Hardness additive to improve edge hardening, and block detergent containing hardness additive

Abstract

To provide a solid detergent composition designed to maintain the solid integrity throughout the production of a pressed solid, and during mechanical conveying of the solid and during releasing of the solid from a mold.SOLUTION: A solid detergent composition having unexpected immediate block hardness without a curing step, is provided by the inclusion therein of a hardness additive composition comprising a synergetic ratio of a polycarboxylic acid polymer chelating agent relative to an aminocarboxylate chelating agent. A method of producing a solid detergent composition at least having a cleaning performance substantially similar to a solid detergent composition not including the hardness additive composition, and the solid detergent composition are also provided.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to Provisional Application No. 62 / 811,656, filed on 28 February 2019 under Section 119 of the United States Patent Act, which is incorporated herein by reference in its entirety.

[0002] This invention relates to a solid detergent composition designed to maintain the integrity of the solid during mechanical transport and discharge from the mold throughout the production of a pressed solid. The solid detergent composition provides a solid having an unexpected immediate block hardness exceeding that of a solid composition, without a curing step, as a result of a hardness additive composition using a dispersant polymer therein. The hardness additive composition contains a synergistic ratio of dispersant polymers, namely a polycarboxylic acid polymer chelator versus an aminocarboxylate chelator (chelant). Methods for preparing the solid detergent composition and the solid detergent composition itself are also provided. [Background technology]

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

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

[0005] Therefore, the object of the claimed composition is to provide improved solid block hardness / rigidity by incorporating a hardness additive composition using a dispersant polymer suitable for use in various compositions, including solid detergent compositions.

[0006] A further objective of this composition and the hardness additive composition is to provide block hardness / rigidity immediately after block pressing is completed, i.e., without requiring a hardening step for solidification.

[0007] Another objective of this composition and the 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 solid.

[0008] Other purposes, advantages, and characteristics of the detergent compositions disclosed herein, and their uses, will become apparent from the following specification in conjunction with the accompanying drawings. [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The hardness additive compositions disclosed herein, and solid compositions containing them, and the advantages of their use, are the improved hardness of the solid compositions. The solids do not have brittle or fragile edges that cause loss of solid material. [Means for solving the problem]

[0010] In one embodiment, the present invention provides a solid hardness additive composition comprising: at least one polycarboxylic acid polymer chelating agent comprising polyacrylate or polyacrylic acid polymer or homopolymer in an amount of about 5% to about 40% by weight of the composition; and 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) in an amount of about 60% to about 95% by weight of the composition; and polycarboxylic acid polymer chelating agent vs. polyacrylate or polyacrylic acid The polymer ratio is one of the following: (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 approximately 0.3:1 to approximately 0.9:1; (B) the ratio of polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or its salt is approximately 0.06:1 to approximately 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 approximately 0.2:1 to approximately 0.5:1.

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

[0012] In another embodiment, provided herein is a method for producing a solid composition comprising: combining a hardness additive composition with an alkali source, at least one surfactant, and at least one additional functional component; mixing them to form a homogeneous mixture; and pressing them in a mold to form a solid composition, wherein the solid is a block having edge hardness immediately upon pressing and removal from the mold.

[0013] Although several embodiments are disclosed, further embodiments of the detergent compositions disclosed herein will become apparent to those skilled in the art from the following embodiments for carrying out the invention, illustrating and describing exemplary embodiments of the detergent compositions disclosed herein. Therefore, the drawings and embodiments for carrying out the invention should be considered illustrative and not limiting. [Brief explanation of the drawing]

[0014] [Figure 1] The box plots of total loose powder lost in three press solid tests demonstrate an immediate improvement in block edge hardness between the control formulation (without hardness additive composition) and the formulation containing the hardness additive composition. [Figure 2] The box plots show the total loose powder lost during press solid production of formulations containing hardness additive compositions compared to a negative control formulation. [Figure 3] The box plots of total loose powder lost in four press solid tests demonstrate the improvement in immediate block edge hardness of control formulations (containing the hardness additive composition (positive control) and not containing it (negative control)) compared to the formulation containing the hardness additive composition. [Figure 4] This shows a box plot comparison of the scrap rate of the resulting pressed solid containing the hardening additive composition ("new") compared to a formulation without the hardening additive composition ("original").

[0015] Various embodiments of the detergent compositions disclosed herein will be described in detail with reference to the drawings, where similar reference numbers represent similar parts in several figures. References to various embodiments do not limit the compositions and methods disclosed herein, nor the scope of their use. The figures shown herein are not limited to the various embodiments of the detergent compositions disclosed herein, but are provided for illustrative purposes of the detergent compositions disclosed herein. [Modes for carrying out the invention]

[0016] The detergent compositions, hardness additive compositions, methods for producing them, and embodiments of their use disclosed herein are not limited to any particular detergent composition, which may vary and be understood by those skilled in the art, and may include, for example, additive systems for various compositions, including solids that are soft or sticky and need to harden immediately. It should be further understood that all technical terms used herein are solely for the purpose of describing a particular embodiment and are not intended to be limiting in any way or to any extent. For example, as used herein and in the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the content clearly indicates otherwise. Furthermore, all units, prefixes, and symbols may be shown in their SI-approved form.

[0017] Numerical ranges enumerated herein include numbers within a defined range. Throughout this disclosure, various aspects or embodiments of the compositions or methods disclosed herein are presented in range form. It should be understood that descriptions in range form are for convenience and brevity only and should not be construed as a rigid limitation to the scope of the invention. Accordingly, the range descriptions should be considered to specifically disclose all possible subranges and individual numbers within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0018] Certain terms are first defined so that the detergent compositions and hardness additive compositions disclosed herein, and their uses, may be more readily understood. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which embodiments of the present invention relate. Many methods and materials similar, modified, or equivalent to those described herein can be used in carrying out embodiments of the present invention without excessive experimentation, and preferred materials and methods are described herein. In describing and claiming embodiments of the present invention, the following technical terms are used according to the definitions set forth below.

[0019] When used herein, the term "approximately" refers to variations in quantity that may arise, for example, from typical measurement and liquid handling procedures used in the preparation of concentrates or solutions in the real world; from unforeseen errors in those procedures; from differences in the preparation, source, or purity of components used in the preparation of compositions or the execution of methods. The term "approximately" also encompasses different quantities resulting from different equilibrium conditions for compositions arising from a particular initial mixture. Whether modified by the term "approximately" or not, the claims include equivalent quantities.

[0020] The terms “active substance,” “percentage of active substance,” “weight percentage of active substance,” or “concentration of active substance” are used interchangeably herein and refer to the concentration of a purifying component expressed as a percentage after subtracting inert components such as water or salt.

[0021] As used herein, the terms “alkyl” or “alkyl group” refer to saturated hydrocarbons having one or more carbon atoms, and include linear alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cycloalkyl groups (or “cycloalkyl,” “alicyclic,” or “carbocyclic” groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched 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 that substitute one or more hydrogens of one or more carbons in a hydrocarbon skeleton. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinato, shea Possible examples include amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0023] In some embodiments, the substituted alkyl group may include a heterocyclic group. As used herein, the term “heterocyclic group” includes a ring-closed structure similar to a carbocyclic group in which one or more carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur, or oxygen. The heterocyclic group may be saturated or unsaturated. Examples of heterocyclic groups, but not limited to these, include aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thiethane, dioxetane, dithiethane, dithiethone, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0024] As used herein, the term “cleaning” refers to a method used to facilitate or assist in the removal of dirt.

[0025] The term "hard surface" refers to solid, substantially inflexible surfaces such as countertops, tiles, floors, walls, panels, windows, sanitary fixtures, kitchen and bathroom furniture and appliances, engines, circuit boards, and dishes. Hard surfaces may 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, terpolymers such as block, graft, random, and alternating copolymers, and higher-order “x”mers, and further includes their derivatives, combinations, and blends. Furthermore, unless otherwise specifically limited, the term “polymer” includes, but is not limited to, all possible isomeric configurations of a molecule, including isotactic, syndiotactic, and random symmetry, and combinations thereof. Furthermore, unless otherwise specifically limited, the term “polymer” includes all possible geometric configurations of a molecule.

[0027] As used herein, the term “scrap rate” refers to the number or amount of solid composition that is unsuitable for use. It is desirable that a scrap rate of less than about 5%, preferably less than about 3%, and most preferably about 0%, be achieved by using hardness additive compositions. For commercial or large-scale production of solid block compositions, the scrap rate may be calculated based on the total number of blocks that are defective and therefore unusable. For example, if 316,000 kg of solid composition are produced in one year, this corresponds to 105,334 blocks, and a 5% scrap rate would correspond to <5267 defective blocks, while a more preferable 3% scrap rate would correspond to <3160 defective blocks. For the purpose of calculating the scrap rate under experimental conditions such as those described herein, the scrap rate is defined with respect to the total amount of lost loose powder from the solid block composition, which represents the scrap rate in commercial production.

[0028] As used herein, the term “dirt” refers to polar or nonpolar organic or inorganic substances, including but not limited to carbohydrates, proteins, fats, and oils. These substances may exist in their organic state or may form inorganic complexes with metals.

[0029] As used herein, the terms “substantially absent,” “absent,” “substantially absent from,” or “absent” refer to a composition that either completely lacks a component or has a component present in such small an amount that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and must not be present in an amount 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 equivalent cleaning performance" means that the same degree of cleanliness (or at least not significantly inferior) or the same amount of effort (or at least not significantly inferior) or both are generally achieved by substitute cleaning products or systems. As referred to herein, a solid detergent composition containing a hardening additive composition provides a solid detergent having substantially equivalent cleaning performance to a solid detergent composition without a hardening additive composition.

[0031] The terms "weight percent," "wt%," "percent by weight," and "% by weight," and their variations, as used herein, refer to the concentration of a substance obtained by dividing its weight by the total weight of the composition and multiplying by 100. As used herein, "percent," "%," etc., are intended to be synonymous with "weight percent," "wt%," etc.

[0032] The methods, hardness additive compositions, and detergent compositions disclosed herein include, essentially consist of, or may 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. Where used herein, “essentially consist of” means that the methods and compositions may include additional steps, components, or ingredients, provided that the additional steps, components, or ingredients do not substantially alter the basic and novel features of the claimed methods and compositions.

[0033] Hardness additive composition The hardness additive composition is suitable for a variety of solid compositions, including, for example, solid detergent compositions for improving the hardness of a solid composition immediately after pressing, i.e., block edge rigidity. Beneficially, the hardness additive composition is added to a variety of solid compositions such as solid detergent compositions, solid formulations that have sticky consistency and benefit from enhanced hardening, caustic formulations, manual detergents, and laundry detergents. A further benefit is that 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 most fragile and brittle parts of a pressed solid. This immediate improvement in the hardness of a pressed 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 specific mechanism of action for improving the hardness of a solid composition, hardness additive compositions provide a ratio of dispersant polymers that are chelating agents as block hardening additives, i.e., polycarboxylic acid polymer chelators to aminocarboxylate chelators for inhibiting water hardness, and the combination thereof synergistically hardens the composition. It is unexpected that a particular combination of chelating agents provides improved solid hardness. A chelating agent is a molecule that can coordinate (i.e., bind) metal ions commonly found in natural water so as to prevent the metal ions from interfering with the action of other cleaning components of the cleaning composition. However, when a hardness additive composition is included in a solid composition, it is used in a unique ratio of polycarboxylic acid polymer chelator to aminocarboxylate chelator, and furthermore, the polycarboxylic acid polymer chelator (e.g., Acusol polymer) may be incorporated into the solid composition on a weight basis of less than about 4% by weight, and preferably about 2% by weight. These are lower concentrations than the conventional use of polycarboxylic acid polymers for chelating.

[0035] An exemplary range of hardness additive compositions is shown in Table 1 by weight percentage of the composition. 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 curing of the block. In one embodiment, the ratio of the polycarboxylic acid polymer chelating agent to the aminocarboxylate, preferably methylglycine diacetic acid (MGDA) or a salt thereof, 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 a ratio between these, for example, including about 0.06:1 to about 0.48:1, or about 0.06:1 to about 0.12:1. In a further embodiment, the ratio of the polycarboxylic acid polymer chelating agent to the aminocarboxylate, preferably 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 at least about 0.3:1 to about 1:1, or about 0.3:1 to about 0.9:1. In yet another embodiment, the ratio of the polycarboxylic acid polymer chelating agent to the aminocarboxylate, preferably ethylenediamine-N,N-tetraacetic acid (EDTA) or a salt thereof, is about 0.2:1 to about 0.5:1. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges of ratios include the number defining the range, and each integer within the defined range of ratios.

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

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

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

[0040] The detergent compositions disclosed herein may be solid concentrates. “Solid” composition refers to a composition that is in a solid form, such as powder, particles, aggregates, flakes, granules, pellets, tablets, lozenges, packs, briquettes, bricks, solid blocks, unit doses, or other solid forms 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 a solid form when exposed to high temperatures of 100°F, 112°F, preferably 120°F. Pressed solids can take any form, including blocks. Where 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 simply gravity. For example, a solid will retain the shape of the mold when removed from it. The degree of hardness of a solid composition may be a range of degrees, but it is desirable that a pressed solid containing a hardness additive composition has a relatively dense and hard molten solid block hardness, similar to concrete.

[0041] Detergent compositions containing hardening additive compositions benefit from the absence of chips and gauges in the solid blocks. As a further benefit, the solid blocks do not exhibit brittle edges and can beneficially withstand physical stress from the pressing, conveying, and packaging systems used.

[0042] The detergent compositions disclosed herein can be made available as concentrates to be diluted before or during use (or as multiple concentrates to be diluted and combined) to provide a solution for use on various surfaces, i.e., hard surfaces. The advantage of providing concentrates to be combined or diluted later is that it is less expensive to transport and store concentrates than solutions for use, and is more sustainable because fewer packages are used, thus reducing transportation and storage costs.

[0043] Polycarboxylic acid polymer chelating agent The hardness additive composition (and the solid composition using the same) contains 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 agents are phosphorus-free chelating agents. Examples of polycarboxylates include polyacrylic acid homopolymers, polymaleic acid homopolymers, maleic acid / olefin copolymers, sulfonated copolymers or terpolymers, acrylic / maleic acid copolymers or terpolymers, polymethacrylic acid homopolymers, polymethacrylic acid copolymers or terpolymers, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and chelating agent polymers having pendant carboxylate (-CO2-) groups, such as polyacrylic acid homopolymers, polymaleic acid homopolymers, maleic acid / olefin copolymers, polymethyl For further consideration of chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol. 5, pp. 339–366 and Vol. 23, pp. 319–320, whose disclosure is incorporated herein by reference. These materials may also function as crystallizing agents when used at a quasi-stoichiometric level.

[0044] Polycarboxylic acid polymer chelating agents may include polyacrylic acid homopolymers and polymaleic acid homopolymers, as well as polymers modified with fatty acid terminal groups. Exemplary polyacrylic acid homopolymers have molecular weights 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 (a completely neutralized acrylic acid homopolymer), Acusol 448, and Acusol 944, all available from Dow Chemical.

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

[0046] In one embodiment, the hardness additive composition disclosed herein comprises about 5% to about 40% by weight of a polycarboxylic acid polymer chelating agent, about 10% to about 35% by weight of a polycarboxylic acid polymer chelating agent, about 10% to about 30% by weight of a polycarboxylic acid polymer chelating agent, preferably about 10% to about 25% by weight of a polycarboxylic acid polymer chelating agent. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0047] In yet another embodiment, a solid detergent composition containing a hardness additive composition comprises about 0.1% to about 5% by weight of a polycarboxylic acid polymer chelating agent, about 0.5% to about 5% by weight of a polycarboxylic acid polymer chelating agent, about 1% to about 5% by weight of a polycarboxylic acid polymer chelating agent, about 1% to about 4% by weight of a polycarboxylic acid polymer chelating agent, or about 1% to about 2% by weight of a polycarboxylic acid polymer chelating agent. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0048] Aminocarboxylate chelating agent The hardness additive composition (and the solid composition using the 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 do not contain NTA. Examples of aminocarboxylates include, for example, N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA) (also known herein as ethylenediamine-N,N-tetraacetic acid, 2,2',2'',2'''-(ethane-1,2-diyldinitrilo)tetraacetic acid), methylglycinediacetic 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 preferred embodiments, the aminocarboxylate comprises, consists of, or is essentially composed of, ethylenediamine-N,N-tetraacetic acid, methylglycine diacetic acid, and glutamic acid N,N-diacetic acid.

[0050] In various embodiments, the hardness additive composition and the solid detergent composition use a chelating agent that is substantially free of NTA-containing compounds, thereby making the composition more environmentally acceptable.

[0051] In one embodiment, the hardness additive composition disclosed herein comprises about 60% to about 95% by weight of an aminocarboxylate chelating agent, about 65% to about 90% by weight of an aminocarboxylate chelating agent, about 70% to about 90% by weight of an aminocarboxylate chelating agent, preferably about 75% to about 90% by weight of an aminocarboxylate chelating agent. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0052] In yet another embodiment, a solid detergent composition containing a hardness additive composition comprises about 5% to about 45% by weight of an aminocarboxylate chelating agent, about 5% to about 40% by weight of an aminocarboxylate chelating agent, about 5% to about 35% by weight of an aminocarboxylate chelating agent, about 5% to about 30% by weight of an aminocarboxylate chelating agent, or about 5% to about 25% by weight of an aminocarboxylate chelating agent. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0053] Alkaline source In one embodiment, the detergent composition disclosed herein includes an alkali source. In one embodiment, the alkali 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, it is further understood that the alkali metal carbonate and alkali metal hydroxide include bicarbonates and sesquicarbonates. It should also be understood that, with respect 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 alkali source is an alkali metal carbonate. In some other preferred embodiments, the alkali source is an alkali metal carbonate that does not contain unreacted alkali metal hydroxides. In a further preferred embodiment, the alkaline cleaning composition does not contain an organic alkali source.

[0054] The alkali source is provided in an amount sufficient to provide a working solution of the detergent composition 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 working solution is preferably about 8.0 to about 13.0, more preferably about 10 to 12.5.

[0055] In one embodiment, the detergent composition comprises about 20% to about 90% by weight of an alkali source, about 20% to about 80% by weight of an alkali source, about 30% to about 80% by weight of an alkali source, about 40% to about 80% by weight of an alkali source, about 40% to about 75% by weight of an alkali source, preferably about 50% to about 80% by weight of an alkali source. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0056] Additional functional ingredients The components of the claimed detergent composition can be further combined with various functional components suitable for use in utensil cleaning and other applications using alkaline detergents or cleaning compositions. In some embodiments, the claimed detergent composition (including polycarboxylic acid polymer chelating agents and aminocarboxylate chelating agents), an alkali source, a nonionic surfactant, and any additional chelating agents / builders, including a hardness additive composition, constitute the majority, or substantially all, of the total weight of the detergent composition. For example, in some embodiments, additional functional components are present in little to no form.

[0057] In other embodiments, additional functional components may be included in the claimed detergent composition. Functional components provide the composition with desired properties and functionality. For the purposes of this application, the term “functional component” includes materials that, when dispersed or dissolved in a working 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, but the specific materials discussed are merely examples, and a variety of other functional components may be used. For example, many of the functional materials discussed below relate to materials used in cleaning, specifically in utensil cleaning applications. However, other embodiments may include functional components for use in other applications.

[0058] In a preferred embodiment, the detergent composition does not contain the chelating agent NTA. In a more preferred embodiment, the detergent composition does not contain silicates. In yet another preferred embodiment, the detergent composition does not contain phosphates and / or phosphonates. In yet another preferred embodiment, the detergent composition does not contain silicates, NTAs, phosphates and / or phosphonates.

[0059] This composition may also contain additional defoamers, anti-redeposition agents, bleachers, solubility modifiers, dispersants, rinsing aids, metal protectants (etching inhibitors), enzymes, stabilizers, corrosion inhibitors, metal catalysts, additional sequestering agents and / or chelating agents, fragrances and / or dyes, rheology modifiers or thickeners, hydrotropes or colorants, buffers, solvents, etc.

[0060] defoaming agent The detergent compositions disclosed herein may optionally include 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 of the formula RO-(PO) 0-5 (EO) 1-30 (PO) 1-30 , or RO-(PO) 1-30 (EO) 1-30 (PO) 1-30 A nonionic surfactant having the following properties, where R is C 8-18 The alkyl groups are linear or branched alkyl groups, EO = ethylene oxide, and PO = propylene oxide. Examples of suitable alkoxylated surfactants include ethylene oxide / propylene block copolymers (EO / PO copolymers), capped EO / PO copolymers, partially capped EO / PO copolymers, fully capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, and mixtures thereof, such as those available under the names Pluronic or Plurafac®.

[0061] Other antifoaming agents include silicone compounds, such as silica dispersed in polydimethylsiloxane, polydimethylsiloxane, and functionalized polydimethylsiloxane, such as those 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. Discussions of antifoaming agents can be found, for example, in U.S. Patent No. 3,048,548 by Martin et al., U.S. Patent No. 3,334,147 by Brunelle et al., and U.S. Patent No. 3,442,242 by 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 organic hydrophobic and organic hydrophilic groups and are typically produced by the condensation of an organoliphatic, alkyl aromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkali oxide moiety, which is conventionally ethylene oxide or its polyhydrate product, polyethylene glycol, etc. 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 polyhydrate additive, or a mixture thereof with an alkoxylene such as propylene oxide, to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety that condenses with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound having a desired balance between hydrophilic and hydrophobic properties. According to the present invention, nonionic surfactants useful in the composition are low-foaming nonionic surfactants. 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 initiator-reactive hydrogen compounds. Examples of polymer compounds produced from the sequential propoxylation and ethoxylation of initiators are commercially available from BASF Corp. under the trade names Pluronic® and Tetronico. Pluronic® compounds are bifunctional (two reactive hydrogen) compounds formed by condensing ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule has a molecular weight of 1,000 to 4,000. Then, ethylene oxide is added so as to sandwich this hydrophobic substance between hydrophilic groups, and its length is controlled to constitute approximately 10% to 80% by weight of the final molecule. Tetronic® compounds are tetrafunctional block copolymers obtained from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotype ranges from 500 to 7,000, and the hydrophilic ethylene oxide is added to constitute 10% to 80% by weight of the molecule.

[0064] A condensation product of 1 mole of alkylphenol and 3 to 50 moles of ethylene oxide, wherein the alkyl chain, having a linear or branched configuration, or a single or double alkyl configuration, contains 8 to 18 carbon atoms. The alkyl group may be represented, for example, by diisobutylene, diamyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants may 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 1 mole of a saturated or unsaturated, straight-chain or branched-chain alcohol having 6 to 24 carbon atoms and 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 sold under the trade names Neodol® manufactured by Shell Chemical Co. and Alfonic® manufactured by Vista Chemical Co.

[0066] The condensation product of 1 mole of a saturated or unsaturated, straight-chain or branched-chain carboxylic acid having 8 to 18 carbon atoms and 6 to 50 moles of ethylene oxide. The acid portion can consist of a mixture of acids within the carbon atom range defined above or can 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 A compound having, wherein R is a straight-chain or branched alkyl group of C8~18, EO = ethylene oxide, PO = propylene oxide.

[0068] Ethylene oxide is added to ethylene glycol to provide a hydrophilic substance of a specified molecular weight; then propylene oxide is added to obtain a hydrophobic block on the outer (ends) of the molecule, thereby modified and substantially inverted compounds from (1). The hydrophobic portion of this molecule has a molecular weight of 1,000 to 3,100, and the central hydrophilic substance contains 10 wt% to 80 wt% of the final molecule. These reverse Pluronics® are manufactured by BASF Corporation under the trade name of Pluronic® R surfactants.

[0069] Alkoxylated diamines are produced by the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The hydrophobic portion of this molecule has a molecular weight of 250 to 6,700, and the central hydrophilic substance accounts for 0.1% to 50% by weight of the final molecule. Examples of commercially available compounds of this chemistry are available from BASF Corporation under the trade name Tetronic® surfactants.

[0070] Alkoxylated diamines are produced by the sequential addition of ethylene oxide and propylene oxide to ethylenediamine. The hydrophobic portion of this molecule has a molecular weight of 250 to 6,700, and the central hydrophilic substance accounts for 0.1% to 50% by weight of the final molecule. Examples of commercially available compounds of this chemistry are available from BASF Corporation under the trade name Tetronic® surfactants.

[0071] Compounds modified by "capping" or "end blocking" the terminal hydroxyl groups (of the polyfunctional moiety) to reduce foaming during reactions between hydrophobic small molecules such as propylene oxide, butylene oxide, and benzyl chloride and short-chain fatty acids, alcohols, or alkyl halides containing 1 to 5 carbon atoms, or mixtures thereof. Also disclosed are reactants such as thionyl chloride, which converts terminal hydroxyl groups to chloride groups. Such modifications to terminal hydroxyl groups may result in fully blocked, blocked-hetero, hetero-blocked, or fully heterononionic materials.

[0072] The polyoxyalkylene surfactants that can be advantageously used in the compositions of the present invention are of the formula: P[(C3H6O) n (C2H4O) m H] xCorresponding to the formula, P is a residue of an organic compound having 8 to 18 carbon atoms and 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 chain may optionally, but advantageously, contain a small amount of ethylene oxide, and the oxyethylene chain may optionally, but advantageously, contain a small amount of propylene oxide.

[0073] Alkoxylated amines, or more specifically, alcohol alkoxylated / amination / alkoxylated surfactants. These nonionic surfactants are at least partially related to 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 It can be represented by H, In the formula, R 20 is an alkyl, alkenyl, or other aliphatic group, or alkyl-aryl group, having 8 to 20, preferably 12 to 14 carbon atoms; EO is oxyethylene; PO is oxypropylene; s is 1 to 20, preferably 2 to 5; t is 1 to 10, preferably 2 to 5; and u is 1 to 10, preferably 2 to 5. Other variations in the range of these compounds can be expressed in alternative formulas. R 20 --(PO) v --N[(EO) w H][(EO) z H] It can be expressed by, where R 20The above definition is as follows, where 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 a product line marketed by Huntsman Chemicals as nonionic surfactants. A preferred chemical in this class is Surfonic PEA25 amine alkoxylate.

[0074] In one embodiment, the detergent composition comprises about 0% to about 15% by weight of an antifoaming agent, about 0.5% to about 10% by weight of an antifoaming agent, about 0.5% to about 5% by weight of an antifoaming agent, and preferably about 0.5% to about 3% by weight, about 1% by weight, about 3% by weight, about 5% by weight, or about 10% by weight of an antifoaming agent. In addition, although not limited to the detergent compositions disclosed herein, all enumerated ranges include the number defining the range, and each integer within the defined range.

[0075] Phosphonate In some embodiments, the claimed detergent composition may include a phosphonate. Examples of phosphonates include phosphinosuccinate oligomers (PSOs) described in U.S. Patents No. 8,871,699 and No. 9,255,242; 2-phosphibutane-1,2,4-tricarboxylic acid (PBTC), 1-hydroxyethane-1,1-diphosphonic acid, CH2C(OH)[PO(OH)2]2; aminotri(methylenephosphonic acid), N[CH2PO(OH)2]3; aminotri(methylenephosphonic acid) (Honate), 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), C9H (28-x) N3Na x O 15 P5 (x=7); Hexamethylenediamine (tetramethylenephosphonate), potassium salt, C10 H (28-x) N2K x O 12 Examples of phosphorates include, but are not limited to, P4(x=6); bis(hexamethylene)triamine(pentamethylenephosphonic 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. It is preferable that the phosphonate or phosphonate alkali, or a combination of phosphonate and alkali source, be neutralized before being added to the mixture, so that little or no heat or gas is generated by the neutralization reaction when the phosphonate is added. However, in one embodiment, the claimed detergent composition does not contain phosphorus.

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

[0077] surfactant In some embodiments, the detergent compositions disclosed herein include a surfactant. In some other embodiments, the detergent compositions disclosed herein include a nonionic antifoaming surfactant or agent. In some other embodiments, the detergent compositions disclosed herein include an additional surfactant along with the nonionic antifoaming 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 some further embodiments, the detergent compositions disclosed herein do not include an additional surfactant other than one or more nonionic antifoaming surfactants or agents.

[0078] In some embodiments, the detergent compositions disclosed herein include, in addition to a nonionic antifoaming surfactant or agent, about 0% to about 50% by weight of additional surfactants, 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%, 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 surfactants.

[0079] Anionic surfactants Surface active substances classified as anionic surfactants because the hydrophobic group has a negative charge, or surfactants in which the hydrophobic portion of the molecule is uncharged unless the pH rises above neutral (e.g., carboxylic acids), are also useful in the detergent compositions disclosed herein. Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium, and potassium confer water solubility, ammonium and substituted ammonium ions provide both water 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 cleaning surfactants and are therefore preferred additions to strong detergent compositions.

[0080] Suitable anionic sulfate surfactants for use in the claimed detergent composition 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, and C5-C 17Examples include acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, as well as sulfates of alkyl polysaccharides such as alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as ethylene oxide and nonylphenol sulfates or concentrated products (typically containing 1 to 6 oxyethylene groups per molecule).

[0081] Suitable anionic sulfonate surfactants for use in the claimed detergent composition include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0082] Suitable anionic carboxylate surfactants for use in the claimed detergent composition include carboxylic acids (and salts), e.g., alkanic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, sulfonated fatty acids, e.g., sulfonated oleic acid. Such carboxylates include alkylethoxycarboxylates, alkylarylethoxycarboxylates, alkylpolyethoxypolycarboxylate surfactants, and soaps (e.g., alkylcarboxyls). Useful secondary carboxylates in this composition include those containing a carboxyl unit connected to a secondary carbon. The secondary carbon may be in a cyclic structure, for example, as in p-octylbenzoic acid or as in alkyl-substituted cyclohexylcarboxylate. Secondary carboxylate surfactants generally do not contain ether bonds, ester bonds, or hydroxyl groups. Furthermore, they generally lack a nitrogen atom in the head group (amphiphilic moiety). Suitable secondary soap surfactants generally contain 11 to 13 total carbon atoms, but more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acyl amino acids (and salts) such as acyl glutamates, acyl peptides, sarcosinates (e.g., N-acyl sarcosinates), and taurates (e.g., fatty acid amides of N-acyl taurates and methyl taurides).

[0083] Suitable anionic surfactants include alkyl or alkylarylethoxycarboxylates of the following formulas: RO-(CH2CH2O) n (CH2) m -CO2X (3) In the formula, R is C8-C 22 It is an alkyl group, or [ka] , R 1 C4-C 16It is an alkyl group, where 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, or 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 C8-C 16 It is an alkyl group. In some embodiments, R is C 12 -C 14 It is an alkyl group, where n is 4 and m is 1.

[0084] In other embodiments, R is [ka] And R 1 C6-C 12 It is an alkyl group. In yet another embodiment, R 1 It is a C9 alkyl group, where n is 10 and m is 1.

[0085] Such alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically available in acid form, and they can be readily converted to anionic or salt form. A commercially available carboxylate is Neodox 23-4, C 12-13 Examples include alkyl polyethoxy(4)carboxylic acid (Shell Chemical) and Emcol CNP-110, C9 alkylaryl polyethoxy(10)carboxylic acid (Witco Chemical). Carboxylates, for example, product Sandopan® DTC, C 13 Alkyl polyethoxy(7)carboxylic acids are also available from Clariant.

[0086] Cationic surfactants Cationic quaternary surfactant / quaternary alkylamine alkoxylate Cationic quaternary surfactants are substances based on a nitrogen-centered cation moiety that has a net positive change. Suitable cationic surfactants contain a quaternary ammonium group. Suitable cationic surfactants, in particular, have the general formula: N (+) R 1 R 2 R 3 R 4 X (-) This includes those, and in the formula, R 1 , R 2 , R 3 , and R 4 These are, independently of each other, alkyl groups, aliphatic groups, aromatic groups, alkoxy groups, polyoxyalkylene groups, alkylamide groups, hydroxyalkyl groups, aryl groups, and H + An ion is represented, each having 1 to 22 carbon atoms, and the group R 1 , R 2 , R 3 , and R 4 The condition is that at least one of the groups has at least eight atoms, and X(-) represents an anion, such as a halogen, acetate, phosphate, nitrate, or alkyl sulfate, preferably a chloride. The aliphatic group may also contain a crosslinking group or other group, such as an additional amino group in addition to carbon and hydrogen atoms.

[0087] Examples of specific cationic active ingredients include, 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 or inorganic salts of quaternary ammonium-containing compounds, or mixtures thereof.

[0088] Cationic surfactants preferably comprise, and more preferably refer to, compounds containing at least one long-carbon hydrophobic group and at least one positively charged nitrogen atom. The long-carbon group may be directly bonded to the nitrogen atom by simple substitution, or more preferably indirectly bonded by a crosslinking functional group in so-called interrupted alkylamines and amidoamines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more readily soluble in water by co-surfactant mixtures, and / or water-soluble. For increased water solubility, additional primary, secondary, or tertiary amino groups may be introduced, or the amino nitrogen may be quaternized using a low molecular weight alkyl group. Furthermore, the nitrogen may be part of a branched or linear portion with varying degrees of unsaturation, or part of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants may contain complex bonds having two or more cationic nitrogen atoms.

[0089] Surfactant compounds classified as amine oxides, amphoteric substances, and zwitterionic compounds are generally cationic in solutions with 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, namely amine salts and quaternary ammonium compounds, can be schematically described as follows: [ka] It can be schematically described as follows, where R represents a long alkyl chain, R', R'', and R''' may be a long alkyl chain, a smaller alkyl or aryl group, 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 as follows: [ka] It can be schematically represented as shown above, where R represents a C8-C18 alkyl or alkenyl, 1 and R 2 x is a C1-C4 alkyl group, n is 10-25, and x is an anion selected from halides or methyl sulfate.

[0092] Most cationic surfactants used on a large scale in commercial applications are known to those skilled in the art and can be subdivided into four main 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 quaternary products such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, and tetraalkylammonium salts. Cationic surfactants are known to possess a variety of properties that can be beneficial in this composition. These desirable properties may include cleaning power in compositions with a neutral pH or lower, antimicrobial efficacy, and thickening or gelling in conjunction with other agents.

[0093] A cationic surfactant useful in the claimed detergent composition herein is a surfactant of formula R 1 m R 2 x Those having YLZ (wherein each R 1 This is an organic group containing a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxyl groups and optionally interrupted in up to four of the following structures: [ka] Or it includes 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 one or fewer R groups in the molecule. 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 This is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, and has 1 or fewer R groups in the molecule. 2 is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remaining carbon atoms at any position on the Y group are filled with hydrogen.

[0094] Y is as follows: [ka] The group may also include, but is not limited to, a mixture thereof.

[0095] Preferably, L is 1 or 2, and when L is 2, the Y group has 1 to 22 carbon atoms and 2 free carbon single bonds. 1 and R 2 It is separated by a portion selected from analogs (preferably alkylene or alkenylene). Z is a water-soluble anion such as a sulfate anion, methyl sulfate anion, hydroxide anion or nitrate anion, and is particularly preferably a number of sulfate anions or methyl sulfate anions that confer electrical neutrality to the cationic component.

[0096] A suitable concentration of the cationic quaternary surfactant in the claimed detergent composition may be about 0% to about 10% by weight of the claimed detergent composition.

[0097] Amphoteric surfactants Amphoteric or amphoteric electrolyte surfactants contain both basic and acidic hydrophilic groups as well as organic hydrophobic groups. These ionic entities may be either anionic or cationic groups as described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups employed as basic and acidic hydrophilic groups. In some surfactants, sulfonates, sulfates, phosphonates, or phosphates provide a negative charge.

[0098] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be linear or branched, and one of the aliphatic substituents contains about 8 to 18 carbon atoms, and another contains an anionic water-soluble group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are known to those skilled in the art and are subdivided into two main classes described in the "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104(2) 69-71 (1989), which is incorporated herein by reference. The first class includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkyl amino acids and their salts. Some amphoteric surfactants may be conceivable to belong to both classes.

[0099] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethylimidazoline is synthesized by condensation and ring closure of a long-chain carboxylic acid (or derivative) with a dialkylethylenediamine. Commercially available amphoteric surfactants are derivatized using, for example, chloroacetic acid or ethyl acetate by subsequent hydrolysis and ring opening of the imidazoline ring by alkylation. During alkylation, one or two carboxyalkyl groups react to form a tertiary amine and an ether linkage, and different alkylating agents yield different tertiary amines.

[0100] The long-chain imidazole derivatives that have applications in the present invention generally have the following general formula: [ka] Neutral pH zwitterion amphoteric sulfonates [ka] In the formula, R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation, generally sodium, for neutralizing the charge of the anion. Commercially well-known amphoteric compounds derived from imidazolines that can be used in this composition include, for example, cocoamphopropionate, cocoamphocarboxy-propionate, cocoamphoglycinate, cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate, and cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced from aliphatic imidazolines, where the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0101] In this specification, the carboxymethylated compounds (glycinates) described above are often referred to as betaines. Betaines are a special class of amphoteric compounds described below in the following 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 having linear or branched alkyl, 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. The most commercially available N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercially available N-alkylamino acid amphoteric electrolytes that have applications in the present invention include alkylbeta-aminodipropionates, RN(C2H4COOM)2 and RNHC2H4COOM. In one embodiment, R may be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M may be a cation for neutralizing 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, ethylenediamine moieties, alkanolamide moieties, amino acid moieties, e.g., glycine, or combinations thereof, and aliphatic substituents of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkylamphodicarboxylic acids. These amphoteric surfactants are 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 + It may include a chemical structure represented as (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is one preferred amphoteric surfactant, commercially available from Rhodia Inc., Cranbury, NJ under the trade name Miranol® FBS. Another preferred coconut-derived amphoteric surfactant having the chemical name disodium cocoamphodiacetate is also sold by Rhodia Inc., Cranbury, NJ under the trade name Mirataine® JCHA.

[0104] A typical list of amphoteric classes and species of these surfactants is described in U.S. Patent No. 3,929,678, published December 30, 1975, to Laughlin and Heuring. Further examples are described in “Surface Active Agents and Detergents” (Vol. 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 anionic charges. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants contain a positively charged quaternary ammonium, or optionally a sulfonium or phosphonium ion, a positively 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, potentially leading to a strong "internal salt" attraction between positive and negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radical can be linear or branched, and one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-soluble group, such as a carboxyl, sulfonate, sulfate, phosphate, or phosphonate.

[0106] Betaine and sultaine surfactants are examples of zwitterionic surfactants for use herein. The general formulas of these compounds are as follows: [ka] In the formula, R 1Y comprises an alkyl, alkenyl, or hydroxyalkyl radical with 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 atoms, phosphorus atoms, and sulfur atoms, and R 2 x is an alkyl group or monohydroxyalkyl group containing 1 to 3 carbon atoms, where x is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen atom or a phosphorus atom, and R 3 Z is an alkylene or hydroxyalkylene or hydroxyalkylene with 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-trioxatetracosanphosphonio]-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, and 3-(N,N-dimethyl-N- Examples include 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-hydroxypentane-1-sulfate. The alkyl group contained in the detergent surfactant may be linear or branched, and may be saturated or unsaturated.

[0108] The zwitterionic surfactants suitable for use in the present composition include betaines having the following general structure. [Chemical formula] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH values or do not show a decrease in water solubility within their isoelectric ranges. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyldimethylbetaine, hexadecyldimethylbetaine, C 12-14 acylamidopropylbetaine, C 8-14 acylamidohexyldiethylbetaine, 4-C 14-16 acylmethylamidodiethylammonio-1-carboxybutane, C 16-18 acylamidodimethylbetaine, C 12-16 acylamidopentanediethylbetaine, and C 12-16 acylmethylamidodimethylbetaine.

[0109] The sultaines useful in the present invention include compounds having the formula (R(R 1 )2N + R 2 SO 3- , where R is a C6-C 18 hydrocarbyl group, each R 1 is typically independently a C1-C3 alkyl, such as methyl, and R 2 is a C1-C6 hydrocarbyl group, such as a C1-C3 alkylene or hydroxyalkylene group.

[0110] A typical list of zwitterionic classes and species of these surfactants is provided in U.S. Patent No. 3,929,678, issued December 30, 1975, by Laughlin and Heuring. Further examples are provided in “Surface Active Agents and Detergents” (Vol. 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 may further contain enzymes that contribute to the removal of dirt, prevention of re-adhesion, and additionally, the promotion of a reduction in foam in the solution of use of the cleaning composition. The purpose of the enzymes is to break down sticky dirt, such as starchy or proteinaceous materials, which are typically found on soiled surfaces and are removed by the detergent composition and enter the wash water source. The enzymes remove the dirt from the substrate and prevent the dirt from re-adhering to the substrate surface. The enzymes provide additional cleaning and detergent effects, such as antifoaming.

[0112] Exemplary types of enzymes that can be incorporated into detergent compositions or detergent solutions include amylase, protease, lipase, cellulase, cutinase, gluconase, peroxidase, and / or mixtures thereof. The detergent compositions disclosed herein may use multiple enzymes of any suitable origin, such as plant, animal, bacterial, fungal, or yeast origin. However, according to preferred embodiments of the detergent compositions disclosed herein, the enzyme is a protease. As used herein, the terms “protease” or “proteinase” refer to an enzyme that catalyzes the hydrolysis of peptide bonds.

[0113] As those skilled in the art will see, enzymes are designed to work on specific types of stains. For example, according to one embodiment of the present invention, protease enzymes may be used in dishwashing applications because they are effective in high-temperature dishwashers and are effective in reducing protein-based stains. Protease enzymes are particularly useful for cleaning protein-containing stains such as blood, skin scales, mucus, grass, and food (e.g., eggs, milk, spinach, meat scraps, tomato sauce). Protease enzymes can cleave the links of macromolecular proteins of amino acid residues, converting the substrate into smaller fragments that readily dissolve or disperse in the aqueous solution used. Proteases are often referred to as cleaning enzymes due to their ability to break down stains through a chemical reaction known as hydrolysis. Protease enzymes can be obtained, for example, from Bacillus subtilis, Bacillus licheniformis, and Streptomyces griceus. Protease enzymes are also commercially available as serine endoproteases. Examples of commercially available protease enzymes are available under the following brand names: Esperase, Purafect, Purafect L, Purafect Ox, Everlase, Liquanase, Savinase, Prime L, Prosperase, and Blap.

[0114] For the detergent compositions disclosed herein, the enzymes may vary based on the specific cleaning application and the type of dirt to be cleaned. For example, the temperature for a particular cleaning application will affect the enzymes selected for the detergent compositions disclosed herein. For instance, utensil cleaning applications involve cleaning substrates at temperatures above approximately 60°C, above approximately 70°C, or approximately 65–80°C, and enzymes such as proteases are desirable because they have the ability to maintain enzymatic activity at such high temperatures.

[0115] The enzymes for detergent compositions disclosed herein may be independent entities and / or may be formulated in combination with detergent compositions. In addition, enzymes may be formulated in 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 denature upon application of heat, and therefore, the use of enzymes in the claimed detergent compositions requires a method for forming the detergent composition that is not dependent on heat, as a step in a formation process such as coagulation.

[0116] Enzymes can 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 depends on the manufacturing method, which is well known to those skilled in the art, and such manufacturing methods are not important to the present invention.

[0117] Alternatively, the enzyme may be provided separately from the claimed detergent composition, for example, by being added directly to the dishwasher cleaning solution or water for a specific use.

[0118] Further descriptions of enzymes suitable for use in the detergent compositions disclosed herein are, for example, disclosed in U.S. Patents 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, as well as U.S. Patent Publications 2012 / 0046211 and 2004 / 0072714, each of which is incorporated herein by reference in whole. In addition, 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 in its entirety herein.

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

[0120] Methods for creating / improving the hardness of solid blocks The solid compositions disclosed herein may be formed by combining components in the weight percentages and ratios disclosed herein. The detergent compositions disclosed herein may be provided as solids, and a solution for use may be formed during the dishwashing process (or other use applications).

[0121] The solid detergent compositions disclosed herein may be formed using hardness additive compositions which may be provided as a premix, or the individual components of the hardness additive compositions may be individually mixed with additional components of the detergent composition and mixed during manufacturing. The method includes mixing the hardness additive composition with the components of the detergent composition 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 exemplary embodiments, a single-screw or twin-screw extruder is used to combine and mix the components, optionally including 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 components throughout its entire mass and is dimensionally stable.

[0123] Specifically, in the forming process, liquid and solid components are introduced into a final mixing system and continuously mixed until the components form a substantially homogeneous semi-solid mixture in which the components are distributed throughout their entire mass. In exemplary embodiments, 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 longer. The mixture is then discharged from the mixing system into a mold for pressing. The solid is removed from the mold, unexpectedly providing an immediately curing solid, such as a solid block with no brittle edges and requiring no curing step. In one embodiment, the solid is not cured.

[0124] Solid compositions can be formed using various pressures. For example, in some embodiments, the method for producing a solid can use pressures on the solid 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 immediate hardening of the pressed solid is beneficial in maintaining physical integrity throughout the mechanical conveying system, including discharge from the press die. The solid can be packaged immediately after being discharged or removed from the press die. In exemplary embodiments, the formed solid begins to harden into a solid form immediately, within a few seconds to approximately one minute. The solid does not exhibit brittle edges, large or small chips, and / or gauges or chunks that would break apart due to damage in the press's mechanical conveying system. This beneficially enables continuous processing or production systems that do not require the hardening of the solid block, which is generally necessary to remove the solid block from the conveying system (often requiring additional time before packaging).

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

[0127] All publications and patent applications herein represent the ordinary level of art in the art to which the present invention relates. All publications and patent applications are incorporated herein by reference to the same extent as each individual publication or patent application is incorporated by reference specifically and individually. [Examples]

[0128] Embodiments of solid detergent compositions, hardness additive compositions, and methods for producing them disclosed herein are further defined in the following non-limiting embodiments. While these embodiments illustrate specific embodiments of the detergent compositions, hardness additive compositions, and methods for producing them disclosed herein, it should be understood that they are provided merely as illustrative examples. From the above considerations and these embodiments, those skilled in the art will be able to identify the essential features of the embodiments and 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 their spirit and scope. Therefore, various modifications to the embodiments disclosed herein, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to be included within the scope of the appended claims.

[0129] As shown in Table 3 of the Examples, various solid detergent compositions were evaluated. The various components used in Table 3 refer to both their generic names and trade names, including the following: Ash - sodium carbonate, Trilon M-methylglycine-N,N-diacetate sodium salt (MGDA), 78% activity, EDTA-ethylenediamine-N,N-tetraacetic acid, 99% active, GLDA-N,N-dicarboxymethylglutamate tetrasodium salt, Polyacrylic acid available from Acusol 445-DOW Chemical, Acusol 944-DOW Chemical offers acrylic acid homopolymers. 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 block from the conveyor line within 2 minutes of it being discharged from the press.

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

[0133] 3. Using both hands (wearing chemical-resistant gloves), grasp the top quarter of the block. Shake the block back and forth six times to loosen any powder at the edges of the block.

[0134] 4. Immediately after shaking the block, rotate it twice clockwise and twice counterclockwise along its entire bottom edge.

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

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

[0137] 7. Repeat this method with at least 5 blocks from every batch. For long, complete production batches, take 5 blocks from the beginning, middle, and end of the batch.

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

[0139] The initial production of the P0 formulation (control without hardness additive composition) resulted in a significantly high loss rate and failed to achieve a production yield of 97%. The evaluation is intended to identify compositions containing hardness additive composition that show improvement over P0 (control) in terms of total loose powder loss. According to the box plot, 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 scrap rate of 5% or less), and most preferably <1.08 grams. If the solid block composition is 3000 grams, measurements of 1.82 grams to 2.75 grams result in a scrap rate of about less than 5%, and less than 1.36 grams results in a scrap rate of about 0%. Those skilled in the art can calculate the desired scrap rate based on different sizes (i.e., total block weight) of the solid composition using the hardness additive composition.

[0140] An evaluation of the total loose powder from P0 (a control block without hardening additive compositions) was conducted compared to formulations P1 and P7. The results are shown in Figure 1 in box plots showing the total loose powder from the three evaluations; the first evaluation included 12-13 days of hardening of the block (providing the block with an additional 12-13 days of hardening); the second and third evaluations did not include hardening, and instead, edge hardness evaluations were performed immediately after the block was removed from the press mold. The first dataset, which evaluated formulation P0 (control without hardening additive compositions) even after 12-13 days of hardening, showed powder loss from the block exceeding an 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 hardening additive compositions in the formulations improve edge hardness immediately after pressing (without hardening period).

[0141] Example 2 The additional block edge hardness 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 remained unable to exhibit sufficient block hardness, as measured by the total loose powder mass loss. Improved block hardness is shown by formulations P1, P2, P3, and P4, demonstrating a reduction in the total loose powder mass loss. Each of these formulations exhibited a loss of approximately <2.75 grams, illustrating that the hardness additive composition in the formulations improves edge hardness immediately after pressing (without curing period).

[0142] Example 3 The 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. The tests were performed for P8 and P0 in a separate location (same setup and methodology) from the rest of the tests. As illustrated in Figure 3, in addition to the mass weight loss (grams) of the blocks, the overall percentage of pressed blocks considered defective due to insufficient curing immediately after pressing results in powder loss due to brittle edges of the blocks. As shown, the threshold described in Example 1 as commercially acceptable is having 5% or less block defects overall, preferably 0% defects.

[0143] Figure 3 shows that the P0 negative control formulation yielded a pressed solid with an unacceptable level of loose powder mass loss, including a rejection rate of at least 25% or at least 50%. The P0 formulation failed to cure (unlike Example 1 and Figure 1), indicating that the immediate block hardness of the P0 negative control was inferior to the cured block strength. This further demonstrates that the block hardness immediately after pressing the solid is a more difficult condition to satisfy. The deformation of the P7 formulation was a 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 various evaluated formulations P1, P2, P3, P4, and P7. Positive controls P8, P9, and P10, which do not contain the curing additive composition, also functioned well and provided immediate hardness, which is thought to be the result of P8 and P9 formulations that do not contain Acusol 445, as well as P10 which contains Acusol 448, resulting in P8 formulation and P9 which is a silicated formulation with increased phosphate in the formulation.

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

[0145] As the present invention is described in this manner, it will be apparent that the present invention can be modified in many ways. Such modifications should not be considered departures from the spirit and scope of the invention, and all such modifications are intended to be included within 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 present invention falls within the claims.

[0146] The features disclosed in the above description, or in the following claims or accompanying drawings, expressed in a particular form, or in terms of means for performing the function of disclosure, or methods or processes for achieving the results of disclosure, may be used, as appropriate, separately, or in any combination of such features, to realize the present invention in its various forms.

Claims

1. A hardness additive composition for adjusting the hardness of a pressed solid block composition comprising an alkali metal carbonate and a nonionic surfactant, wherein the hardness additive composition comprises The composition comprises a polyacrylic acid homopolymer, and at least one polycarboxylic acid polymer chelating agent in an amount of 5% to 40% by weight of the composition, The composition comprises 60% to 95% by weight of an aminocarboxylic acid chelating agent containing ethylenediamine-N,N-tetraacetic acid (EDTA), methylglycine diacetic acid (MGDA), and glutamic acid N,N-diacetic acid (GLDA), A hardness additive composition in which the weight ratio of a polycarboxylic acid polymer chelating agent to glutamic acid N,N-diacetic acid (GLDA) combined with ethylenediamine-N,N-tetraacetic acid (EDTA) is 0.17:1 to 0.42:

1.

2. The composition according to claim 1, wherein the weight ratio of the polycarboxylic acid polymer chelating agent to methylglycine diacetic acid (MGDA) or a salt thereof is 0.06:1 to 0.12:

1.

3. The composition according to claim 1 or 2, wherein 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.

4. The composition according to any one of claims 1 to 3, wherein the polycarboxylic acid polymer chelating agent is contained in an amount of 10% to 30% by weight of the composition, and the aminocarboxylic acid chelating agent is contained in an amount of 70% to 90% by weight of the composition.

5. A hardness additive composition according to any one of claims 1 to 4, Alkaline source and A solid detergent composition comprising at least one nonionic surfactant, The polycarboxylic acid polymer chelating agent in the hardness additive composition is contained in an amount of less than 4% by weight of the composition. The aforementioned composition is a detergent composition in the form of a pressed solid block.

6. The detergent composition according to claim 5, wherein the alkali source is an alkali metal carbonate.

7. The detergent composition according to claim 5 or 6, wherein the nonionic surfactant comprises an alcohol ethoxylate and / or an ethylene oxide / propylene block copolymer.

8. The detergent composition according to any one of claims 5 to 7, further comprising an additional chelating agent.

9. The detergent composition according to claim 8, wherein the composition comprises 15% to 50% by weight of the hardness additive composition, 20% to 80% by weight of the alkali source, 1% to 25% by weight of the nonionic surfactant, and 1% to 20% by weight of at least one additional functional component.

10. The detergent composition according to any one of claims 5 to 9, further comprising at least one enzyme.

11. The detergent composition according to any one of claims 5 to 10, wherein the composition does not contain silicate, NTA, phosphate, and / or phosphonate.

12. A method for improving the hardness of a solid block, wherein the method is: The hardness additive composition according to any one of claims 1 to 4 is combined with an alkali source, at least one surfactant, and at least one additional functional component. To mix and form a homogeneous mixture, Forming a solid composition by pressing it in a mold, A method comprising removing the solid composition from the mold.

13. The method according to claim 12, further comprising the step of packaging the solid composition immediately after pressing and removing it from the mold.

14. The method according to claim 13, wherein the packaging includes shrink wrapping.

15. The method according to any one of claims 12 to 14, wherein the scrap rate of solid block production is less than 5%, and the scrap rate is evaluated according to the following procedure. (1) Within two minutes after the pressed solid composition is discharged from the mold, take the solid composition, (2) Place the solid composition into a plastic container capable of collecting all loose powder that falls from the solid composition, so that the bottom of the solid composition is in contact with the plastic container. (3) Using both hands (wearing chemical-resistant gloves), grasp the upper quarter of the solid composition and shake 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 twice clockwise and twice counterclockwise around the entire circumference of the bottom edge of the solid composition. (5) Use your available hand to brush away any remaining loose powder that has not fallen into the plastic container, but do so in a manner that removes the loose powder rather than forcibly brushing it away. (6) Take the powder remaining in the plastic container, weigh it, record it as loss by mass %, and then, (7) Repeat this procedure with at least five solid compositions for each batch, and in the case of a long, complete production batch, with the first, middle, and last five solid compositions of the batch, and the scrap rate is calculated as the average loss by mass %.

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