises an alcohol ethoxylate and / or an ethylene oxide / propylene block copolymer.

6. 6. The detergent composition of any one of claims 3 to 5, further comprising an additional chelating agent.

7. 7. The detergent composition of any one of claims 3 to 6, wherein the composition comprises 15wt% to 50wt% of the hardness additive composition, 20wt% to 80wt% of the alkaline source, 1wt% to 25wt% of the nonionic surfactant, and 1wt% to 20wt% of at least one additional functional ingredient.

8. 8. The detergent composition according to any one of claims 3 to 7, further comprising at least one enzyme.

9. A detergent composition according to any one of claims 3 to 8, wherein the composition is free of silicates, NTAs, phosphates and / or phosphonates.

10. 1. A method for improving solid block hardness, said method comprising: Combining the hardness additive composition of claim 1 or 2 with an alkalinity source, at least one surfactant, and at least one additional functional ingredient; mixing to form a uniform mixture; pressing in a mold to form a solid composition; and removing the solid composition from the mold.

11. 11. The method of claim 10, further comprising packaging the solid composition immediately after pressing and removing it from the mold.

12. The method of claim 11 , wherein the packaging comprises shrink wrapping.

13. 13. The method according to any one of claims 10 to 12, wherein the scrap rate of the solid block production is less than 5%, said scrap rate being assessed according to the following procedure. (1) removing the pressed solid composition within 2 minutes after the pressed solid composition is ejected from the mold; (2) inserting the solid composition into a plastic container capable of collecting any loose powder that falls from the solid composition so that the bottom of the solid composition is in contact with the plastic container; (3) Grasping the top quarter of the solid composition with both hands (using chemical resistant gloves) and rocking the solid composition back and forth six times to loosen any powder on the edges of the solid composition; (4) Immediately after shaking the solid composition, rotate the solid composition two times clockwise and two times counterclockwise around the entire bottom edge of the solid composition; (5) Using your available hand, brush off any remaining loose powder that has not fallen into the plastic container, but do not forcefully brush off the powder, but rather remove the loose powder; (6) Remove the powder remaining in the plastic container, weigh it, and record the weight loss as a percentage; and (7) This procedure is repeated with at least five solid compositions for each batch, and in the case of long, complete production batches, five solid compositions each from the beginning, middle, and end of the batch, and the scrap rate is calculated as the average % mass loss.

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