Solid nonionic surfactant compositions

Abstract

To provide solidification of liquid nonionic surfactants with a binder, a carrier, or both a binder and a carrier to form a solidified surfactant composition.SOLUTION: Specifically, the invention relates to solidification of liquid nonionic surfactants utilizing drying devices, where the feed composition contains at least one liquid nonionic surfactant and the binder, carrier, or binder and carrier to form a solidified surfactant composition. The solidified surfactant compositions can be useful in various cleaning compositions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] cross reference This application is related to and claims priority under 35 U.S.C. § 119 to U.S. Provisional Patent Application No. 62 / 864,937, entitled "SOLIDIFYING NONIONIC SURFACTANTS," filed June 21, 2019, the entire contents of which are expressly incorporated herein by reference.

[0002] The present invention relates to the solidification of liquid nonionic surfactants with a binder, a carrier, or both a binder and a carrier. Specifically, the present invention relates to the solidification of liquid nonionic surfactants using a drying device, wherein the feed composition contains at least one surfactant and a water-soluble binder, a carrier, or both a binder and a carrier. [Background technology]

[0003] Many nonionic surfactants are only available in liquid form.To make solid cleaning compositions, it is desirable that many of these surfactants are provided in solid form.Because many of these surfactants are only available in liquid form, they cannot be easily incorporated into solid formulations, or the active concentration that can be incorporated into formulations is limited.Liquid nonionic surfactants are incorporated into some liquid cleaning compositions.However, these same nonionic surfactants are difficult or prohibited to be incorporated into solid formulations, which has limited the effectiveness of solid cleaning products or the ability to make solid cleaning products. Summary of the Invention [Problem to be solved by the invention]

[0004] It is therefore an object of the claimed invention to develop a solidified nonionic surfactant composition from a liquid nonionic surfactant, and a method for making the same.

[0005] It is a further object of the present invention to provide a solidified nonionic surfactant composition that is free-flowing.

[0006] It is a further object of the present invention to provide a cleaning composition comprising a solidified nonionic surfactant composition.

[0007] Other objects, advantages and features of the present invention will become apparent from the following specification taken in conjunction with the accompanying drawings. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention relates to solidifying a liquid nonionic surfactant with a binder, a carrier, or both a binder and a carrier to form a solidified surfactant composition. Solidified surfactant compositions have many advantages over existing formulations that contain the same surfactant in liquid form, which can hinder or prevent the surfactant, including but not limited to pressed solids, from being used in certain types of solid formulations. For example, many specific nonionic surfactants are only available in liquid form. Converting liquid nonionic surfactants into solidified surfactant compositions allows for their use at higher concentrations in solid compositions, expanding their usefulness in solid formulations. Unexpectedly, once solidified, solidified liquid nonionic surfactants have been found to be difficult to incorporate into solid cleaning compositions, including pressed solid compositions. Due to the high surfactant activity, solid cleaning compositions incorporating solidified nonionic surfactants have been found to suffer from processing challenges in manufacturing and stability issues as solid compositions. This application describes methods for solidifying liquid nonionic surfactants to form solid nonionic surfactant compositions, as well as methods for preparing solid cleaning compositions incorporating solid nonionic surfactants. Solid cleaning compositions containing solidified nonionic surfactants provided substantially similar performance in terms of foam and soil removal properties, which is indicative of good overall surfactant performance. This demonstrates the utility of solidified surfactant compositions in solid cleaning compositions, including, but not limited to, pressed solids.

[0009] The embodiments of the present invention may vary and are not limited to specific methods and / or products understood by those skilled in the art. It should be further understood that all terminology used herein is solely for the purpose of describing specific embodiments and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms "a," "an," and "the" may include plural referents unless the content clearly dictates otherwise. Furthermore, all units, prefixes, and symbols may be denoted in their SI-recognized form.

[0010] Numerical ranges described herein are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of the invention are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to specifically disclose all possible subranges, fractions, and individual numbers within that range. For example, a description of a range such as 1 to 6 should be considered to specifically disclose subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numbers within that range, e.g., 1, 2, 3, 4, 5, and 6, and decimals and fractions, e.g., 1.2, 3.8, 1½, and 4¾. This applies regardless of the broadness of the range.

[0011] In order that the present invention may be more readily understood, certain terms are first defined. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the embodiments of the present invention pertain. Many methods and materials similar, modified, or equivalent to those described herein can be used to practice the embodiments of the present invention without undue experimentation, and preferred materials and methods are described herein. In describing and claiming the embodiments of the present invention, the following terminology will be used in accordance with the definitions set forth below.

[0012] As used herein, the term "about" refers to variations in a quantity that can be made, for example, through typical measurement techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, and distance. Furthermore, given the solid and liquid handling procedures used in the real world, there are certain inadvertent errors and variations that are likely due to differences in the manufacture, source, or purity of the components used to make a composition or perform a method, etc. The term "about" also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. The term "about" also encompasses these variations. Whether modified by the term "about," the claims include equivalents to the amounts.

[0013] The terms "actives" or "percent actives" or "percent actives by weight" or "actives concentration" are used interchangeably herein and refer to the concentration of those ingredients involved in cleaning expressed as a percentage minus inactive ingredients such as water or salt.

[0014] As used herein, the term "alkyl" or "alkyl group" refers to a saturated hydrocarbon having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

[0015] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to an alkyl group having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonato, phosphinato, cyano, methyl ... The substituents may include nitro, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0016] In some embodiments, substituted alkyls can include heterocyclic groups. As used herein, the term "heterocyclic group" includes closed ring structures similar to carbocyclic groups in which one or more carbon atoms in the ring is an element other than carbon, such as nitrogen, sulfur, or oxygen. Heterocyclic groups can be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0017] "Anti-redeposition agents" refer to compounds that help to remain suspended in water instead of redepositing on the object being cleaned. Anti-redeposition agents are useful in the present invention to help reduce the redeposition of removed soil on the surface being cleaned.

[0018] As used herein, the term "cleaning" refers to methods used to promote or assist in stain removal, bleaching, microbial population reduction, and any combination thereof.

[0019] The term "laundry" refers to items or articles washed in a laundry washing machine. Generally, laundry refers to any item or article made from or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials can include natural or synthetic fibers, such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. Fibers can be treated or untreated. Exemplary treated fibers include those treated for flame retardancy. It should be understood that the term "linen" is often used to describe certain types of laundry items, including bed sheets, pillowcases, towels, table linens, tablecloths, bar mops, and uniforms. The present invention additionally provides compositions and methods for treating surfaces, including non-laundry items and hard surfaces such as dishes, glasses, and other utensils.

[0020] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers, such as block, graft, random, and alternating copolymers, terpolymers, and higher order "x"-mers, and further includes derivatives, combinations, and blends thereof. Furthermore, unless otherwise specifically limited, the term "polymer" is intended to include all possible isomeric configurations of the molecule, including, but not limited to, isotactic, syndiotactic, and random symmetries, and combinations thereof. Furthermore, unless otherwise specifically limited, the term "polymer" is intended to include all possible geometric configurations of the molecule.

[0021] As used herein, the term "soil" or "stain" refers to non-polar, oily substances, which may or may not contain specific substances such as mineral clays, sand, natural minerals, carbon black, graphite, kaolin, environmental dust, etc.

[0022] As used herein, the term "substantially free" refers to a composition that is completely devoid of the component or has such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or contaminant and must be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight, and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0023] The term "threshold agent" refers to compounds that inhibit the crystallization of hard water ions from solution but do not necessarily form specific complexes with the hard water ions. Threshold agents include, but are not limited to, polyacrylates, polymethacrylates, olefin / maleic acid copolymers, and the like.

[0024] As used herein, the term "ware" refers to items such as eating and cooking utensils, tableware, and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, transportation vehicles, and floors. As used herein, the term "warewashing" refers to the washing, cleaning, or rinsing of ware. Ware also refers to items made of plastic. Types of plastics that may be cleaned with the compositions according to the present invention include, but are not limited to, those containing polypropylene polymer (PP), polycarbonate polymer (PC), melamine formaldehyde resin or melamine resin (melamine), acrylonitrile-butadiene-styrene polymer (ABS), and polysulfone polymer (PS). Other exemplary plastics that may be cleaned using the compounds and compositions of the present invention include polyethylene terephthalate (PET) polystyrene polyamide.

[0025] As used herein, the terms "water-soluble" and "water-miscible" mean that a component (e.g., carrier or solvent) is soluble or dispersible in water at a concentration of greater than about 0.2 g / L, preferably about 1 g / L or greater, more preferably 10 g / L or greater, and most preferably about 50 g / L or greater at about 20°C.

[0026] As used herein, "weight percent," "% by weight (wt%)," "percent by weight," "% by weight," and variations thereof refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition multiplied by 100. As used herein, it is understood that "percent," "%," and the like are intended to be synonymous with "weight percent," "% by weight," and the like.

[0027] The methods, systems, devices, and compositions of the invention may comprise, consist essentially of, or consist of the components and ingredients of the invention, as well as other components described herein. As used herein, "consisting essentially of" means that the methods, systems, devices, and compositions may include additional steps, components, or ingredients only if the additional steps, components, or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, devices, and compositions.

[0028] Method for solidifying nonionic surfactants Drying as a process function is utilized to remove liquid from a liquid-solid system to produce a dry solid. The liquid removed is typically water, although other organic liquids may be removed via the drying process. The selection of drying device and / or configuration depends on the feed stream conditions, the desired product form, and the temperature sensitivity of the feed, in addition to general considerations of fluid dynamics, heat and mass transfer, chemical reaction rates, and gas-solid interactions. The selection of equipment depends on the material properties, the drying characteristics of the material, product quality, and dust / solvent recovery.

[0029] Drying devices are typically classified into three types. First, the operating mode of the drying device / system is classified as batch or continuous. Generally, batch drying is employed when the required production rate is 500 pounds of dried product per hour or less. Continuous drying is preferred when more than 500 pounds of dried product per hour is required. Second, drying devices are classified by the mode of heat transfer used to remove moisture. Directly heated dryers (also known as adiabatic or convection dryers) contact the material with hot gas to evaporate and remove moisture. When utilized in continuous operation, the airflow can be designed to be countercurrent, cocurrent, or crosscurrent to the material. Indirectly heated dryers (also known as non-adiabatic dryers) provide heat through conduction and / or radiation from a hot surface. These dryers can be operated under vacuum to reduce the temperature at which moisture evaporates. Third, dryers can also be classified based on the degree of agitation of the material. The feed can be either static or fluidized. A good drying device will provide a transition zone at the inlet to atomize the fluid or premix it with recycled solids to improve flow. When heat-sensitive solids are present, dryers with precise temperature control and / or vacuum conditions may be preferred. As one skilled in the art will understand, solidification of surfactants and other useful detergent chemicals requires careful consideration and weighing of process variables to select an appropriate drying device.

[0030] In one embodiment of the present invention, the drying device is, for example, a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower dryer, a vibrating conveyor dryer, a drum dryer, a screw conveyor dryer, a fluidized bed, a spouted bed, a pneumatic conveyor, a spray dryer, or a combination thereof. The drying devices may be arranged in parallel or in series, with one or more drying devices in a row. Preferred drying devices include, but are not limited to, spray dryers and fluidized beds (also called fluidized beds).

[0031] Surprisingly, we have found that it is preferable to first dilute the nonionic surfactant with water or a water-miscible solvent before the drying step. While not wishing to be bound by theory, we have found that high (often 100%) active concentrations of nonionic surfactants present drying challenges and are difficult to process. Furthermore, even once dried, the solidified nonionic surfactant presents challenges in incorporating into solid cleaning compositions. We have found that these challenges in drying liquid nonionic surfactants and incorporating the solidified nonionic surfactant composition into cleaning compositions can be overcome by combining the liquid nonionic surfactant and / or carrier with water. Water can be added to the nonionic surfactant, the carrier, or both. In a preferred embodiment, the liquid nonionic surfactant is diluted with water. Whether water is added to the surfactant, the carrier, or both, it is preferably added at a weight ratio of nonionic surfactant to water of about 1:1 to about 1:20, more preferably about 1:2 to about 1:15, and most preferably about 1:4 to about 1:11. In one preferred embodiment, when combined with water, the non-ionic surfactant and / or carrier is insoluble but soluble in the slurry, preferably the dispersed slurry.

[0032] In one embodiment of the present invention, the solidified surfactant composition contains less than about 12% by weight water, preferably less than about 10% by weight water, more preferably less than about 5% by weight water, even more preferably less than about 2% by weight water, even more preferably less than about 1% by weight water, and most preferably less than about 0.5% by weight water.

[0033] In one preferred embodiment of the invention, the method according to the claimed invention provides a dry composition comprising at least about 10% by weight, preferably at least about 25% by weight, preferably at least 40% by weight, more preferably at least 50% by weight of active surfactant.

[0034] Fluidized bed In one preferred embodiment of the present invention, solidification of the liquid nonionic surfactant is carried out using a fluidized bed, where dry powder is fed into the bed where a liquid is applied and then may be dried with hot gas. Without wishing to be limited by a particular configuration or theory of the present invention, a fluidized bed dryer consists of a fluidization chamber in which wet particles are blown through a heater into a plenum chamber below the bed and then fluidized by hot gas through a distribution plate which fluidizes the particles above.

[0035] Fluidized beds can be used to carry out agglomeration processes involving solid binders and / or carriers, or granulation processes involving only liquid components. Agglomeration processes use liquid addition to bind particles from a powder feed to form larger particles of a desired size and composition. Granulation processes differ from agglomeration processes in that no powder feed is required. Rather, granulation processes are carried out by continuously spraying a liquid coating onto seed material from the process, continuously coating and drying the liquid to form solid granules of a desired size and composition. Furthermore, it has been discovered that this process can be carried out without seed material, or indeed without material in the bed. In one embodiment, where there is no material in the bed at the start of the process, the process can begin by granulating to form seed material, which can then be continued by agglomeration or further granulation.

[0036] The air velocity within the fluidized bed depends on the characteristics of the starting material, the drying rate, and the desired particle size, and typically ranges from about 0.001 to about 1000 feet per second, preferably from about 0.01 to about 500 feet per second, more preferably from about 0.1 to about 100 feet per second, and most preferably from about 1 to about 60 feet per second.

[0037] Preferably, the liquid flow rate is between about 0.001 lb / min / lb of bed material and about 0.15 lb / min / lb of bed material, more preferably between about 0.01 lb / min / lb of bed material and about 0.10 lb / min / lb of bed material. It should be understood that in an embodiment in which the process begins without seed material and without starting material in the bed, the starting bed material is zero, so the liquid flow rate per mass per minute per mass of bed material is initially incalculable. However, bed material is present almost immediately after the process begins as material is added to the bed for initial granulation. In such an embodiment, the ratio of liquid added to bed material is initially higher due to the small amount of bed material. For example, when there is no starting material in the bed, the preferred liquid flow rate is between about 0.1 lb / min / lb of bed material and about 2 lb / min / lb of bed material, more preferably between about 0.5 lb / min / lb of bed material and about 1.5 lb / min / lb of bed material.

[0038] The atomization air pressure within the fluidized bed can be from about 0 to about 100 psig per nozzle, preferably from about 1 to about 75 psig per nozzle, and more preferably from about 10 to about 60 psig per nozzle.

[0039] spray drying In a preferred embodiment of the present invention, the solidification of the liquid nonionic surfactant is carried out using a spray dryer. Spray dryers are compatible with slurry or solution feeds and provide the evaporation desired for heat-sensitive materials and lightweight, porous products. The spray dryer configuration may require consideration of the pressure effect on the liquid feed and solid product to ensure drying without damaging the product. Generally, the liquid or slurry is fed into the dryer process unit and then sprayed into a hot air stream as fine droplets. Therefore, the feed composition must be able to withstand the pressure required to form droplets. Upon entering the spray dryer, liquid evaporation occurs rapidly, while the product temperature remains relatively low. The process selection and design must also take into account gas-solid interactions. Specifically, the inlet and outlet conditions of the solids, as well as the flow capacity and residence time, should be designed with respect to the diffusivity and heat transfer rate.

[0040] In one embodiment of the invention, the inlet temperature of the inlet feed ranges from about 20° C. to about 250° C., preferably from about 100° C. to about 250° C., and more preferably from about 150° C. to about 200° C. In a further embodiment of the invention, the outlet temperature, aspirator, and pump speeds depend on the decomposition of the surfactant while in the spray dryer.

[0041] The value of the outlet temperature can vary based on the decomposition temperatures of the components in the solidified surfactant composition. Thus, in certain embodiments, the temperature may be higher or lower than those described herein. However, in embodiments of the present invention, the outlet temperature is less than about 150°C, more preferably from about 0°C to about 120°C, and most preferably from about 20°C to about 100°C.

[0042] Solidified surfactant composition Some nonionic surfactants are available only in liquid or cast / paste form. Other nonionics are solid at room temperature and require a high-temperature room to melt, making them unprocessable solids. However, they are not available as free-flowing powders. It would be desirable to provide many such surfactants in solid, free-flowing powder form. An embodiment of the present invention is found in a solidified nonionic surfactant composition. Another embodiment of the present invention is found in a method for preparing a solidified nonionic surfactant surfactant composition. In one embodiment, the solidified surfactant composition comprises a liquid nonionic surfactant and a binder. In one embodiment, the solidified surfactant composition comprises a liquid nonionic surfactant, a binder, a carrier, and an optional co-surfactant. In one embodiment, the solidified surfactant composition comprises a liquid nonionic surfactant and a carrier. Additional components may be present depending on the desired properties of the solidified surfactant composition.

[0043] In one aspect of the present invention, the components are fed into a selected drying device to form a solidified surfactant composition. The solidified surfactant composition is preferably a powder. Preferred powder forms include, but are not limited to, agglomerated solids and granulated solids. Thus, in some embodiments, the solidified surfactant composition is an agglomerated solid or a granulated solid.

[0044] Binder The solidified surfactant composition may include a binder. In one aspect of the present invention, the binder is a solid in the form of bricks, powder, granules, beads, and flakes. Preferably, the binder is dissolved and then dried together with the liquid nonionic surfactant. The binder can be added to the liquid nonionic surfactant alone or together with a carrier to form the solidified surfactant composition. Preferably, the binder is water-soluble. In a most preferred embodiment, the binder has a water solubility of about 0.2 g / L or more at 20°C.

[0045] Suitable binders can be liquid (aqueous or non-aqueous), semi-solid, or solid. Preferred binders include, but are not limited to, natural polymers such as urea, urea derivatives, organic salts (such as sodium acetate), inorganic salts (such as sodium salts and sulfates, including magnesium sulfate and sodium sulfate), polyacrylates, PEG, alkali metal carbonates (including, but not limited to, sodium carbonate, potassium carbonate, bicarbonates, sesquicarbonates, and mixtures thereof), and combinations thereof. Preferred natural polymers include, but are not limited to, polysaccharides and their derivatives (e.g., gums, cellulose, cellulose esters, chitin, chitosan, starch, chemically modified starches, and combinations thereof), proteins (e.g., zein, whey, gluten, collagen), lignin, natural rubber, and combinations thereof. Preferably, the PEG has a melting point of at least about 40°C, more preferably from about 42°C to about 100°C. Preferred PEGs include PEG1450, PEG3350, PEG4000, PEG4600, and PEG8000.

[0046] The binder and liquid nonionic surfactant can be added to the drying device in suitable amounts to achieve a solidified surfactant product. The amount of each component can depend on the particular liquid nonionic surfactant to be solidified, the binder used, and any other optional components that may also be included in the solidified surfactant product. Preferably, the ratio of the actives of the binder and surfactant is about 4:1 to about 1:60, or about 3:1 to about 1:50, or about 2:1 to about 1:30, or about 1:1 to about 1:30.

[0047] Since one of the objectives of the present invention is to be able to incorporate liquid nonionic surfactants into solid cleaning compositions in solid form, it is preferred that the surfactant in the solidified surfactant composition has a high concentration or ratio relative to the binder and other ingredients.However, this is limited by the desired physical characteristics of the solidified surfactant composition.For example, in a preferred embodiment of the present invention, the surfactant is a solidified granule, not a paste.In another preferred embodiment of the present invention, the solidified surfactant composition has reduced or no stickiness, so that it is free-flowing and does not caking, agglomerate, or caking during storage.

[0048] Carrier The solidified surfactant composition may include a carrier. Preferably, the carrier is solid at room temperature. In embodiments employing a granulation process, the carrier may be in liquid form and therefore dissolved. Suitable solid carriers include, but are not limited to, powder, granule, bead, and flake forms. Preferred carriers include, but are not limited to, anionic surfactants, organic salts, and inorganic salts. Preferably, the carrier is water-soluble. In the most preferred embodiment, the carrier has a water solubility of about 0.2 g / L or greater at 20°C. The carrier can be added to a liquid nonionic surfactant alone or together with a binder to form the solidified surfactant composition.

[0049] Preferred anionic surfactants include, but are not limited to, sulfonate surfactants, sulfate surfactants, and combinations thereof. In a preferred embodiment, the anionic surfactant carrier is solid. Most preferred anionic surfactants include, but are not limited to, alpha olefin sulfonates, linear alkyl sulfonates, sodium lauryl sulfate, sodium alkyl sulfate, and combinations thereof.

[0050] Preferred organic salts include, but are not limited to, alkali and alkaline metal carbonates (such as sodium carbonate and magnesium carbonate), alkali and alkaline metal acetates (such as sodium acetate and magnesium acetate), and combinations thereof.

[0051] Preferred inorganic salts include, but are not limited to, alkali and alkaline metal sulfates (such as sodium sulfate and magnesium sulfate), sodium chloride, and combinations thereof.

[0052] The carrier and liquid nonionic surfactant can be added to the drying device in suitable amounts to achieve a solidified surfactant product. The amount of each component can depend on the particular liquid nonionic surfactant to be solidified, the carrier used, and any other optional components that may also be included in the solidified surfactant product. Preferably, the ratio of the actives of the carrier and surfactant is about 2:1 to about 1:20, or about 2:1 to about 1:15, or about 1:1 to about 1:10, or about 1:1 to 1:8.

[0053] Since one of the objectives of the present invention is to be able to incorporate liquid nonionic surfactants into solid cleaning compositions in solid form, it is preferred that the surfactant in the solidified surfactant composition has a high concentration or ratio relative to carrier and other components.However, this is limited by the desired physical characteristics of the solidified surfactant composition.For example, in a preferred embodiment of the present invention, the surfactant is a solidified granule, not a paste.In another preferred embodiment of the present invention, the solidified surfactant composition has reduced or no stickiness, so that it is free-flowing and does not caking, agglomerate, or caking during storage.

[0054] chelating agents In some embodiments, the solidifying surfactant composition can optionally contain a chelating agent. Preferred chelating agents include aminocarboxylates. Preferred aminocarboxylates include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), glutamic acid-N,N-diacetic acid (GLDA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), methylglycine-diacetic acid (MGDA), nitrilotriacetic acid (NTA), ethylenediaminetetraproprionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanoldiglycine, salts and derivatives of the foregoing, alkali metal, ammonium, and substituted ammonium salts thereof, and mixtures thereof.

[0055] When included in the solidified surfactant composition, the chelating agent is preferably present at a concentration of about 0% to about 50% by weight, more preferably about 5% to about 35% by weight, and most preferably about 10% to about 25% by weight.

[0056] Nonionic Liquid Surfactants Some surfactants are primarily available in liquid form. It is desirable for many such surfactants to be provided in solid form. In one aspect of the present invention, a liquid nonionic surfactant is added to a drying device along with a binder, a carrier, or both a binder and a carrier to form a solidified surfactant composition. Any suitable liquid nonionic surfactant can be included in the solidified surfactant composition. Preferred liquid nonionic surfactants include, but are not limited to, block copolymers, alcohol alkoxylates, alkoxylated surfactants, reverse EO / PO copolymers, alkyl polysaccharides, alkoxylated amines, fatty acid alkoxylates, fatty acid amide alkoxylates, alkanoates, and combinations thereof.

[0057] Nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group, and are typically produced by the condensation of an organic aliphatic, alkylaromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety, typically ethylene oxide or its polyhydration product, polyethylene glycol. Specifically, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide or its polyhydration product, or a mixture thereof with an alkoxylene such as propylene oxide, to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety condensed with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound with the desired balance between hydrophilic and hydrophobic properties.

[0058] Preferred liquid nonionic surfactants include, but are not limited to: 1. Block polyoxypropylene-polyoxyethylene polymer compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine as the initiator reactive hydrogen compound. Examples of polymer compounds made from sequential propoxylation and ethoxylation of the initiator are commercially available under the trade names Pluronic® and Tetronic®, manufactured by BASF Corp. 2. Condensation products of one mole of saturated or unsaturated straight- or branched-chain alcohol having from about 6 to about 24 carbon atoms with from about 3 to about 50 moles of ethylene oxide. The alcohol portion can comprise, consist essentially of, or consist of a mixture of alcohols within the carbon range delineated above, or it can consist of an alcohol having a specific number of carbon atoms within this range, or it can be a Guerbet alcohol ethoxylate. Examples of similar commercial surfactants are available under the trade names Lutensol™ from BASF, Neodol™ from Shell Chemical Co., and Alfonic™ from Vista Chemical Co. In addition to ethoxylated carboxylic acids, commonly referred to as polyethylene glycol esters, glycerides, glycerin, and other alkanoic acid esters formed by reaction with polyhydric (sugar or sorbitan / sorbitol) alcohols have application in the present invention in specific embodiments. All of these ester moieties have one or more reactive hydrogen sites on their molecules that can be subjected to further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these materials. Care must be taken when adding these fatty esters or acylated carbohydrates to compositions of the present invention containing amylase and / or lipase enzymes due to potential incompatibilities. 3. Ethoxylated C6 to C 18 Fatty alcohols and C6-C 18Mixed ethoxylated and propoxylated fatty alcohols, especially those that are water soluble, are suitable surfactants for use in the present compositions. Suitable ethoxylated fatty alcohols are C6-C8 fatty acids having a degree of ethoxylation of 3 to 50. 18 Contains ethoxylated fatty alcohols. 4. Suitable nonionic surfactants for use with the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, blocked EO / PO copolymers, alcohol alkoxylates, blocked alcohol alkoxylates, mixtures thereof, and the like. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers, such as Pluronic and reverse Pluronic surfactants, alcohol alkoxylates, such as Dehypon LS-54 (R-(EO)5(PO)4), Dehypon LS-36 (R-(EO)3(PO)6), and Tomadol 91-6, and capped alcohol alkoxylates, such as Plurafac LF221, Plurafac RA300, and Plurafac SLF-180, mixtures thereof, and the like. 5. Compounds from (1) modified, essentially reversed, by adding ethylene oxide to ethylene glycol to provide a hydrophile of specified molecular weight; then adding propylene oxide to obtain a hydrophobic block on the outside (end) of the molecule. These reverse Pluronics™ are manufactured by BASF Corporation under the trade name Pluronic™ R surfactants. Similarly, Tetronic (商標) R surfactants are manufactured by BASF Corporation. 6. Nonionic alkyl polysaccharide surfactants particularly suitable for use in the present compositions include those disclosed in U.S. Patent No. 4,565,647, issued January 21, 1986, to Llenado. These surfactants contain a hydrophobic group containing about 6 to about 30 carbon atoms and a hydrophilic group containing about 1.3 to about 10 sugar units, such as polyglycosides. Any reducing sugar containing 5 or 6 carbon atoms can be used; for example, glucose, galactose, and galactosyl moieties can be substituted for glucosyl moieties. (Optionally, the hydrophobic group is attached at the 2-, 3-, 4-, etc. position, thus resulting in glucose or galactose, as opposed to glucoside or galactoside.) The intersugar bond can be, for example, between one position of the additional sugar unit and the 2-, 3-, 4-, and / or 6-position on the preceding sugar unit. 7. Suitable nonionic surfactants include the class defined as alkoxylated amine or, most specifically, alcohol alkoxylated / aminated / alkoxylated surfactants. These nonionic surfactants can be at least partially represented by the general formula R 20 --(PO) S N--(EO) t H, R 20 --(PO) S N--(EO) t H(EO) t H, and R 20 --N(EO) t H, where R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of 8 to 20, preferably 12 to 14 carbon atoms; EO is oxyethylene; PO is oxypropylene; s is 1 to 20, preferably 2 to 5; t is 1 to 10, preferably 2 to 5; and u is 1 to 10, preferably 2 to 5. Other variations within these compounds include compounds of the alternative formula: R 20 --(PO) V --N[(EO) w H][(EO) z H], wherein R 20is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1 to 10, preferably 2 to 5. These compounds are commercially represented by the product line sold under the Surfonic® name. 8. Suitable nonionic surfactants also include fatty acid amide alkoxylates. Preferably, such surfactants have the structural formula R2CON R1 Z, where R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy group, or mixtures thereof, and R2 is a C5-C6 hydrocarbyl which may be linear. 31 Z is a hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z can be derived from a reducing sugar in a reductive amination reaction, such as a glycityl moiety. Alkyl ethoxylate condensation products of aliphatic alcohols with about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Fatty acid amide surfactants suitable for use in the present compositions include those having the formula: RCON(R) where R is an alkyl group containing 7 to 21 carbon atoms and each R is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(CHO). X H, where x is in the range of 1 to 3. 9. Suitable nonionic surfactants also include nonionic alkanoates. Suitable alkanoates are nonionic esters or salts thereof formed from the reaction of an alkanoic acid with an alkanol.

[0059] Water and / or water-miscible solvents As described above, it has been found that liquid nonionic surfactants, when combined with water or a water-miscible solvent before drying, process well through the drying system to form a flowable powder. This water is largely removed from the solidified nonionic composition during the drying process. A small amount of water may remain in the form of water of hydration. Preferably, the solidified surfactant composition contains less than about 12% by weight of added water, preferably less than about 10% by weight, more preferably less than about 5% by weight, even more preferably less than about 2% by weight, even more preferably less than about 1% by weight, and most preferably less than about 0.5% by weight. Added water refers to the amount of water added to the composition and does not include the amount of water present in other ingredients, such as the alkalinity source or surfactant. Preferably, the solidified surfactant composition contains less than about 12% by weight of total water, preferably less than about 10% by weight, more preferably less than about 5% by weight, even more preferably less than about 2% by weight, even more preferably less than about 1% by weight, and most preferably less than about 0.5% by weight. Total water refers to the water added to the composition and the water present in other ingredients, such as the alkalinity source or surfactant. It should be understood that the amount of added water and total water may depend on the type of solid composition being prepared, as some methods require more water than others.

[0060] In another aspect of the invention, the claimed method provides at least about 30%, preferably at least about 50%, more preferably at least about 65%, and most preferably at least about 85% liquid feed to result in a solidified surfactant composition, where liquid feed is the amount by weight of liquid material added to a drying device.

[0061] Solid cleaning composition The solidified surfactant compositions of the present invention can be included in solid cleaning compositions. These cleaning compositions can include, but are not limited to, detergent compositions, including utensil cleaning compositions and laundry compositions, rinse aids, and hard surface cleaning compositions. Exemplary embodiments of these compositions are provided in Tables 1A-1D below. Such compositions are exemplary and not limiting. For example, other cleaning compositions can be prepared with the solidified surfactant compositions of the present disclosure, and the cleaning compositions reflected below are provided as examples of preferred formulations. In a preferred embodiment, the cleaning composition can remove soil from a surface. In a preferred embodiment, where the cleaning composition is a rinse aid, the cleaning composition preferably reduces, and more preferably prevents, soil redeposition on the surface. [Table 1] [Table 2] [Table 3] [Table 4]

[0062] In embodiments of the present invention, additional ingredients can be included in the solid cleaning composition. The additional ingredients provide the composition with desired properties and functionality. For purposes of this application, the term "functional ingredient" includes materials that provide beneficial properties for a particular use. Some specific examples of functional materials are discussed in more detail below, but the specific materials discussed are provided by way of example only, and a variety of other functional ingredients may be used. For example, many of the functional materials discussed below relate to materials used in cleaning, specifically warewashing applications. However, other embodiments may include functional ingredients for use in other applications. Examples of such functional materials include chelating / sequestering agents, bleaching agents or activators, disinfectants / antimicrobial agents, activators, builders or fillers, anti-redeposition agents, optical brighteners, dyes, odorants or fragrances, preservatives, stabilizers, processing aids, corrosion inhibitors, fillers, solidifying agents, hardening agents, solubility modifiers, pH adjusters, humectants, hydrotropes, or a wide variety of other functional materials, depending on the desired characteristics and / or functionality of the composition. In the context of some embodiments disclosed herein, functional materials or ingredients are optionally included within the solid cleaning composition for their functional properties. Some more specific examples of functional materials are discussed in more detail below, although it should be understood by those skilled in the art and others that the specific materials discussed are given by way of example only, and that a wide variety of other functional materials may be used.

[0063] In one aspect of the present invention, the solidified surfactant composition may include any of the additional ingredients described below. Preferred additional ingredients that may be incorporated into the solidified surfactant composition include, but are not limited to, co-surfactants, dyes, and / or fragrances (odorants).

[0064] acid source In some embodiments of the present invention, the cleaning composition may include an acid source. Suitable acid sources may include organic and / or inorganic acids. Examples of suitable organic acids include, but are not limited to, carboxylic acids such as hydroxyacetic acid (glycolic acid), citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid. Organic dicarboxylic acids such as oxalic acid, malonic acid, gluconic acid, itaconic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid are also useful in accordance with the present invention. Any combination of these organic acids may also be used, mixed, or with other organic acids that allow for the proper formation of the compositions of the present invention.

[0065] Inorganic acids useful according to the present invention include, among others, sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid, and nitric acid. These acids may also be used in combination with other inorganic acids or with these organic acids mentioned above. In a preferred embodiment, the acid is an inorganic acid.

[0066] In some embodiments of the present invention, the cleaning composition may have an acidic pH. In one such embodiment, the pH is preferably between 1 and 7. In another aspect of the present invention, an acid source may be included in the basic composition as a pH adjuster or neutralizer to achieve the desired pH.

[0067] activator In some embodiments, cleaning compositions can have improved antibacterial or bleaching activity by adding a material that reacts with active oxygen to form an activating component upon use of the composition. For example, in some embodiments, a peracid or persalt salt is formed. For example, in some embodiments, tetraacetylethylenediamine can be included in the composition to react with active oxygen to form a peracid or persalt salt that acts as an antimicrobial agent. Other examples of active oxygen activators include transition metals and their compounds, compounds containing carboxyl, nitrile, or ester moieties, or other such compounds known in the art. In embodiments, the activator includes tetraacetylethylenediamine, a transition metal, a compound containing a carboxyl, nitrile, amine, or ester moiety, or a mixture thereof.

[0068] In some embodiments, the activator component may comprise up to about 75% by weight of the cleaning composition, in some embodiments, from about 0.01 to about 20% by weight, or in some embodiments, from about 0.05 to 10% by weight of the cleaning composition. In some embodiments, the activator for the active oxygen compound combines with the active oxygen to form an antimicrobial agent.

[0069] The activator can be linked to the solid cleaning composition by any of a variety of methods for linking one solid cleaning composition to another. For example, the activator can be in the form of a solid that is bonded, stuck, glued, or otherwise adhered to the solid cleaning composition. Alternatively, the solid activator can be formed around and encapsulate the solid cleaning composition. As a further example, the solid activator can be linked to the solid cleaning composition by a container or packaging for the composition, such as by plastic or shrink wrap or film.

[0070] Alkaline source The cleaning composition may include an effective amount of one or more alkalinity sources. An effective amount of one or more alkalinity sources should be considered an amount that provides the composition with a pH of about 7 to about 14. In certain embodiments, the cleaning composition may have a pH of about 7.5 to about 13.5. During the wash cycle, the use solution may have a pH of about 6 to about 14. In certain embodiments, the use solution may have a pH of about 6 to 14. When the cleaning composition includes an enzyme composition, the pH may be adjusted to provide an optimal pH range for the effectiveness of the enzyme composition. In one particular embodiment of the present invention in which an enzyme composition is incorporated into the cleaning composition, the optimal pH is about 10 to about 11.

[0071] Examples of suitable alkaline sources for the cleaning composition include, but are not limited to, carbonate-based alkaline sources including carbonates such as alkali metal carbonates, and caustic-based alkaline sources including alkali metal hydroxides. Other suitable alkaline sources may include metal silicates, metal borates, and organic alkaline sources. Exemplary alkali metal carbonates that can be used include, but are not limited to, sodium carbonate, potassium carbonate, bicarbonates, sesquicarbonates, and mixtures thereof. Exemplary alkali metal hydroxides that can be used include, but are not limited to, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Exemplary metal silicates that can be used include, but are not limited to, sodium or potassium silicate or metasilicate. Exemplary metal borates include, but are not limited to, sodium or potassium borate.

[0072] Organic alkalinity sources are often strong nitrogen bases, including, for example, ammonia (ammonium hydroxide), amines, alkanolamines, and aminoalcohols. Typical examples of amines include primary, secondary, or tertiary amines and diamines bearing at least one nitrogen-bonded hydrocarbon group, which represents a saturated or unsaturated, linear or branched alkyl group having at least 10 carbon atoms, preferably 16 to 24 carbon atoms, or an aryl, aralkyl, or alkaryl group containing up to 24 carbon atoms; optional other nitrogen-bonded groups are formed by optionally substituted alkyl, aryl, or aralkyl groups or polyalkoxy groups. Typical examples of alkanolamines include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine, and the like. Typical examples of amino alcohols include 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, hydroxymethylaminomethane, and the like.

[0073] Generally, alkalinity sources are commonly available in either aqueous or powder form. Preferably, the alkalinity source is in solid form. The alkalinity can be added to the composition in any form known in the art, including solid beads dissolved in an aqueous solution, granulated or particulate form, or a combination thereof.

[0074] Generally, it is expected that the cleaning composition will contain an amount of alkaline source from about 0.01% to about 99% by weight. In some embodiments, the alkaline source will be from about 35% to about 95% by weight of the total weight of the cleaning composition. When diluted into a use solution, the compositions of the present invention may contain from about 5 ppm to about 25,000 ppm of alkaline source.

[0075] Anti-redeposition agent The cleaning composition may optionally include an anti-redeposition agent, which can promote continued suspension of soils in the wash or rinse solution and prevent removed soils from redepositing on the substrate being washed and / or rinsed. Some examples of suitable anti-redeposition agents may include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene-maleic anhydride copolymers, and cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose, and the like. The cleaning composition may include up to about 10% by weight, and in some embodiments, in the range of about 1 to about 5% by weight, of the anti-redeposition agent.

[0076] bleach The cleaning composition may optionally include a bleaching agent. Bleaching agents can be used to lighten or whiten substrates and typically produce Cl, Br, -OCl under conditions encountered during the cleansing process. - , and / or -OBr -The bleaching agent may include a bleaching compound capable of liberating active halogen species, such as chlorine, hypochlorite, chloramine, etc. Suitable bleaching agents for use may include chlorine-containing compounds such as, for example, chlorine, hypochlorite, chloramine, etc. Some examples of halogen-releasing compounds include alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, alkali metal hypochlorite, monochloramine, dichloramine, etc. An encapsulated chlorine source may also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Pat. Nos. 4,618,914 and 4,830,773, the disclosures of which are incorporated herein by reference). The bleaching agent may also include an agent that contains or acts as an active oxygen source. The active oxygen compound acts to provide an active oxygen source, for example, by releasing active oxygen into an aqueous solution. The active oxygen compound may be inorganic or organic, or a mixture thereof. Some examples of active oxygen compounds include peroxygen compounds or peroxygen compound adducts. Some examples of active oxygen compounds or sources include hydrogen peroxide, perboric acid, sodium carbonate perhydrogenate, phosphate peroxyhydrate, potassium peroxymonosulfate, and sodium perborate monohydrate and sodium perborate tetrahydrate, with or without an activator such as tetraacetylethylenediamine. The cleaning compositions may also include small but effective amounts of bleach, for example, in some embodiments in the range of up to about 10% by weight, and in some embodiments in the range of about 0.1 to about 6% by weight.

[0077] Chelating Agents / Sequestering Agents The cleaning composition may also include an effective amount of a chelating / sequestering agent, also referred to as a builder. In addition, the cleaning composition may optionally include one or more additional builders as functional ingredients. Generally, chelating agents are molecules capable of coordinating (i.e., binding) metal ions commonly found in water sources to prevent the metal ions from interfering with the operation of other components of the rinse aid or other cleaning compositions. When included in an effective amount, the chelating / sequestering agent can also function as a water conditioning agent. In some embodiments, the cleaning composition may include a range of up to about 70% by weight, or a range of about 1-60% by weight, of the chelating / sequestering agent.

[0078] In many cases, the cleaning compositions are also phosphate and / or sulfate free. In phosphate-free solid cleaning composition embodiments, the additional functional materials, including builders, exclude phosphorus-containing compounds such as condensed phosphates and phosphonates.

[0079] Suitable additional builders include aminocarboxylates and polycarboxylates. Some examples of aminocarboxylates useful as chelating / sequestering agents include N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), glutamic acid-N,N-diacetic acid (GLDA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), methylglycine-diacetic acid (MGDA), and the like. Some examples of polymeric polycarboxylates suitable for use as sequestering agents include those having pendant carboxylate (—CO) groups, such as polyacrylic acid, maleic acid / olefin copolymers, acrylic / maleic acid copolymers, polymethacrylic acid, acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers, and the like.

[0080] In embodiments of the solid cleaning composition that are not phosphate-free, added chelating / sequestering agents may include, for example, condensed phosphates, phosphonates, etc. Some examples of condensed phosphates include sodium and potassium orthophosphate, sodium and potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, etc. Condensed phosphates can also assist, to a limited extent, in solidifying the composition by fixing free water present in the composition as water of hydration.

[0081] In embodiments of the phosphate-free solid cleaning composition, the composition comprises 1-hydroxyethane-1,1-diphosphonic acid CHC(OH)[PO(OH)], aminotri(methylenephosphonic acid) N[CHPO(OH)], aminotri(methylenephosphonate), sodium salt [ka] 2-Hydroxyethyliminobis(methylenephosphonic acid) HOCH2CH2N\[CH2PO(OH)2] 2、 Diethylenetriaminepenta(methylenephosphonic acid) (HO)2POCH2N\[CH2N\[CH2PO(OH)2]2] 2、 Diethylenetriaminepenta(methylenephosphonate), sodium salt CH (28-x) N3Na x O 15 P5(x=7), hexamethylenediamine(tetramethylenephosphonate), potassium salt C 10 H (28-x) N2K x O 12Examples of suitable phosphonates include P4 (x=6), bis(hexamethylene)triamine(pentamethylenephosphonic acid) (HO2)POCH2N[(CH2)6N[CH2PO(OH)2]2]2, and phosphorus-containing acid H3PO3. In some embodiments, combinations of phosphonates such as ATMP and DTPMP can be used. Neutralized or alkaline phosphonates, or combinations of phosphonates and alkalinity sources prior to addition to the mixture, can be used so that there is little or no heat or gas generated by the neutralization reaction when the phosphonate is added.

[0082] For a further discussion of chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339-366 and volume 23, pages 319-320, the disclosures of which are incorporated herein by reference.

[0083] Dyes / Odors Various dyes, odorants including perfumes, and other aesthetic enhancers can also be included in the solid cleaning composition.Dyes can be included to modify the appearance of the composition, such as, for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keystone Analine and Chemical), Metanilic Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue / Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), etc.

[0084] Fragrances or perfumes that can be included in the solid cleaning composition include, for example, terpenoids such as citronellol, aldehydes such as amylcinnamaldehyde, jasmines such as C1S-jasmine or jasmal, vanillin, and the like.

[0085] Filler The solid cleaning composition may optionally contain a small but effective amount of one or more fillers. Some examples of suitable fillers include C1-C2 carboxylic acids such as sodium chloride, starch, sugars, propylene glycol, etc. 10 These may include alkylene glycols, sulfates, PEG, urea, sodium acetate, magnesium sulfate, sodium carbonate, etc. In some embodiments, fillers may be present in an amount ranging up to about 50% by weight, and in some embodiments, in an amount ranging from about 1-15% by weight.

[0086] Functional polydimethylsiloxone The solid cleaning composition may also optionally contain one or more functional polydimethylsiloxones. For example, in some embodiments, polyalkylene oxide-modified polydimethylsiloxanes, nonionic surfactants, or polybetaine-modified polysiloxane amphoteric surfactants may be employed as additives. Both, in some embodiments, are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted via a hydrosilylation reaction. Some examples of specific siloxane surfactants are known as SILWET® surfactants available from Union Carbide or ABIL® polyether or polybetaine polysiloxane copolymers available from Goldschmidt Chemical Corp. and are described in U.S. Pat. No. 4,654,161, which is incorporated herein by reference. In some embodiments, the specific siloxanes used may be described, for example, as having low surface tension, high wetting ability, and excellent lubricity. For example, these surfactants are said to be among the few surfactants capable of wetting polytetrafluoroethylene surfaces. The siloxane surfactant employed as an additive can be used alone or in combination with a fluorochemical surfactant. In some embodiments, the fluorochemical surfactant employed as an additive, optionally in combination with a silane, can be, for example, a nonionic fluorohydrocarbon, such as fluorinated alkyl polyoxyethylene ethanol, fluorinated alkyl alkoxylate, and fluorinated alkyl ester.

[0087] Further descriptions of such functional polydimethylsiloxane and / or fluorochemical surfactants are found in U.S. Patent Nos. 5,880,088, 5,880,089, and 5,603,776, all of which are incorporated herein by reference. For example, it has been found that the use of certain polysiloxane copolymers in a mixture with a hydrocarbon surfactant provides an excellent rinse aid for plastic ware. It has also been found that the combination of certain silicone polysiloxane copolymers and fluorocarbon surfactants with conventional hydrocarbon surfactants provides an excellent rinse aid for plastic ware. This combination has been found to be superior to the individual components, with the exception of certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine polysiloxane copolymers, which are approximately equally effective. Thus, some embodiments include the polysiloxane copolymer alone, and the combination with the fluorocarbon surfactant can involve a nonionic siloxane surfactant, polyether polysiloxane. Polybetaine polysiloxane copolymer, an amphoteric siloxane surfactant, can be employed alone as an additive in cleaning compositions to provide the same results.

[0088] In some embodiments, the composition may include a functionalized polydimethylsiloxone in an amount ranging up to about 10% by weight. For example, some embodiments may include a polyalkylene oxide-modified polydimethylsiloxane or a polybetaine-modified polysiloxane in an amount ranging from about 0.1 to 10% by weight, optionally in combination with about 0.1 to 10% by weight of a fluorinated hydrocarbon nonionic surfactant.

[0089] Hardener / Solidifier / Solubility Adjuster In some embodiments, one or more solidifying agents may be included in the cleaning composition. Examples of hardening agents include urea, amides, such as stearic acid monoethanolamide or lauric acid diethanolamide or alkylamides, sulfates or sulfated surfactants, and aromatic sulfonates, solid polyethylene glycols, solid EO / PO block copolymers, starches that have been rendered water-soluble through acid or alkali treatment processes, and various inorganic substances that impart solidifying properties to heated compositions upon cooling. Such compounds can also change the solubility of the composition in aqueous media during use, allowing active ingredients to be dispensed from the solid composition over an extended period of time.

[0090] Suitable aromatic sulfonates include, but are not limited to, sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate, and / or sodium butyl naphthalene sulfonate. Preferred aromatic sulfonates include sodium xylene sulfonate and sodium cumene sulfonate.

[0091] The amount of solidifying agent included in the cleaning composition can be influenced by the desired effect. Generally, an effective amount of solidifying agent is considered to be an amount that acts to solidify the cleaning composition, with or without other ingredients. Typically, in solid embodiments, the amount of solidifying agent in the cleaning composition ranges from about 10 to about 80% by weight of the cleaning composition, preferably from about 20 to about 75% by weight, and more preferably from about 20 to about 70% by weight of the cleaning composition. In one aspect of the invention, the solidifying agent is substantially sulfate-free. For example, the cleaning composition can have less than 1% by weight, preferably less than 0.5% by weight, and more preferably less than 0.1% by weight of sulfate. In a preferred embodiment, the cleaning composition is sulfate-free.

[0092] In certain embodiments, it may be desirable to have a second solidifying agent. In compositions containing a second solidifying agent, the composition may include the second solidifying agent in an amount ranging up to about 50% by weight. In some embodiments, the second solidifying agent may be present in an amount ranging from about 5 to about 35% by weight, often from about 10 to about 25% by weight, and sometimes from about 5 to about 15% by weight.

[0093] In some embodiments, one or more additional stiffening agents may be included in the solid cleaning composition if desired. Examples of stiffening agents include amides, such as stearic acid monoethanolamide or lauric acid diethanolamide or alkylamides, solid polyethylene glycols, or solid EO / PO block copolymers; starches rendered water-soluble through acid or alkali treatment processes; and various inorganic compounds that impart solidifying properties to heated compositions upon cooling. Such compounds can also alter the solubility of the composition in aqueous media during use, allowing ingredients to be dispensed from the solid composition over an extended period of time. The composition may include a second stiffening agent in an amount ranging up to about 30% by weight. In some embodiments, the second stiffening agent may be present in an amount ranging from about 5 to about 25% by weight, often from about 10 to about 25% by weight, and occasionally from about 5 to about 15% by weight.

[0094] moisturizer The solid cleaning composition may optionally also contain one or more humectants. A humectant is a substance that has an affinity for water. The humectant may be provided in an amount sufficient to help reduce the visibility of a film on the substrate surface. The visibility of a film on the substrate surface is particularly a concern when the rinse water contains more than 200 ppm of total dissolved solids. Thus, in some embodiments, the humectant is provided in an amount sufficient to reduce the visibility of a film on the substrate surface when the rinse water contains more than 200 ppm of total dissolved solids, compared to a rinse agent composition that does not contain a humectant. The term "water-solid film formation" or "film formation" refers to the presence of a visible, continuous layer of material on the substrate surface, which gives the appearance that the substrate surface is not clean.

[0095] Some exemplary humectants that can be used include materials containing more than 5% water by weight (based on the dry humectant) when equilibrated at 50% relative humidity and room temperature. Exemplary humectants that can be used include glycerin, propylene glycol, sorbitol, alkyl polyglycosides, polybetaine polysiloxanes, and mixtures thereof. In some embodiments, the rinse agent composition may include a humectant in an amount ranging up to about 75% by weight based on the total composition, and in some embodiments, from about 5% to about 75% by weight based on the weight of the composition.

[0096] Hydrable salts Solid cleaning compositions according to the present invention may optionally include at least one hydratable salt. In embodiments, the hydratable salt is sodium carbonate (also known as soda ash or ash) and / or potassium carbonate (also known as potash). In preferred embodiments, the hydratable salt is sodium carbonate, excluding potassium carbonate. The hydratable salt may be provided in a range of about 20% to about 90% by weight, preferably about 25% to about 90% by weight, and more preferably about 30% to about 70% by weight of a hydratable salt such as sodium carbonate. Those skilled in the art will recognize other suitable component concentration ranges to achieve comparable properties of the solidifying matrix.

[0097] In other embodiments, the hydratable salt may be combined with other solidifying agents. For example, the hydratable salt may be used with an additional solidifying agent that is inorganic in nature, and may optionally also act as an alkalinity source. In certain embodiments, the secondary solidifying agent may include, but is not limited to, additional alkali metal hydroxides, anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous sodium acetate, and other known hydratable compounds, or combinations thereof. According to a preferred embodiment, the second hydratable salt includes sodium metasilicate and / or anhydrous sodium metasilicate. The amount of secondary solidifying agent required to achieve solidification depends on several factors, including the exact solidifying agent employed, the amount of water in the composition, and the hydration capacity of other cleaning composition components. In certain embodiments, the secondary solidifying agent may also function as an additional alkalinity source.

[0098] polymer The cleaning composition may include a polymer or polymer system comprised of at least one polycarboxylic acid polymer, copolymer, and / or terpolymer. Particularly suitable polycarboxylic acid polymers of the present invention include, but are not limited to, polymaleic acid homopolymers, polyacrylic acid copolymers, and maleic anhydride / olefin copolymers.

[0099] Polymaleic acid (C4H2O3)x or hydrolyzed polymaleic anhydride, or cis-2-butenedioic acid homopolymer, has the following structural formula: [ka] where n and m are any integers. Examples of polymaleic acid homopolymers, copolymers, and / or terpolymers (and their salts) that can be used in the present invention are specific, and preferably have a molecular weight of about 0 to about 5,000, more preferably about 200 to about 2,000 (these MWs may be confirmed). Commercially available polymaleic acid homopolymers include Belclene 200 series maleic acid homopolymers from BWA™ Water Additives (979 Lakeside Parkway, Suite 925, Tucker, GA 30084, USA) and Aquatreat AR-801 available from AkzoNobel. The polymaleic acid homopolymers, copolymers, and / or terpolymers can be present in the cleaning composition at about 0.01% to about 30% by weight.

[0100] The cleaning compositions of the present invention may use polyacrylic acid polymers, copolymers, and / or terpolymers. Polyacrylic acid has the following structural formula: [ka] where n is any integer. Examples of suitable polyacrylic acid polymers, copolymers, and / or terpolymers include polyacrylic acid, (C3H4O2) n , or 2-propenoic acid, acrylic acid, polyacrylic acid, polymers, copolymers, and / or terpolymers of propenoic acid.

[0101] In one embodiment of the present invention, particularly suitable acrylic acid polymers, copolymers, and / or terpolymers have a molecular weight of about 100 to about 10,000, in a preferred embodiment about 500 to about 7000, in an even more preferred embodiment about 1000 to about 5000, and in a most preferred embodiment about 1500 to about 3500. Examples of polyacrylic acid polymers, copolymers, and / or terpolymers (or salts thereof) that can be used in the present invention include, but are not limited to, Acusol 448 and Acusol 425 from The Dow Chemical Company (Wilmington, Delaware, USA). In certain embodiments, it may be desirable to have acrylic acid polymers (and salts thereof) with a molecular weight greater than about 10,000. Examples include, but are not limited to, Acusol 929 (10,000 MW) and Acumer 1510 (60,000 MW), both available from Dow Chemical, and AQUATREAT AR-6 (100,000 MW) from AkzoNobel Strawinskylaan 2555 1077 ZZ Amsterdam Postbus 75730 1070 AS Amsterdam. The polyacrylic acid polymer, copolymer, and / or terpolymer may be present in the composition from about, and may be present from 0.01% to about 30% by weight in the cleaning composition.

[0102] Maleic anhydride / olefin copolymer is a copolymer of polymaleic anhydride and an olefin. Maleic anhydride ((C2H2(CO)2O)) has the following structure: [ka] Some maleic anhydride derivatives are maleimides, N-alkyl (C 1~4 ) Maleimide, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid, alkyl of the aforementioned acids (C 1~18 ) esters of the aforementioned acids, cycloalkyl (C 3~8 ) esters, sulfated castor oil, etc.

[0103] At least 95% by weight of the maleic anhydride polymer, copolymer, or terpolymer has a number average molecular weight in the range of about 700 to about 20,000, preferably about 1000 to about 100,000.

[0104] A wide variety of straight and branched chain alpha-olefins can be used for the purposes of this invention. Particularly useful alpha-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-1,5-hexadiene; dienes containing 4 to 8 carbon atoms, preferably C, such as isobutylene, 1-butene, 1-hexene, 1-octene, and the like. 4~10 It is a 1-alkene containing

[0105] In one embodiment of the present invention, particularly suitable maleic anhydride / olefin copolymers have a molecular weight of about 1000 to about 50,000, in a preferred embodiment about 5000 to about 20,000, and in a most preferred embodiment about 7500 to about 12,500. Examples of maleic anhydride / olefin copolymers that can be used in the present invention include, but are not limited to, Acusol 460N from The Dow Chemical Company (Wilmington, Delaware, USA). The maleic anhydride / olefin copolymer can be present in the cleaning composition at about 0.01% to about 30% by weight.

[0106] preservatives The solid cleaning composition can also contain an effective amount of preservative.Preferred preservatives for use in the solid cleaning composition include, but are not limited to, methylchloroisothiazolinone, methylisothiazolinone, pyrithione derivatives and salts, glutaraldehyde, or mixtures thereof.A preferred blend of methylchloroisothiazolinone and methylisothiazolinone is available from Dow Chemical under the trade name KATHON™ CG.A preferred pyrithione salt is sodium pyrithione.

[0107] When a preservative is included in the solid cleaning composition, it may be present at about 0.01 to about 5 wt. %, preferably about 0.01 to about 3 wt. %, more preferably about 0.05 to about 2 wt. %, and even more preferably about 0.05 to about 1 wt. %.

[0108] Cleaning Agents / Antimicrobial Agents The cleaning composition may optionally contain a disinfectant. Disinfectants, also known as antimicrobial agents, are chemical compositions that can be used in solid functional materials to prevent microbial contamination and deterioration of material systems, surfaces, etc. Generally, these materials are divided into specific classes, including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, analides, organic sulfur and sulfur-nitrogen compounds, and other compounds.

[0109] It should also be understood that active oxygen compounds, such as those discussed in the bleach section above, can also act as antimicrobial agents and even provide germicidal activity. Indeed, in some embodiments, the ability of active oxygen compounds to act as antimicrobial agents reduces the need for additional antimicrobial agents in the composition. For example, percarbonate compositions have been demonstrated to provide excellent antimicrobial activity. Nevertheless, some embodiments incorporate additional antimicrobial agents.

[0110] Depending on the chemical composition and concentration, a given antimicrobial agent can simply limit the further growth of microbial populations or destroy all or part of the microbial population. The terms "microbe" and "microorganism" typically refer primarily to bacteria, viruses, yeast, spores, and fungal microorganisms. When used, the antimicrobial agent is typically formed into a solid functional material, which is optionally diluted, for example, using a water stream, to form an aqueous disinfectant or sanitizer composition that can contact various surfaces when dispensed, preventing the growth of or killing a portion of the microbial population. A 3-log reduction in the microbial population results in a sanitizer composition. The antimicrobial agent can be encapsulated, for example, to improve its stability.

[0111] Some examples of common antimicrobial agents include phenolic antimicrobials such as pentachlorophenol, orthophenylphenol, chloro-p-benzylphenol, and p-chloro-m-xylenol. Halogen-containing antimicrobial agents include bromine compounds such as sodium trichloroisocyanurate, sodium dichloroisocyanurate (anhydrous or dihydrate), iodo-poly(vinylpyrolidinone) complex, 2-bromo-2-nitropropane-1,3-diol, and quaternary antimicrobial agents such as benzalkonium chloride, didecyldimethylammonium chloride, choline diiodochloride, and tetramethylphosphonium tribromide. Other antimicrobial compositions, such as hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates such as sodium dimethyldithiocarbamate, and various other materials, are known in the art for their antimicrobial properties.

[0112] In embodiments of the solid cleaning composition that are phosphate-free and / or sulfate-free and also include an antimicrobial agent, the antimicrobial agent is selected to meet these requirements. Embodiments of the solid cleaning composition that include only GRAS ingredients may exclude or omit the antimicrobial agents described in this section.

[0113] In some embodiments, the cleaning composition comprises an antimicrobial component in the range of up to about 10% by weight of the composition, in some embodiments up to about 5% by weight, or in some embodiments, in the range of about 0.01 to about 3% by weight of the composition, or in the range of 0.05 to 1% by weight.

[0114] Additional Surfactants The solidified surfactant composition may contain an optional co-surfactant. Preferably, the co-surfactant is in solid form. Furthermore, the solidified surfactant composition of the present invention can be incorporated into cleaning compositions. These cleaning compositions may include, but are not limited to, detergent compositions, utensil cleaning compositions, laundry compositions, rinse aids, and hard surface cleaning compositions. Surfactants that can be included as co-surfactants in the solidified surfactant composition and / or as surfactants in the cleaning composition include nonionic surfactants, semi-polar nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures or combinations thereof.

[0115] When a co-surfactant carrier is included in the solidified surfactant composition of the present invention, the co-surfactant is preferably present in a weight ratio of about 1:0 to about 0:1 relative to the liquid surfactant. In further embodiments of the present invention, the co-surfactant carrier is present in an amount of about 20% to about 90% by weight, more preferably about 30% to about 90% by weight, and more preferably about 40% to about 80% by weight.

[0116] Nonionic surfactants The solid cleaning composition may optionally include one or more additional nonionic surfactants. Suitable additional nonionic surfactants may include, but are not limited to: Condensation products of one mole of alkylphenol, in which the alkyl chain, of straight or branched chain configuration, or single or double alkyl members, contains from about 8 to about 18 carbon atoms, with from about 3 to about 50 moles of ethylene oxide. The alkyl group can be represented, for example, by diisobutylene, di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemistry are available under the trade names Igepal® from Solvay and Triton® from Dow.

[0117] The condensation product of one mole of a saturated or unsaturated straight- or branched-chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid portion may consist of a mixture of acids within the carbon atom range defined above, or may consist of an acid having a specific number of carbon atoms within this range. Examples of commercially available compounds of this chemical structure are available on the market under the trade names Nopalcol™, manufactured by Henkel Corporation, and Lipopeg™, manufactured by Lipo Chemicals, Inc.

[0118] Compounds from groups (1), (2), (3), and (4) modified by "capping" or "end-blocking" the terminal hydroxy group(s) (of the polyfunctional moiety) to reduce foaming by reaction with hydrophobic small molecules such as propylene oxide, butylene oxide, benzyl chloride, and short-chain fatty acids, alcohols, or alkyl halides containing 1 to about 5 carbon atoms, and mixtures thereof. Also included are reactants such as thionyl chloride that convert the terminal hydroxy group to a chloride group. Such modifications to the terminal hydroxy group can result in all-block, block-heteric, heteric-block, or all-heteric nonionics.

[0119] The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486, issued Sep. 8, 1959 to Brown et al., and represented by the formula: [ka] wherein R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.

[0120] Polyalkylene glycol condensates of U.S. Pat. No. 3,048,548, issued Aug. 7, 1962 to Martinet al., having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, wherein the weight of the terminal hydrophobic chains, the weight of the intermediate hydrophobic units, and the weight of the linking hydrophilic units each represent about one-third of the condensate.

[0121] The general formula Z[(OR) where Z is an alkoxylatable material, R is a radical derived from an alkaline oxide, which can be ethylene and propylene, n is an integer, for example, from 10 to 2,000 or more, and z is an integer determined by the number of reactive oxyalkylatable groups. n OH] z The antifoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178, issued May 7, 1968 to Lissant et al., having the formula:

[0122] Formula Y(C3H6O) n (C2H4O) m Conjugated polyoxyalkylene compounds as described in U.S. Pat. No. 2,677,700, issued May 4, 1954 to Jackson et al., corresponding to H, wherein Y is the residue of an organic compound having from about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of at least about 6.4 as determined by the hydroxyl number, and m has a value such that the oxyethylene moieties constitute from about 10% to about 90% by weight of the molecule.

[0123] Formula Y[(C3H6O n (C2H4O) m H] xNo. 2,674,619, issued April 6, 1954 to Lundsted et al., wherein Y is the residue of an organic compound having about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, where x has a value of at least about 2; n has a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900; and m has a value such that the oxyethylene content of the molecule is about 10% to about 90% by weight. Compounds falling within the definition for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, ethylenediamine, and the like. The oxypropylene chains optionally, but beneficially, contain small amounts of ethylene oxide, and the oxyethylene chains also optionally, but beneficially, contain small amounts of propylene oxide.

[0124] Further conjugated polyoxyalkylene surfactants advantageously used in the compositions of the present invention have the formula: P[(CHO) n (C2H4O) m H] x where P is the residue of an organic compound having from about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44, and m has a value such that the oxypropylene content of the molecule is from about 10% to about 90% by weight. In either case, the oxypropylene chains may optionally, but advantageously, contain small amounts of ethylene oxide, and the oxyethylene chains may optionally, but advantageously, contain small amounts of propylene oxide.

[0125] Anionic surfactants Surfactants classified as anionic because the charge on the hydrophobic substance is negative, or surfactants in which the hydrophobic portion of the molecule does not carry a charge unless the pH is raised above neutral (e.g., carboxylic acids), are also useful in the present invention. Carboxylate, sulfonate, sulfate, and phosphate are polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium, and potassium impart water solubility, ammonium and substituted ammonium ions provide both water and oil solubility, and calcium, barium, and magnesium promote oil solubility. As those skilled in the art will appreciate, anionics are excellent detersive surfactants and are therefore preferred additives to heavy-duty detergent compositions.

[0126] Anionic sulfate surfactants suitable for use in the present compositions include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, C5-C 17 These include alkylpolysaccharide sulfates such as acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (usually having 1 to 6 oxyethylene groups per molecule).

[0127] Anionic sulfonate surfactants suitable for use in the present compositions also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substitution.

[0128] Anionic carboxylate surfactants suitable for use in the present compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, and sulfonated fatty acids, such as sulfonated oleic acid. Such carboxylates include alkyl ethoxy carboxylates, alkylaryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates useful in the present compositions include those containing a carboxyl unit attached to a secondary carbon. The secondary carbon can be in a ring structure, as in p-octyl benzoic acid or alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants generally lack ether linkages, ester linkages, and hydroxyl groups. Furthermore, they generally lack a nitrogen atom in the head group (amphiphilic portion). Suitable secondary soap surfactants generally contain 11 to 13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acylamino acids (and salts) such as acylgluamates, acylpeptides, sarcosinates (e.g., N-acylsarcosinates), taurates (e.g., N-acyltaurates, and fatty acid amides of methyl tauride), and the like.

[0129] Suitable anionic surfactants include alkyl or alkylaryl ethoxy carboxylates of the formula: RO-(CH2CH2O) n (CH2) m -CO2X(3) where R is C8-C 22 is an alkyl group, or [ka] , R 1 is C4-C 16is an alkyl group, n is an integer from 1 to 20, m is an integer from 1 to 3, and X is a counterion such as hydrogen, sodium, potassium, lithium, ammonium, or an amine salt such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10 and m is 1. In some embodiments, R is a C8-C 16 In some embodiments, R is an alkyl group. 12 -C 14 It is an alkyl group, n is 4, and m is 1.

[0130] In other embodiments, R is [ka] and R 1 is C6-C 12 In still other embodiments, R 1 is a C9 alkyl group, n is 10, and m is 1.

[0131] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available in the acid form, which can be easily converted to the anionic or salt form. Commercially available carboxylates include Neodox 23-4, C 12-13 Carboxylate, such as the product Sandopan® DTC, C alkyl polyethoxy (4) carboxylic acid (Shell Chemical), and Emcol CNP-110, C alkylaryl polyethoxy (10) carboxylic acid (Witco Chemical). 13 Alkylpolyethoxy(7)carboxylic acids are also available from Clariant.

[0132] cationic surfactants A surfactant is classified as cationic if the charge on the hydrotrope portion of the molecule is positive. Surfactants in which the hydrotrope is uncharged until the pH is lowered to near-neutral or below, but then becomes cationic (e.g., alkylamines), are also included in this group. In theory, cationic surfactants can be synthesized from any combination of elements containing the "onium" structure RnX+Y-- and can include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the cationic surfactant field is dominated by nitrogen-containing compounds, likely because synthetic routes to nitrogenous cationic materials are simple and easy and provide high product yields, which can make them less expensive.

[0133] Cationic surfactants preferably include, and more preferably refer to, compounds containing at least one long-carbon-chain hydrophobic group and at least one positively charged nitrogen. The long-carbon-chain group can be directly attached to the nitrogen atom by simple substitution, or more preferably, indirectly attached through a bridging functional group in so-called interrupted alkylamines and amidoamines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more easily dissolved in water by co-surfactant mixtures, and / or water-soluble. To increase water solubility, additional primary, secondary, or tertiary amino groups can be introduced, or the amino nitrogen can be quaternized with a low-molecular-weight alkyl group. Furthermore, the nitrogen can be part of a branched or linear moiety with various degrees of unsaturation, or part of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants can contain complex bonds with two or more cationic nitrogen atoms.

[0134] Surfactant compounds classified as amine oxides, amphoterics, and zwitterions are themselves typically cationic in solutions 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.

[0135] The simplest cationic amines, amine salts, and quaternary ammonium compounds are depicted schematically as follows: [ka] where R represents an alkyl chain, R', R'', and R''' can be either an alkyl chain or an aryl group or hydrogen, and X represents an anion. Amine salts and quaternary ammonium compounds are preferred for practical use in the present invention due to their high degree of water solubility.

[0136] The majority of commercially available cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art, as described in "Surfactant Encyclopedia," Cosmetics & Toiletries, Vol. 104(2) 86-96 (1989). The first class includes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourth class includes quaternaries such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, and tetraalkylammonium salts. Cationic surfactants are known to have a variety of properties that can be beneficial in the present compositions. These desirable properties may include detergency in compositions below neutral pH, antimicrobial efficacy, thickening or gelling in conjunction with other agents, and the like.

[0137] Cationic surfactants useful in the compositions of the present invention include those of formula R 1 m R 2 x YL Z, wherein each R 1 contains a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxy groups, and up to four of the following structures: [ka] or an isomer or mixture of these structures, containing about 8 to 22 carbon atoms. 1 The group may further contain up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, there is no more than one R 1 The group has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3. R 2 are each alkyl or hydroxyalkyl groups containing 1 to 4 carbon atoms or a benzyl group, and there is not more than one R 2 is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom positions on the Y group are filled with hydrogen.

[0138] Y is [ka] or mixtures thereof. Preferably, L is 1 or 2, and the Y group is an R group having 1 to about 22 carbon atoms and two free carbon single bonds when L is 2. 1 and R 2 Z is a water-soluble anion such as a halide, sulfate, methyl sulfate, hydroxide, or nitrate, with chloride, bromide, iodide, sulfate, or methyl sulfate being preferred in numbers that provide electroneutrality of the cationic component.

[0139] amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups and organic hydrophobic groups. These ionic entities can be either anionic or cationic groups as described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, sulfonates, sulfates, phosphonates, or phosphates provide the negative charge.

[0140] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary amines and aliphatic tertiary amines, in which the aliphatic radical may be linear or branched, one of the aliphatic substituents containing about 8 to 18 carbon atoms, and one containing an anionic water-solubilizing group, such as carboxy, sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are known to those skilled in the art and are subdivided into two major classes, as described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104(2)69-71 (1989), the entire contents of which are incorporated herein by reference. The first class includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkylamino acids and their salts. Some amphoteric surfactants can be considered to fall into both classes.

[0141] Amphoteric surfactants can be synthesized by methods known to those skilled in the art.For example, 2-alkylhydroxyethyl imidazoline is synthesized by condensation and ring closure of long-chain carboxylic acid (or derivative) with dialkylethylenediamine.Commercially available amphoteric surfactants are derivatized by subsequent hydrolysis and alkylation to open the imidazoline ring, for example, using chloroacetic acid or ethyl acetate.During alkylation, one or two carboxy-alkyl groups react to form tertiary amine and ether bond, and different alkylating agents produce different tertiary amines.

[0142] Long chain imidazole derivatives having use in the present invention generally have the following general formula: [ka] [ka] wherein R is an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation, typically sodium, for neutralizing the charge of the anion. Commercially known imidazoline-derived amphoteric compounds that can be used in the present compositions include, for example, cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. Amphocarboxylic acids can be generated from aliphatic imidazolines, where the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0143] The carboxymethylated compounds (glycinates) described hereinabove are often called betaines, which are a special class of amphoteric surfactants discussed herein below in the section entitled Zwitterionic Surfactants.

[0144] Long-chain N-alkyl amino acids are readily prepared by the reaction RNH2, where R = C8-C 18These are aliphatic amines with straight-chain or branched alkyl or halogenated carboxylic acids. Alkylation of the primary amino group of an amino acid results in secondary and tertiary amines. The alkyl substituent may have additional amino groups that provide multiple reactive nitrogen centers. Most commercially available N-alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercial N-alkylamino acid ampholytes that have application in the present invention include alkyl beta-aminodipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In one embodiment, R can be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

[0145] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include, as part of their structure, an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety such as glycine, or a combination thereof, and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkyl amphodicarboxylic acids. These amphoteric surfactants include C 12 -Alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -Alkyl-C(O)-N(H)-CH2-CH2-N + The surfactant may include a chemical structure represented as (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is one suitable amphoteric surfactant and is commercially available from Rhodia Inc., Cranbury, New Jersey, under the trade name Miranol™ FBS. Another suitable coconut-derived amphoteric surfactant having the chemical name disodium cocoamphodiacetate is sold under the trade name Mirataine™ JCHA, also from Rhodia Inc., Cranbury, New Jersey.

[0146] A typical list of amphoteric classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are found in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein by reference in its entirety.

[0147] Zwitterionic surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can contain an anionic charge. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, heterocyclic secondary and tertiary amines, or quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants contain a positively charged quaternary ammonium, or sometimes sulfonium or phosphonium ion, a negatively charged carboxyl group, and an alkyl group. Zwitterionic compounds generally contain cationic and anionic groups that ionize to approximately the same degree in the isoelectric region of the molecule, which can create a strong "inner salt" attraction between the positive and negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds in which the aliphatic radical may be straight or branched, one of the aliphatic substituents contains 8 to 18 carbon atoms, and one contains an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate, phosphate, or phosphonate.

[0148] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein. The general formula for these compounds is: [ka] In the formula, R 1comprises an alkyl, alkenyl, or hydroxyalkyl radical of 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R 2 is an alkyl group or a monohydroxyalkyl group containing 1 to 3 carbon atoms, x is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen atom or a phosphorus atom, and R 3 is an alkylene or hydroxyalkylene or hydroxyalkylene of 1 to 4 carbon atoms, and Z is a radical selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfate group, a phosphonate group, and a phosphate group.

[0149] Examples of zwitterionic surfactants having the above structure include 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate, 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate, 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate, 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate, 3-(N,N-dimethyl-N- Examples of suitable detergent surfactants include S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-propane-1-sulfonate, 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in such detergent surfactants may be straight-chained or branched, saturated or unsaturated.

[0150] Zwitterionic surfactants suitable for use in the present compositions include betaines of the following general structure: [ka] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH or exhibit reduced water solubility in these isoelectric ranges. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C 12-14 Acylamidopropyl betaine, C 8-14 Acylamidohexyldiethylbetaine, 4-C 14-16 Acylmethylamidodiethylammonio-1-carboxybutane, C 16-18 Acylamide dimethyl betaine, C 12-16 Acylamidopentanediethyl betaine, and C 12-16 Acylmethylamidodimethylbetaine is an example.

[0151] Sultaines useful in the present invention have the formula (R(R 1 )2N + R 2 SO 3- where R is C6-C 18 is a hydrocarbyl group, and each R 1 are typically independently C1-C3 alkyl, e.g., methyl, and R 2 is a C1-C6 hydrocarbyl group, for example a C1-C3 alkylene or hydroxyalkylene group.

[0152] A typical list of zwitterionic classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are found in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). Each of these references is incorporated herein in its entirety.

[0153] Method for producing a cleaning composition The solidified surfactant composition of the present invention can be included in various cleaning compositions.Preferably, the cleaning composition is a solid composition.Suitable solid cleaning compositions include, but are not limited to, granular and pelletized solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block compositions, pressed solid compositions, etc.Preferably, the cleaning composition is a pressed solid.

[0154] Solid particulate cleaning compositions can be made by simply blending the dry solid components formed according to the present invention in the appropriate ratio, or by agglomerating the materials in a suitable agglomeration system. Pelletized materials can be produced by compressing solid granules or agglomerated materials in suitable pelletizing equipment to produce appropriately sized pelletized materials. Solid block and cast solid block materials can be made by introducing either a block of pre-hardened material or a castable liquid that hardens into a solid block in the container into a container. Preferred containers include disposable plastic containers or water-soluble film containers. Other suitable packaging for the compositions includes flexible bags, packets, shrink wrap, and water-soluble films such as polyvinyl alcohol.

[0155] In exemplary embodiments, a single- or twin-screw extruder is used to combine and mix one or more components under high shear to form a homogeneous mixture. In some embodiments, the processing temperature is below the melting temperature of the components. The processed mixture can be dispensed from the mixer by molding, casting, or other suitable means, where the cleaning composition hardens into a solid form. The structure of the matrix can be characterized according to its hardness, melting point, material distribution, crystalline structure, and other similar properties by methods known in the art. Generally, the solid cleaning composition processed according to the method of the present invention is substantially homogeneous throughout its mass with respect to the distribution of components and is dimensionally stable.

[0156] In the extrusion 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 the mass. The mixture is then discharged from the mixing system into or through a die or other shaping means. The product is then packaged. In exemplary embodiments, the formed composition begins to harden into a solid form in approximately 1 minute to approximately 3 hours. Specifically, the formed composition begins to harden into a solid form in approximately 1 minute to approximately 2 hours. More specifically, the formed composition begins to harden into a solid form in approximately 1 minute to approximately 20 minutes.

[0157] In the casting process, the liquid and solid components are introduced into a final mixing system and continuously mixed until the components form a substantially homogeneous liquid mixture in which the components are distributed throughout the mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once mixing is complete, the product is transferred to a packaging container where solidification occurs. In an exemplary embodiment, the casting composition begins to harden into a solid form in approximately 1 minute to approximately 3 hours. Specifically, the casting composition begins to harden into a solid form in approximately 1 minute to approximately 2 hours. More specifically, the casting composition begins to harden into a solid form in approximately 1 minute to approximately 20 minutes.

[0158] In the press-solid process, flowable solids, such as granular solids or other particulate solids, are combined under pressure. In the press-solid process, the flowable solids of the composition are placed in a form (e.g., a mold or container). The method can include gently pressing the flowable solids in the form to produce a solid cleaning composition. Pressure can be applied by a block machine or a rotary platen press, etc. Pressure can be applied at about 1 to about 3,000 psi, about 5 to about 2,500 psi, or about 10 psi to about 2,000 psi. As used herein, the term "psi" or "pounds per square inch" refers to the actual pressure applied to the flowable solids being pressed, and not a gauge or water pressure measured at a point on the pressing device. The method can include a curing step to produce the solid cleaning composition. As referred to herein, an uncured composition containing the flowable solids is compressed to provide sufficient surface contact between the particles that make up the flowable solids such that the uncured composition will solidify into a stable solid cleaning composition. A sufficient amount of particles (e.g., granules) in contact with one another provides effective particle-to-particle bonding to create a stable solid composition. Inclusion of an optional curing step can include allowing the pressed solid to solidify for a period of time, such as several hours or about a day (or more). In additional aspects, the method can include vibrating the flowable solid in a mold or form, such as the method disclosed in U.S. Pat. No. 8,889,048, the entire contents of which are incorporated herein by reference.

[0159] The use of pressed solids offers many advantages over conventional solid block or tablet compositions, which require high pressure in a tablet press, or casting, which requires melting the composition, which consumes a significant amount of energy, and / or extrusion, which requires expensive equipment and advanced technical knowledge. Pressed solids overcome various limitations of other solid formulations, which is why it is necessary to create solid cleaning compositions. Furthermore, pressed solid compositions retain their shape under conditions under which the composition may be stored or handled.

[0160] The term "solid" means that the hardened composition will not flow and will substantially retain its shape under moderate stress or pressure or simple gravity. The solid may be in various forms, such as powder, flake, granule, pellet, tablet, drop, puck, briquette, brick, solid block, unit dose, or another solid form known to those skilled in the art. The hardness of the solid cast and / or pressed solid composition may range from that of a relatively dense and hard fused solid product, such as concrete, to a hardness characterized as a hardened paste. Additionally, the term "solid" refers to the state of the cleaning composition under the expected conditions of storage and use of the solid cleaning composition. In general, it is expected that the cleaning composition will remain in solid form when exposed to temperatures up to approximately 100°F, specifically up to approximately 120°F.

[0161] The resulting solid cleaning composition can take forms including, but not limited to, cast solid products, extruded, molded, or formed solid pellets, blocks, tablets, powders, granules, flakes, pressed solids, or the formed solids can be subsequently ground or formed into powders, granules, or flakes. In exemplary embodiments, the extruded pellet material formed by the solidification matrix weighs approximately 50 grams to approximately 250 grams, the extruded solid formed by the composition weighs approximately 100 grams or more, and the solid block detergent formed by the composition has a mass of approximately 1 to approximately 10 kilograms. The solid composition provides a stabilized source of functional materials. In some embodiments, the solid composition may be dissolved, for example, in an aqueous or other medium, to produce a concentrated solution and / or a use solution. This solution may be directed to a storage container for subsequent use and / or dilution, or may be applied directly at the time of use.

[0162] The following patents disclose various combinations of solidifying agents, binders, and / or hardeners that may be utilized in the solid cleaning compositions of the present invention: U.S. Patent Nos. 7,153,820, 7,094,746, 7,087,569, 7,037,886, 6,831,054, 6,730,653, 6,660,707, 6,653,266, 6,583,094, 6,410,495, 6,258,765, 6,583,094, 6,410,495, 6,258,765, 6,583,094, 6,653,26 ... ,177,392, 6,156,715, 5,858,299, 5,316,688, 5,234,615, 5,198,198, 5,078,301, 4,595,520, 4,680,134, RE32,763, and RE32818 are incorporated herein by reference.

[0163] Liquid compositions can typically be prepared by forming components in aqueous liquid or aqueous liquid solvent systems.Such systems are typically prepared by dissolving or suspending active ingredients in water or compatible solvents, and then diluting the product to an appropriate concentration to form either a concentrate or its use solution.Gelled compositions can similarly be prepared by dissolving or suspending active ingredients in a compatible aqueous, aqueous liquid, or mixed aqueous-organic system containing a gelling agent at an appropriate concentration.All publications and patent applications in this specification are indicative of the level of those skilled in the art to which this invention pertains.All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application were specifically and individually incorporated by reference. [Example]

[0164] Embodiments of the present invention are further defined in the following non-limiting examples. These examples, while illustrating specific embodiments of the present invention, should be understood to be given by way of illustration only and are non-limiting. From the above description and these examples, one skilled in the art can ascertain the essential features of the present invention and can make various changes and modifications to the embodiments of the present invention to adapt them to various uses and conditions without departing from the spirit and scope of the present invention. Thus, various modifications of the embodiments of the present invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

[0165] Materials used: BIO-TERGE® AS-90, a 90% active spray-dried C14-C16 sodium alpha olefin sulfonate available from Stepan Co. DEHYPON® LS54: A low-foaming fatty alcohol and ethylene oxide / propylene oxide derivative available from BASF Corp. DEQUEST® 2016D: A hydroxylethylidene-based scale inhibitor available from Italmatch Chemicals. GLUCOPON® 625UP: Available from BASF Corp., an alkyl polyglucoside. LUTENSOL® TDA-3: available from BASF Corp., tridecyl alcohol ethoxylate. LUTENSOL® XL40: A non-ionic branched gel bed containing alkylene oxide, available from BASF Corp. LUTENSOL® XP50: A non-ionic branched gel bed with ethylene oxide available from BASF Corp. PLURAFAC® LF221: A fatty alcohol alkoxylate available from BASF Corp. PLURAFAC® RA300: A fatty alcohol alkoxylate available from BASF Corp. PLURAFAC® SLF-180: available from BASF Corp., fatty alcohol alkoxylate. PLURONIC® 25R2: A propoxylated polyoxyethylene available from BASF Corp. PLURONIC® F68: A difunctional block copolymer with terminal primary hydroxyl groups, available from BASF Corp. PLURONIC® L61: A difunctional block copolymer with terminal primary hydroxyl groups, available from BASF Corp. SURFONIC® L24-7: Linear C available from Huntsman Petrochemical Corp. 12~16 Alcohol ethoxylate. TETRONIC® 1301: A tetrafunctional block copolymer available from BASF Corp. TETRONIC® 150R1: A reverse tetrafunctional block copolymer available from BASF Corp. TOMADOL® 91-6: Available from Evonik 9~11 Ethoxylated alcohols.

[0166] Additional ingredients employed, available from multiple commercial sources, include anhydrous citric acid, polyethylene glycol (PEG 8000), sodium carbonate, sodium chloride (NaCl), anhydrous sodium sulfate, sodium xylene sulfonate (SXS), and urea.

[0167] Example 1 Solidifying liquid nonionic surfactants in a spray dryer Exemplary liquid nonionic surfactants were solidified in a spray drying device.

[0168] Tests were conducted to evaluate the solidification of liquid nonionic surfactants by binders. Table 2 provides the compositions prepared and comments on the powder flow characteristics of the resulting solidified surfactant compositions. The weights of the components in each prepared composition represent the liquid composition before solidification. [Table 5] [Table 6] [Table 7]

[0169] As can be seen from Table 2, the liquid nonionic surfactants, when combined with a binder through solidification using a spray dryer, could be solidified in powder form with good flow properties.

[0170] Example 2 Solidification of liquid nonionic surfactants in a fluidized bed. Exemplary liquid nonionic surfactants were solidified in a fluidized bed. Tests were conducted to evaluate the solidification of liquid nonionic surfactants with binders. Table 3 provides comments on the powder flow characteristics of the prepared compositions and the resulting solidified surfactant compositions. [Table 8]

[0171] As can be seen from Table 3, the liquid nonionic surfactants, when combined with binders through fluidized bed solidification, were able to be solidified in powder form with good flow properties.

[0172] The fluidized bed solidified nonionic liquid surfactant compositions were further compared to nonionic liquid surfactant compositions solidified in a conventional conical blender. Table 4 shows the compositions prepared along with the method used for solidification. [Table 9]

[0173] After solidifying the liquid surfactant composition, two compositions, Composition A and Composition B, solidified via a fluidized bed, resulted in free-flowing powders with a non-sticky consistency and easily broken up clumps (if any). In comparison, Composition C, solidified via a conventional conical blender, resulted in undesirable powder flow, with the powder being sticky and clumpy. Furthermore, the powder of Composition C was not free-flowing. Thus, the results demonstrate the ability of the solidification method employed in the present invention to form free-flowing powders compared to conventional solidification methods utilizing blenders and mixers, which cannot produce free-flowing powders.

[0174] Example 3 Solidification of nonionic surfactants without processing steps Exemplary liquid nonionic surfactants were evaluated for solidification without any processing steps. Tests were conducted to evaluate the solidification of liquid nonionic surfactants with binders. Table 5 provides comments on the prepared compositions and the powder flow characteristics of the resulting solidified surfactant compositions. The compositions were not solidified via a spray dryer or fluidized bed as described herein, but were prepared in a conventional conical blender or conventional ribbon blender. Ground urea and fine SXS powder were used to increase surface area. [Table 10]

[0175] As can be seen in Table 5, conventional mixing processes did not result in free-flowing powders. The results indicate that mixing only a liquid surfactant with a binder or carrier without a drying process does not form a free-flowing powder. These results further distinguish the solidification method employed in the present invention to form a free-flowing powder compared to simply combining the surfactant and binder components.

[0176] Example 4 Pressed solid formulations using nonionic surfactant powders Pre-mix compositions of liquid nonionic surfactant and SXS were formulated into flowable powders for evaluation in rinse aid formulations. Table 6 shows the pre-mix compositions containing nonionic surfactant and SXS before solidification. The compositions were dried in a fluidized bed to form dry flowable powders. The liquid flow rate was maintained at 30 g / min for each pre-mix composition, and the process air flow rate was 90 m 3 / hr, the inlet air temperature was 120° C. and the bed temperature was maintained at 70° C. The percent of dry surfactant in powder is also listed in Table 6. [Table 11]

[0177] The free-flowing powder pre-mix compositions from Table 6 were incorporated into rinse aid formulations and pressed into pressed solids. Table 7 provides pressed rinse aid compositions that were evaluated for their ability to form pressed solids using nonionic surfactants and SXS pre-mix compositions. The components of the solidified rinse aid compositions were combined in a ribbon blender and slowly mixed for approximately 30 seconds. The dye was slowly poured on top and allowed to mix for 1 minute. The blocks, each weighing approximately 0.91 kg, were pressed into pressed solids. The percent of total surfactant in the solidified rinse aid compositions, along with the flow index and particle size distribution of the solidified rinse aid compositions, are further shown below. [Table 12]

[0178] The incorporation of pre-mixed nonionic surfactant and SXS compositions blended well with the additional rinse aid components, as shown in Table 7. Although the batches exhibited uneven dye dispersion, all solidified rinse aid compositions pressed well with little or no buildup on contacted surfaces.

[0179] The features disclosed in the foregoing description or the following claims, whether presented in a specific form, or in terms of means for performing a disclosed function, or a method or process for achieving a disclosed result, can, where appropriate, be utilized separately or in any combination of such features to realize the invention in diverse forms thereof.

[0180] The invention being thus described, it will be apparent that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the invention, and all such modifications are intended to be included within the scope of the following claims. The above specification provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention resides in the claims.

Claims

1. a liquid nonionic surfactant; a solid binder comprising a natural polymer, urea, a urea derivative, a polyacrylate, a chelating agent, PEG, an inorganic acid and / or a salt thereof, an organic salt and / or a salt thereof, an aromatic sulfonate, or a combination thereof; 1. A solidified liquid surfactant composition comprising: the ratio of said solid binder to said liquid surfactant on an actives basis is from about 4:1 to about 1:60; A solidified liquid surfactant composition, wherein the composition is solid and the liquid surfactant is solidified in the composition.

2. 10. The solidified surfactant composition of claim 1, wherein the ratio of actives of the solid binder and the liquid surfactant is from about 3:1 to about 1:

50.

3. 3. The solidified surfactant composition of claim 1 or 2, wherein the liquid nonionic surfactant is a block copolymer, an alcohol alkoxylate, an alkoxylated surfactant, a reverse EO / PO copolymer, an alkyl polysaccharide, an alkoxylated amine, a fatty acid alkoxylate, a fatty acid amide alkoxylate, an alkanoate, and combinations thereof.

4. The solidified surfactant composition of any one of claims 1 to 3, wherein the solidified surfactant composition is a free-flowing powder.

5. The solidified surfactant composition of any one of claims 1 to 4, wherein the binder is urea, a urea derivative, or a combination thereof.

6. 5. The solidified surfactant composition of claim 1, wherein the binder is sodium acetate, sodium chloride, sodium sulfate, magnesium sulfate, sodium xylene sulfonate, an alkali metal carbonate, PEG having a melting point of at least about 40°C, or a combination thereof.

7. 5. The solidifying surfactant composition of claim 1, wherein the binder is a gum, cellulose, cellulose ester, chitin, chitosan, starch, chemically modified starch, protein, lignin, natural rubber, or a combination thereof.

8. The solidified surfactant composition of any one of claims 1 to 7, wherein the binder comprises a chelating agent, and the chelating agent is an aminocarboxylate.

9. 9. The solidified surfactant composition of claim 6, wherein the binder is PEG 1450, PEG 3350, PEG 4000, PEG 4600, PEG 8000, or a combination thereof.

10. The solidified surfactant composition of any one of claims 1 to 9, further comprising a carrier.

11. 11. The solidified surfactant composition of claim 10, wherein the binder and carrier have a water solubility of about 0.2 g / L or greater at 20°C.

12. 12. The solidifying surfactant composition of claim 10 or 11, wherein the carrier is an anionic surfactant, an organic salt, an inorganic salt, or a combination thereof.

13. 13. The solidified surfactant composition of any one of claims 10 to 12, wherein the carrier comprises an alpha olefin sulfonate, a linear alkyl sulfonate, sodium lauryl sulfate, a sodium alkyl sulfate, sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium sulfate, sodium chloride, or a combination thereof.

14. The solidified surfactant composition of any one of claims 1 to 13, wherein the carrier is a solid.

15. The solidified surfactant composition of any one of claims 1 to 14, wherein the solidified surfactant composition has less than about 12% by weight of water.

16. The solidified surfactant composition of any one of claims 1 to 15, wherein the solidified surfactant composition has less than about 10% by weight of water.

17. a liquid nonionic surfactant; a carrier comprising an anionic surfactant, an inorganic acid and / or its salt, an organic salt and / or its salt, or a combination thereof; 1. A solidified liquid surfactant composition comprising: the ratio of said carrier to said liquid surfactant on an actives basis is from about 5:1 to about 1:30; A solidified liquid surfactant composition, wherein the composition is solid and the liquid surfactant is solidified in the composition, resulting in a solidified surfactant composition.

18. 18. The solidified surfactant composition of claim 17, wherein the ratio of actives of the carrier and the liquid surfactant is from about 2:1 to about 1:

20.

19. 19. The solidified surfactant composition of claim 17 or 18, wherein the liquid nonionic surfactant is a block copolymer, an alcohol alkoxylate, an alkoxylated surfactant, a reverse EO / PO copolymer, an alkyl polysaccharide, an alkoxylated amine, a fatty acid alkoxylate, a fatty acid amide alkoxylate, an alkanoate, and combinations thereof.

20. 20. The solidified surfactant composition of any one of claims 17 to 19, wherein the solidified liquid surfactant composition is a free-flowing powder.

21. 21. The solidified surfactant composition of any one of claims 17 to 20, wherein the carrier comprises an anionic surfactant, and the anionic surfactant is a sulfonate, a sulfate, or a combination thereof.

22. 22. The solidified surfactant composition of any one of claims 17 to 21, wherein the carrier is an alpha olefin sulfonate, a linear alkyl sulfonate, sodium lauryl sulfate, a sodium alkyl sulfate, or a combination thereof.

23. 21. The solidified surfactant composition of any one of claims 17 to 20, wherein the carrier is an alkali metal carbonate, an alkali metal carbonate, an alkali metal acetate, an alkali metal acetate, an alkali metal sulfate, an alkali metal sulfate, sodium chloride, or a combination thereof.

24. 24. The solidified surfactant composition of any one of claims 17-20, or 23, wherein the carrier is sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium acetate, or a combination thereof.

25. The solidified surfactant composition of any one of claims 17 to 24, wherein the carrier is a solid.

26. The solidified surfactant composition of any one of claims 17 to 25, wherein the carrier is a powder.

27. The solidified surfactant composition of any one of claims 17 to 24, wherein the carrier is a liquid.

28. 28. The solidified surfactant composition of any one of claims 17 to 27, wherein the carrier has a water solubility of about 0.2 g / L or more at 20°C.

29. 29. The solidified surfactant composition of any one of claims 17 to 28, wherein the solidified surfactant composition has less than about 5% by weight of water.

30. 30. The solidified surfactant composition of any one of claims 1 to 29, wherein the solidified surfactant composition contains at least about 10% by weight of active surfactant.

31. The solidified surfactant composition of any one of claims 1 to 30, wherein the solidified surfactant composition contains at least about 25% by weight of active surfactant.

32. 32. The solidified surfactant composition of any one of claims 1 to 31, wherein the solidified surfactant composition contains at least about 50% by weight of active surfactant.

33. A method for preparing a solidified surfactant composition according to any one of claims 1 to 32, said method comprising: adding the liquid nonionic surfactant, the binder, carrier, or a combination of binder and carrier, and water to a drying device; drying the liquid surfactant, water, and binder, carrier, or combination of binder and carrier to form a solidified surfactant composition; The method wherein the liquid surfactant is solidified in the solidified surfactant composition.

34. 34. The solidified surfactant method of claim 33, wherein the drying device is a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower dryer, a vibratory conveyor dryer, a drum dryer, a screw conveyor dryer, a fluidized bed, a spouted bed, a pneumatic conveyor, a spray dryer, or a combination thereof.

35. 35. The method of claim 33 or 34, wherein at least two drying devices are arranged in series or in parallel.

36. The method of any one of claims 33 to 35, wherein the drying process is carried out in a batch system or a continuous system.

37. 37. The method of any one of claims 33 to 36, wherein the liquid nonionic surfactant and the water added to the drying device have a weight ratio of liquid nonionic surfactant to water of about 1:1 to about 1:

20.

38. The method of any one of claims 33 to 37, wherein the drying device comprises a fluidized bed.

39. 39. The method of claim 38, wherein the fluidized bed has an air velocity of from about 1 to about 100 feet per second.

40. 40. The method of claim 38 or 39, wherein the fluidized bed has a liquid flow rate of from about 0.001 to about 0.15 lb / min of bed material.

41. 41. The method of any one of claims 38 to 40, wherein the fluidized bed has an atomization air pressure of from about 0 psig to about 100 psig per nozzle.

42. 42. The method of any one of claims 38 to 41, wherein the method employs an agglomeration process and the carrier is a solid.

43. 42. The method of any one of claims 38 to 41, wherein the method employs a granulation process and the carrier is a liquid.

44. 38. The method of any one of claims 33 to 37, wherein the drying device comprises a spray dryer.

45. 45. The method of claim 44, wherein the spray dryer has an inlet and an outlet, the inlet temperature being from about 20°C to about 250°C, and the outlet temperature being less than about 150°C.

46. 46. ​​The method of claim 44 or 45, wherein the inlet temperature is from about 100°C to about 250°C and the outlet temperature is from about 20°C to about 100°C.

47. A solidified surfactant composition according to any one of claims 1 to 32; and a solidification agent.

48. 48. The cleaning composition of claim 47, wherein the cleaning composition is a ware cleaning composition, a rinse aid composition, a laundry composition, or a hard surface composition.

49. 49. The cleaning composition of claim 47 or 48, further comprising an alkaline source selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, metal silicates, metal borates, alkanolamines, and combinations thereof.

50. 50. The cleaning composition of claim 49, wherein the alkaline source is in an amount from about 0.01% to about 99% by weight of the cleaning composition.

51. 51. The cleaning composition of claim 49 or 50, wherein the alkaline source is in an amount sufficient to provide a pH of from about 7 to about 14 in the use solution.

52. The cleaning composition of any one of claims 47 to 50, wherein the cleaning composition provides a pH of from about 1 to about 7 in a use solution.

53. 53. The cleaning composition of any one of claims 47 to 52, further comprising an additional surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, semi-polar nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

54. 54. The cleaning composition of any one of claims 47 to 53, wherein the cleaning composition is a granular solid, a pelleted solid, a cast solid, an extruded solid block, or a pressed solid.

55. 55. The cleaning composition of claim 54, wherein the cleaning composition is a pressed solid.

56. 56. The cleaning composition of any one of claims 47-55, further comprising at least one of the following additional ingredients: an acid source, an activator, an anti-redeposition agent, a bleaching agent, a chelating agent, a dye, an odorant, a filler, a functional polydimethylsiloxone, a hardening agent, a hydratable salt, a polymer, or a disinfectant.

57. 1. A method for cleaning a surface, comprising: A method comprising contacting the surface with a cleaning composition according to any one of claims 47 to 56.

58. 58. The method of claim 57, wherein the surface comprises a hard surface, an object, or laundry.

59. 59. The method of any one of claims 57 or 58, further comprising rinsing the surface with water.

60. 60. The method of any one of claims 57 to 59, wherein the cleaning composition provides substantially similar foaming characteristics to a cleaning composition having the same ingredients, except that the solidified surfactant composition is a liquid surfactant.

61. 61. The method of any one of claims 57 to 60, wherein the cleaning composition is a rinse aid and reduces redeposition of soils on surfaces.

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