Curing nonionic surfactants

Abstract

The present invention relates to curing of a liquid nonionic surfactant with an adhesive, a carrier, or both an adhesive and a carrier to form a cured surfactant composition. In particular, the present invention relates to the curing of liquid nonionic surfactants using a drying device wherein the feed composition contains at least one liquid nonionic surfactant and the binder, carrier, or binder and carrier to form a cured surfactant composition. The cured surfactant composition may be suitable for use in a variety of cleaning compositions.

Description

[0001] This application is a divisional application of the invention patent application with application number "202080037662.X", application date "June 22, 2020", and invention title "Cureable Nonionic Surfactant". Cross-references

[0002] This application relates to and claims priority to U.S. Provisional Application Serial No. 62 / 864,937, filed June 21, 2019, entitled “SOLIDIFYING NONIONIC SURFACTANTS”, and is claimed under 35 USC § 119; the entire contents of that patent application are hereby expressly incorporated herein by reference. Technical Field

[0003] This invention relates to the curing of liquid nonionic surfactants using an adhesive, a carrier, or both. Specifically, this invention relates to the curing of liquid nonionic surfactants using a drying apparatus, wherein the feed composition contains at least one liquid nonionic surfactant and a water-soluble adhesive, a carrier, or both. Background Technology

[0004] Most nonionic surfactants are available only in liquid form. Many of these surfactants need to be available in solid form for the preparation of solid cleaning compositions. Because many of these surfactants are only available in liquid form, they are not readily incorporated into solid formulations or are limited in the concentration of active surfactants that can be included in the formulation. Liquid nonionic surfactants have been incorporated into many liquid cleaning compositions. However, the incorporation of these same nonionic surfactants into solid formulations is difficult or prohibited, which has limited the efficacy of solid cleaning products or the ability to manufacture solid cleaning products.

[0005] Therefore, the objective of the claimed invention is to develop a solidified nonionic surfactant and its preparation method from liquid nonionic surfactants.

[0006] Another objective of the present invention is to provide a free-flowing, cured nonionic surfactant composition.

[0007] Another objective of the present invention is to provide a cleaning composition comprising a cured nonionic surfactant composition.

[0008] Other objectives, advantages and features of the present invention will become apparent from the following description. Summary of the Invention

[0009] This invention relates to the curing of liquid nonionic surfactants with an adhesive, a carrier, or both to form a cured surfactant composition. Cured surfactant compositions offer numerous advantages over existing formulations, which include the same surfactants already in liquid form, hindering or prohibiting their use in certain types of solid formulations (including, but not limited to, pressed solids). For example, many nonionic surfactants are available only in liquid form. The conversion of liquid nonionic surfactants to cured surfactant compositions allows for their use in solid compositions at higher concentrations and expands their usefulness in solid formulations. Unexpectedly, we have found that once cured, liquid nonionic surfactants are difficult to incorporate into solid cleaning compositions, including pressed solid compositions. We have found that solid cleaning compositions incorporating cured nonionic surfactants present processing problems and stability issues as solid compositions due to the high activity of the surfactants. This application describes not only methods for curing liquid nonionic surfactants to form solid nonionic surfactant compositions but also methods for preparing solid cleaning compositions incorporating solid nonionic surfactants. Solid cleaning compositions containing cured nonionic surfactants offer substantially similar performance in terms of foam and dirt removal properties, an indicator of good overall surfactant performance. This confirms the usefulness of cured surfactant compositions in solid cleaning compositions (including, but not limited to, pressed solids).

[0010] Embodiments of the present invention are not limited to specific methods and / or products, and may vary and will be understood by those skilled in the art. It should further be understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting in any way or scope. For example, unless otherwise expressly indicated, the singular forms “a,” “an,” and “the” as used in this specification and the appended claims may include plural indicators. Furthermore, all units, prefixes, and symbols may be represented in their SI-acceptable form.

[0011] The numerical ranges listed in the specification include the numbers that define the ranges and include every integer within the defined range. Throughout this disclosure, various aspects of the invention are presented in range format. It should be understood that the use of range format is merely for convenience and clarity and should not be construed as a rigid limitation on the scope of the invention. Therefore, descriptions of ranges should be considered as explicitly disclosing all possible subranges, fractions, and individual numerical values ​​within the range. For example, a description of a range such as 1 to 6 should be considered to have explicitly disclosed 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, such as 1, 2, 3, 4, 5, and 6, and decimals and fractions, such as 1.2, 3.8, 1½, and 4¾. This applies regardless of the range width.

[0012] Therefore, it is easier to understand that certain terms are defined first in this invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain. Many methods and materials similar to, modified, or equivalent to those described herein can be used in the practice of embodiments of the invention without excessive experimentation; preferred materials and methods are described herein. In describing and claiming embodiments of the invention, the following terms will be used according to the definitions set forth below.

[0013] As used herein, the term "about" refers to a change in a numerical quantity that can occur, for example, with respect to any quantifiable variable (including, but not limited to, mass, volume, time, and distance), through typical measuring techniques and equipment. Furthermore, in the case of solid and liquid handling procedures used in the real world, certain unintentional errors and variations exist, which may be due to differences in the manufacture, origin, or purity of the ingredients used to manufacture the composition or carry out the method. The term "about" also covers quantities that differ due to different equilibrium conditions of the composition produced from a particular initial mixture. The term "about" also covers these variations. Whether or not modified by the term "about," the claims include equivalents of this quantity.

[0014] The terms “active substance” or “active substance percentage” or “active substance weight percentage” or “active substance concentration” are used interchangeably in this document and refer to the concentration of those components involved in cleaning, expressed as a percentage after subtracting inert components such as water or salt.

[0015] As used herein, the term "alkyl (alkyl / alkyl groups)" 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.), cycloalkyl groups (or "cycloalkyl" or "alicyclo" or "carbocyclo") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl and cycloalkyl-substituted alkyl groups).

[0016] Unless otherwise stated, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl". As used herein, the term "substituted alkyl" refers to an alkyl group having a substituent for one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkyl carbonyloxy, aryl carbonyloxy, alkoxy carbonyloxy, aryloxy, aryloxy carbonyloxy, carboxylic acid ester, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkyl amino carbonyl, dialkyl amino carbonyl, alkyl thio carbonyl, alkoxy, phosphate ester, phosphonic acid, phosphonite, cyano, amino (including alkyl amino, dialkyl amino, aryl amino, diaryl amino and alkyl aryl amino), amide (including alkyl carbonyl amino, aryl carbonyl amino, carbamoyl and urea), imino, mercapto, alkyl thio, aryl thio, thiocarboxylic acid ester, sulfate ester, alkyl sulfinyl, sulfonate, amino sulfonyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkyl aryl or aromatic (including heteroaromatic) groups.

[0017] In some embodiments, the substituted alkyl group may comprise a heterocyclic group. As used herein, the term "heterocyclic group" includes a closed-ring structure similar to a carbocyclic group in which one or more of the carbon atoms on the ring are non-carbon elements, such as nitrogen, sulfur, or oxygen. The heterocyclic group may be saturated or unsaturated. Exemplary heterocyclic groups include (but are not limited to) aziridine, ethylene oxide (epoxide, ethylene oxide), thioheteropropane (cyclic sulfide), diethylene oxide, azirrocyclobutane, oxacyclobutane, thioheterocyclobutane, dioxacyclobutane, dithiocyclobutene, azirrocyclopentane, pyrrolidine, pyrrololine, oxacyclopentane, dihydrofuran, and furan.

[0018] "Anti-redeposition agent" refers to a compound that helps remain suspended in water rather than be redeposited onto the object being cleaned. Anti-redeposition agents are used in this invention to help reduce the redeposition of removed contaminants onto the cleaned surface.

[0019] As used herein, the term "cleaning" refers to methods used to promote or assist in the removal of dirt, bleaching, reduction of microbial communities, and any combination thereof.

[0020] The term "clothing" refers to articles or articles washed in a washing machine. Generally, clothing refers to any article or article made of or including textile materials, woven fabrics, nonwoven fabrics, and knitted fabrics. Textile materials may include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers (such as nylon), acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. Fibers may be treated or untreated. Exemplary treated fibers include those treated for flame retardancy. It should be understood that the term "linen" is commonly used to describe certain types of clothing articles, including sheets, pillowcases, towels, linen tablecloths, tablecloths, strip mops, and uniforms. The present invention additionally provides compositions and methods for treating non-clothing articles and surfaces including hard surfaces such as plates, glasses, and other utensils.

[0021] As used herein, the term "polymer" generally includes, but is not limited to, homopolymers, copolymers such as block, graft, random and alternating copolymers, terpolymers and higher "x" polymers, as well as their derivatives, combinations and blends. Furthermore, unless otherwise expressly limited, the term "polymer" should include all possible isomer configurations of the molecule, including but not limited to isotactic, syndiotactic and random symmetries, and combinations thereof. Additionally, unless otherwise specifically limited, the term "polymer" will encompass all possible geometric configurations of the molecule.

[0022] As used herein, the terms “dirt” or “stain” refer to nonpolar oily substances that may or may not contain particulate matter such as mineral clay, sand, natural minerals, carbon black, graphite, kaolin, environmental dust, etc.

[0023] As used herein, the term "substantially free" means a composition that is completely lacking in the component or has a small amount of the component such that the component does not affect the properties of the composition. The component may be present as an impurity or contaminant and should be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1 wt%, and in yet another embodiment, the amount of the component is less than 0.01 wt%.

[0024] The term "threshold agent" refers to a compound that inhibits the crystallization of hard ions from solution without forming a specific complex with the hard ions. Threshold agents include (but are not limited to) polyacrylates, polymethacrylates, olefin / maleic acid copolymers, etc.

[0025] As used herein, the term "utensil" refers to articles such as eating and cooking utensils, plates, and other hard surfaces such as showerheads, sinks, toilets, bathtubs, countertops, windows, mirrors, transport vehicles, and floors. As used herein, the term "utensil cleaning" refers to washing, cleaning, or rinsing utensils. Utensils also refer to articles made of plastic. Types of plastics that can be cleaned using the compositions according to the invention include, but are not limited to, those comprising polypropylene polymers (PP), polycarbonate polymers (PC), melamine-formaldehyde resins or melamine resins (melamine), acrylonitrile-butadiene-styrene polymers (ABS), and polysulfone polymers (PS). Other exemplary plastics that can be cleaned using the compounds and compositions of the invention include polyethylene terephthalate (PET) and polystyrene polyamide.

[0026] As used herein, the terms “water-soluble” and “water-miscible” mean that a component (e.g., an adhesive or solvent) is soluble or dispersible in water at a concentration 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.

[0027] As used herein, the terms “weight percent,” “% of weight,” “percent by weight,” “% of weight,” and their variations refer to the concentration of a substance, which is the weight of the substance divided by the total weight of the composition and multiplied by 100. It should be understood that “percentage,” “%,” etc., as used herein are intended to be synonymous with “weight percent,” “% of weight,” etc.

[0028] The methods, systems, apparatus, and compositions of the present invention may comprise, consist substantially of, or consist of the components and ingredients of the present invention, as well as other ingredients described herein. As used herein, "consistently of" means that the methods, systems, apparatus, and compositions may include additional steps, components, or ingredients, provided that the additional steps, components, or ingredients do not substantially alter the essential and novel features of the claimed methods, systems, apparatus, and compositions.

[0029] Methods for curing nonionic surfactants Drying, as a process function, removes liquid from a liquid-solid system to produce dried solids. While the removed liquid is typically water, other organic liquids can be removed via the drying process. The selection of drying equipment and / or its configuration depends on factors beyond general considerations such as fluid dynamics, heat and mass transfer, chemical kinetics, and gas-solid interactions, including the feed flow conditions, desired product form, and feed temperature sensitivity. Equipment selection also depends on material properties, the material's drying characteristics, product quality, and dust / solvent recovery.

[0030] Drying equipment is generally classified in three ways. First, it is classified by the operating mode of the drying equipment / system as batch drying or continuous drying. Generally, batch drying is used when the required production rate is 500 pounds of dried product per hour or less. Continuous drying is advantageous when a rate greater than 500 pounds of dried product per hour is required. Second, drying equipment is classified by the mode of heat transfer used to remove moisture. Direct-heated dryers (also known as adiabatic or convection dryers) bring the material into contact with hot gas and remove moisture in the case of evaporation. When used in continuous operation mode, the airflow can be designed to flow in the opposite direction to, simultaneously with, or cross-flow with the material. Indirect-heated dryers (also known as non-adiabatic dryers) provide heat from the conduction and / or radiation of hot surfaces. These dryers can operate under vacuum to lower 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 static or fluidized. Successful drying equipment provides a transition zone at the inlet to atomize the fluid or premix it with recycled solids to enhance flow. In the presence of heat-sensitive solids, a dryer with precise temperature control and / or vacuum conditions can be advantageous. As those skilled in the art will appreciate, the curing of surfactants and other applicable detergent chemicals requires careful consideration and trade-offs of process variables in order to select an appropriate drying device.

[0031] In one embodiment of the invention, the drying apparatus is, for example, a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower shrinker, a vibrating conveyor shrinker, a drum dryer, a screw conveyor dryer, a fluidized bed, a jet bed, a pneumatic conveyor, a spray dryer, or a combination thereof. The drying apparatuses may be arranged in parallel or in series, with a series comprising one or more drying apparatuses. Preferred drying apparatuses include, but are not limited to, spray dryers and fluidized beds (also referred to as fluidized beds).

[0032] Surprisingly, we found it preferred to dilute the nonionic surfactant with water or a water-miscible solvent before the drying step. While not wishing to be bound by theory, we found that high (typically 100%) activity concentrations of nonionic surfactants are problematic for drying, causing difficult processing. Furthermore, even once dried, cured nonionic surfactants become problematic in incorporation into solid cleaning compositions. We found that these problems with drying liquid nonionic surfactants and incorporating cured nonionic surfactant compositions into cleaning compositions can be overcome by mixing the liquid nonionic surfactant and / or carrier with water. Water can be added to the nonionic surfactant, carrier, or both. In a preferred embodiment, the liquid nonionic surfactant is diluted with water. Regardless of whether water is added to the surfactant, carrier, or both, it is preferred to add it at a weight ratio of nonionic surfactant to water between about 1:1 and about 1:20; more preferably between about 1:2 and about 1:15; and most preferably between about 1:4 and about 1:11. In a preferred embodiment, when mixed with water, the nonionic surfactant and / or carrier do not dissolve but remain in the slurry, preferably dispersed in the slurry.

[0033] In one embodiment of the invention, the cured surfactant composition contains less than about 12% by weight of water, preferably less than about 10% by weight of water, more preferably less than about 5% by weight of water, still more preferably less than about 2% by weight of water, even more preferably less than about 1% by weight of water, and most preferably less than about 0.5% by weight of water.

[0034] In a preferred embodiment of the invention, a dried composition having at least about 10% by weight, preferably at least about 25% by weight, preferably at least 40% by weight, and more preferably at least 50% by weight of an active surfactant is provided according to the claimed method of the invention.

[0035] fluidized bed In a preferred embodiment of the invention, the curing of a liquid nonionic surfactant is performed using a fluidized bed, wherein dry powder can be fed into a bed to which the liquid is applied, and then dried with hot gas. Without attempting to be limited by the specific configuration or theory of the invention, the fluidized bed dryer comprises a fluidization chamber in which moistened particles are fluidized by hot gas blown through a heater into an air chamber below the bed, and then through a distributor plate that fluidizes the particles.

[0036] Fluidized beds can be used for coalescence processes involving solid binders and / or carriers, or for granulation processes involving only liquid components. Coalescence processes use liquid additions to bind particles from a powder feed to form larger particles of the desired size and composition. Granulation processes differ from coalescence processes because they do not require a powder feed; instead, granulation processes are carried out by continuously spraying a liquid coating onto seed material from the process to continuously coat and dry the liquid, thereby forming solid particles of the desired size and composition. Furthermore, we have found that the processes can be carried out without seed material or with virtually no material in the bed. In one embodiment where there is no material in the bed at the start of the process, the process can be initiated by granulation to form seed material, and then continued by coalescence or further granulation.

[0037] The air velocity within the fluidized bed depends on the characteristics of the starting material, the drying rate, and the desired particle size, and is typically in the range of about 0.001 to about 1000 feet per second, preferably about 0.01 to about 500 feet per second, more preferably about 0.1 to about 100 feet per second, and most preferably about 1 to about 60 feet per second.

[0038] Preferably, the liquid flow rate is between about 0.001 lb / min / lb bed material and about 0.15 lb / min / lb bed material, more preferably between about 0.01 lb / min / lb bed material and about 0.10 lb / min / lb bed material. In one embodiment, the process is started with no starting material (including no seed material) on the bed. It should be understood that the initial liquid flow rate in mass / min / bed material is not calculable because the initial bed material is zero. However, bed material is present almost immediately after the start of the process because material is added to the bed for initial granulation. In this embodiment, the liquid-to-bed material ratio is initially high due to the low amount of bed material. For example, the preferred liquid flow rate when there is no starting material in the bed is between about 0.1 lb / min / lb bed material and about 2 lb / min / lb bed material, more preferably between about 0.5 lb / min / lb bed material and about 1.5 lb / min / lb bed material.

[0039] The atomizing pressure in 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.

[0040] spray drying In a preferred embodiment of the invention, a spray dryer is used to perform the curing of a liquid nonionic surfactant. The spray dryer is compatible with slurry or solution feeds and provides the evaporation required for heat-sensitive materials and photosensitive and porous products. The configuration of the spray dryer may require verification of the pressure effects on the liquid feed and solid product to ensure drying without damaging the product. Generally, the liquid or slurry is fed into the dryer processing unit and then sprayed as fine droplets into a hot gas stream. Therefore, the feed composition must be able to withstand the pressure required for droplet formation. Once in the spray dryer, liquid evaporation occurs rapidly, while the product temperature remains relatively low. The interaction between the gas and solid must also be considered in the selection and design of the process. Specifically, the inlet and outlet conditions of the solid, as well as the fluid capacity and residence time, should be designed with regard to diffusion and heat transfer rates.

[0041] In one embodiment of the invention, the inlet temperature of the feedstock is in the range of about 20°C to about 250°C, preferably about 100°C to about 250°C, and more preferably about 150°C to about 200°C. In another embodiment of the invention, the outlet temperature, the suction device, and the pump speed depend on the degradation of the surfactant within the spray dryer.

[0042] The outlet temperature can vary based on the degradation temperature of the components in the cured surfactant composition. Therefore, in some embodiments, the temperature may be higher or lower than the temperature described herein. However, in embodiments of the invention, the outlet temperature is less than about 150°C, more preferably between about 0°C and about 120°C, and most preferably between about 20°C and about 100°C.

[0043] Curing surfactant composition Many nonionic surfactants are available only in liquid or tubular / paste form. Other nonionic substances are in solid form, which is unprocessable because they are solid at room temperature and require melt preparation in a hot chamber. However, they cannot be obtained as flowable powders. There is a need to provide many such surfactants in solid flowable powder form. One embodiment of the invention is found in a cured nonionic surfactant composition. Another embodiment of the invention is found in a method for preparing a cured nonionic surfactant composition. In one embodiment, the cured surfactant composition comprises a liquid nonionic surfactant and a binder. In one embodiment, the cured surfactant composition comprises a liquid nonionic surfactant, a binder, a carrier, and optionally a co-surfactant. In one embodiment, the cured surfactant composition comprises a liquid nonionic surfactant and a carrier. Additional components may be present depending on the desired properties of the cured surfactant composition.

[0044] In one aspect of the invention, the components are fed into a selected drying apparatus to form a cured surfactant composition. The cured 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 cured surfactant composition is an agglomerated solid or a granular solid.

[0045] adhesives The curing surfactant composition may include a binder. In one aspect of the invention, the binder is a solid in the form of bricks, powders, granules, beads, and flakes. Preferably, the binder is dissolved and then dried together with a liquid nonionic surfactant. The binder may be added alone or together with a carrier to the liquid nonionic surfactant to form a curing surfactant composition. Preferably, the binder is water-soluble. In a most preferred embodiment, the water solubility of the binder at 20°C is about 0.2 g / L or greater.

[0046] Suitable adhesives can be liquids (aqueous or non-aqueous), semi-solids, or solids. Preferred adhesives may include, but are not limited to, natural polymers such as urea, urea derivatives, organic salts (e.g., sodium acetate), inorganic salts (e.g., sodium and sulfate salts 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 starch, and combinations thereof), proteins (e.g., corn gluten, whey, gluten, collagen), lignin, natural rubber, and combinations thereof. Preferably, the PEG has a melting point of at least about 40°C, more preferably between about 42°C and about 100°C. Preferred PEGs include PEG 1450, PEG 3350, PEG 4000, PEG 4600, and PEG 8000.

[0047] An appropriate amount of binder and liquid nonionic surfactant can be added to the drying apparatus to cure the surfactant product. The amount of each component may depend on the specific liquid nonionic surfactant being cured, the binder being used, and any other optional components that may also be included in the cured surfactant product. Preferably, the ratio of the active amounts of binder and surfactant is between about 4:1 and about 1:60; or between about 3:1 and about 1:50; or between about 2:1 and about 1:30; or between about 1:1 and about 1:30.

[0048] One objective of this invention is to enable the incorporation of liquid nonionic surfactants into solid cleaning compositions in solid form, with a higher concentration or ratio of the surfactant to other components in the binder and curing surfactant composition being preferred. However, this is limited by the desired physical properties of the curing surfactant composition. For example, in a preferred aspect of the invention, the surfactant is a cured particle rather than a paste. In another preferred aspect of the invention, the curing surfactant composition has reduced viscosity or no viscosity, allowing it to flow freely without clumping, agglomerating, or forming clumps during storage.

[0049] carrier The cured 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 in soluble form. Suitable solid carriers include, but are not limited to, powders, granules, beads, and flakes. Preferred carriers may include, but are not limited to, anionic surfactants, organic salts, and inorganic salts. Preferably, the carrier is water-soluble. In a most preferred embodiment, the water solubility of the carrier at 20°C is about 0.2 g / L or greater. The carrier may be added alone or together with a binder to the liquid nonionic surfactant to form the cured surfactant composition.

[0050] 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, α-olefin sulfonates, linear alkyl sulfonates, sodium lauryl sulfate, sodium alkyl sulfate, and combinations thereof.

[0051] Preferred organic salts include, but are not limited to, alkali metal and alkaline metal carbonates (such as sodium carbonate and magnesium carbonate), alkali metal and alkaline metal acetates (such as sodium acetate and magnesium acetate), and combinations thereof.

[0052] Preferred inorganic salts include, but are not limited to, alkali metal and alkaline metal sulfates (such as sodium sulfate and magnesium sulfate), sodium chloride, and combinations thereof.

[0053] The carrier and liquid nonionic surfactant can be added in appropriate amounts to the drying apparatus to cure the surfactant product. The amount of each component may depend on the specific liquid nonionic surfactant being cured, the carrier being used, and any other optional components that may be included in the cured surfactant product. Preferably, the ratio of the active amounts of the carrier and the surfactant is between about 2:1 and about 1:20; or between about 2:1 and about 1:15; or between about 1:1 and about 1:10; or between about 1:1 and about 1:8 of the active substance.

[0054] One objective of this invention is to enable the incorporation of liquid nonionic surfactants into solid cleaning compositions in solid form, preferably with a higher concentration or ratio of the surfactant to the carrier and other components in the cured surfactant composition. However, this is limited by the desired physical properties of the cured surfactant composition. For example, in a preferred aspect of the invention, the surfactant is a cured particle rather than a paste. In another preferred aspect of the invention, the cured surfactant composition has reduced viscosity or no viscosity, allowing it to flow freely without clumping, agglomerating, or forming clumps during storage.

[0055] Chelating agents In some embodiments, the cured surfactant composition may optionally include a chelating agent. Preferred chelating agents include aminocarboxylate salts. Preferred aminocarboxylate salts include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), glutamic acid-N,N-diacetic acid (GLDA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), methyl-glycine-diacetic acid (MGDA), hypoazinetriacetic acid (NTA), ethylenediaminetetrapropionate, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid, and ethanol diglycine, salts and derivatives of the above substances, alkali metal salts, ammonium salts and substituted ammonium salts thereof, and mixtures thereof.

[0056] If included in the curing surfactant composition, the concentration of the chelating agent is preferably between about 0% by weight and about 50% by weight; more preferably between about 5% by weight and about 35% by weight; and most preferably between about 10% by weight and about 25% by weight. Liquid nonionic surfactants Many surfactants are available primarily in liquid form. There is a need to provide many such surfactants in solid form. In one aspect of the invention, a liquid nonionic surfactant is added to a drying apparatus along with an adhesive, a carrier, or both to form a cured surfactant composition. Any suitable liquid nonionic surfactant may be included in the cured 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 amide alkoxylates, alkyl esters, and combinations thereof.

[0057] Nonionic surfactants are typically characterized by the presence of both organic hydrophobic and organic hydrophilic groups, and are usually produced by the condensation of an organic aliphatic, alkyl aromatic, or polyoxyethylene hydrophobic compound with a hydrophilic basic oxide moiety, typically ethylene oxide or its polyhydrated form, or polyethylene glycol. In fact, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can be condensed with ethylene oxide, its polyhydrated adduct, or a mixture thereof with an alkyl oxide (e.g., propylene oxide) to form a nonionic surfactant. The length of the hydrophilic polyoxyethylene moiety condensed with any particular hydrophobic compound can be readily adjusted to produce a water-dispersible or water-soluble compound with a desired balance between hydrophilic and hydrophobic properties.

[0058] Preferred liquid nonionic surfactants include, but are not limited to: 1. Block polyoxypropylene-polyoxyethylene polymers based on reactive hydrogen compounds initiated by propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine. Examples of polymers prepared by sequential propoxylation and ethoxylation of the initiator can be found under the trademarks Pluronic® and Tetronic. ® Commercial purchase, manufactured by BASF.

[0059] 2. A condensation product of one mole of a saturated or unsaturated, straight-chain or branched alcohol having about 6 to about 24 carbon atoms and about 3 to about 50 moles of ethylene oxide. The alcohol moiety may comprise, consist essentially of, or be a mixture of alcohols within the carbon range described above, or may consist of alcohols having a specific number of carbon atoms within this range, or may be a guerbet alcohol ethoxylate. Examples of similar commercial surfactants include those marketed under the names Lutensol™ (manufactured by BASF) and Neodol. TM (Manufactured by Shell Chemicals) and Alfonic TM Purchased (manufactured by Vista Chemical).

[0060] In addition to ethoxylated carboxylic acids commonly referred to as polyethylene glycol esters, other alkyl esters formed by reacting with glycerol esters, glycerol, and polyhydroxy (sugar or dehydrated sorbitol / sorbitol) alcohols also have applications in certain embodiments of the present invention. All these ester moieties have one or more reactive hydrogen sites on their molecules, which can be further acylated or added to ethylene oxide (alkoxide) to control the hydrophilicity of these substances. Special care must be taken when adding these fatty esters or acylated carbohydrates to compositions of the present invention containing amylase and / or lipase, due to potential incompatibilities.

[0061] 3. Ethoxylated C6-C18 fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols are surfactants suitable for the compositions of the present invention, especially water-soluble ones. Suitable ethoxylated fatty alcohols comprise C6-C fatty alcohols with an ethoxylation degree of 3 to 50. 18 Ethoxylated fatty alcohols.

[0062] 4. Suitable nonionic surfactants for use with the compositions of the present invention comprise alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, terminated EO / PO copolymers, alcohol alkoxylates, terminated alcohol alkoxylates, mixtures thereof, etc. Suitable alkoxylated surfactants used 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 terminated alcohol alkoxylates, such as Plurafac LF22, Plurafac RA 300, and Plurafac SLF-180; mixtures thereof, etc.

[0063] 5. Compounds from (1) that are modified, substantially inversely, by adding ethylene oxide to ethylene glycol to provide a hydrophilic compound having a specified molecular weight; and then adding propylene oxide to obtain a hydrophobic block at the molecule's exterior (end). These inverse Pluronics TM Manufactured by BASF, under the brand name Pluronic TM R surfactant. Similarly, Tetronic TM The surfactant R is manufactured by BASF.

[0064] 6. Suitable nonionic alkyl polysaccharide surfactants, particularly those disclosed in U.S. Patent No. 4,565,647, issued January 21, 1986, are particularly suitable for use in the compositions of the present invention. These surfactants comprise a hydrophobic group containing about 6 to about 30 carbon atoms; and a polysaccharide, such as a polysaccharide glycoside containing about 1.3 to about 10 sugar units, with a hydrophilic group. Any reducing sugar containing 5 or 6 carbon atoms may be used, for example, glucose, galactose, and galactosyl moieties may be used to replace the glucosyl moieties. (Optionally, the hydrophobic group is attached at positions 2, 3, 4, etc., thus yielding glucose or galactose as opposed to glucosides or galactosides.) The interglycosylation may be, for example, between a position of an additional sugar unit and positions 2, 3, 4, and / or 6 on the aforementioned sugar unit.

[0065] 7. Suitable nonionic surfactants also include categories defined as alkoxylated amines or, most specifically, alcohol alkoxylated / amined / alkoxylated surfactants. These nonionic surfactants can be represented, at least in part, by the following 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 The alkyl, alkenyl, or other aliphatic or alkyl-aryl groups having 8 to 20, preferably 12 to 14 carbon atoms, EO being ethylene oxide, PO being propylene oxide, s being 1 to 20, preferably 2-5, t being 1-10, preferably 2-5, and u being 1-10, preferably 2-5. Other variations in the range of these compounds can be expressed by the following substitutions: R 20 --(PO) V --N[(EO) w H][(EO) z H], where R 20 As defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4 (preferably 2)), and w and z are independently 1-10, preferably 2-5. These compounds are commercially known as Surfonic. ® A range of products for sale as a representative.

[0066] 8. Suitable nonionic surfactants also include fatty acid amide alkoxylates. Preferably, such surfactants include those having the structural formula R2CONR1Z, wherein: R1 is H, a C1-C4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof; R2 is C5-C... 31 The hydrocarbon group may be linear; and Z is a polyhydroxy hydrocarbon group or its alkoxylated derivative (preferably ethoxylated or propoxylated) having a linear hydrocarbon chain with at least three hydroxyl groups directly linked to the chain. Z may be derived from reducing sugars in reductive amination reactions, such as glycidyl moiety.

[0067] Alkyl ethoxylation condensation products of fatty alcohols with about 0 to about 25 moles of ethylene oxide are suitable for use in the compositions of the present invention. The alkyl chain of the fatty alcohol may be a straight-chain or branched primary or secondary alkyl chain, and generally contains 6 to 22 carbon atoms.

[0068] Fatty acid amide surfactants suitable for use in the compositions of the present invention include fatty acid amide surfactants having the following formula: R6CON(R7)2, wherein R6 is an alkyl group containing 7 to 21 carbon atoms and each R7 is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(C2H4O). X H, where x is in the range of 1 to 3.

[0069] 9. Suitable nonionic surfactants also include nonionic alkyl esters. Suitable alkyl esters are nonionic esters or salts thereof formed by the reaction of alkyl acids and alkyl alcohols.

[0070] Water and / or water-miscible solvents As described above, we have found that if the liquid nonionic surfactant is mixed with water or a water-miscible solvent before drying, the liquid nonionic surfactant is better processed into a flowable powder by the drying system. During the drying process, most of this water is removed from the cured nonionic composition. Some small amounts of water may be retained as hydrated water. Preferably, the cured 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, excluding the amount of water present in other components (such as alkalinity sources or surfactants). Preferably, the cured surfactant composition contains less than about 12% by weight of total water, more preferably less than about 10% by weight, more preferably less than about 5% by weight, even more preferably less than about 2% by weight, and even more preferably less than about 1% by weight, and most preferably less than about 0.5% by weight. Total water refers to water added to the composition and water present in other components, such as alkalinity sources or surfactants. It should be understood that the amount of water added and the total water content can depend on the type of solid composition being prepared, as some methods require more water than others.

[0071] In another aspect of the invention, at least about 30% of the liquid feed is provided according to the claimed method of the invention to produce a cured surfactant composition, preferably at least about 50%, more preferably at least about 65%, and most preferably at least about 85%. The liquid feed is the amount of liquid material added to the drying apparatus by weight.

[0072] Solid cleaning compositions The cured surfactant compositions of the present invention may be included in solid cleaning compositions. These cleaning compositions may include, but are not limited to, detergent compositions, including, for example, appliance cleaning compositions and laundry compositions; rinsing aids; and hard surface cleaning compositions. Exemplary embodiments of such compositions are provided in Tables 1A to 1D below. Such compositions are exemplary and not limiting; for example, other cleaning compositions may be prepared using the cured surfactant compositions of this disclosure, and the cleaning compositions reflected below are provided as examples of preferred formulations. In a preferred embodiment, the cleaning composition can remove dirt from a surface. In a preferred embodiment, wherein the cleaning composition is a rinsing aid, the cleaning composition preferably reduces, more preferably prevents, redeposition of dirt on the surface.

[0073] Table 1A. Exemplary manual appliance washing compositions Table 1B. Exemplary Rinsing Aid Compositions Table 1C. Exemplary laundry compositions Table 1D. Exemplary Hard Surface Cleaning Compositions In embodiments of the present invention, additional ingredients may be included in the solid cleaning composition. These additional ingredients provide the composition with desired properties and functionality. For the purposes of this application, the term "functional ingredient" includes materials that provide beneficial properties in a particular application. Some specific examples of functional materials are discussed in more detail below, but the specific materials discussed are given by way of example only, and a wide variety of other functional ingredients can be used. For example, many of the functional materials discussed below relate to materials used in cleaning, particularly dishwashing applications. However, other embodiments may include functional ingredients for other applications. Depending on the desired characteristics and / or functionality of the composition, examples of such functional materials include chelating agents / polyvalent chelating agents; bleaching agents or activators; disinfectants / antimicrobial agents; activators; synergists or fillers; anti-redeposition agents; optical brighteners; dyes; flavorings or fragrances; preservatives; stabilizers; processing aids; corrosion inhibitors; fillers; curing agents; hardeners; solubility adjusters; pH adjusters; humectants; water-soluble agents; or a wide variety of other functional materials. In some of the embodiments disclosed herein, functional materials or ingredients are optionally included in the solid cleaning composition for their functional properties. Some more specific examples of functional materials are discussed in more detail below, but those skilled in the art and others should understand that the specific materials discussed are given by way of example only, and a wide variety of other functional materials can be used.

[0074] In one aspect of the invention, some of the additional ingredients described below may be included in the cured surfactant composition. Preferred additional ingredients that may be incorporated into the cured surfactant composition include, but are not limited to, co-surfactants, dyes, and / or fragrances (flavor enhancers).

[0075] acid source In some embodiments of the invention, the cleaning composition may include an acid source. Suitable acid sources may include organic acids and / or inorganic acids. Examples of suitable organic acids include carboxylic acids, particularly, but not limited to, hydroxyacetic acid (ethanol), citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid. Organic dicarboxylic acids, particularly oxalic acid, malonic acid, gluconic acid, itaconic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid, may also be used according to the invention. Any combination of these organic acids may also be miscible with or used with other organic acids that allow for the substantial formation of the compositions of the invention.

[0076] The inorganic acids applicable to this invention include sulfuric acid, aminosulfonic acid, methylaminosulfonic acid, hydrochloric acid, hydrobromic acid, and nitric acid. These acids can also be used in combination with other inorganic acids or with the organic acids mentioned above. In a preferred embodiment, the acid is an inorganic acid.

[0077] In some embodiments of the invention, the cleaning composition may have an acidic pH. In such embodiments, the pH is preferably between 1 and 7. In another aspect of the invention, an acid source may be included in the alkaline composition as a pH adjuster or neutralizer to achieve the desired pH.

[0078] Activator In some embodiments, the cleaning composition may have improved antimicrobial or bleaching activity by adding materials that react with reactive oxygen species (ROS) upon application of the composition to form an activating component. For example, in some embodiments, a peracid or peracid salt is formed. For example, in some embodiments, tetraacetylethylenediamine may be included in the composition to react with ROS and form a peracid or peracid salt that acts as an antimicrobial agent. Other examples of ROS activators include transition metals and their compounds, compounds containing carboxylic acid, nitrile, or ester moieties, or other such compounds known in the art. In embodiments, the activator includes tetraacetylethylenediamine; transition metals; compounds containing carboxylic acid, nitrile, amine, or ester moieties; or mixtures thereof.

[0079] In some embodiments, the activator component may be included in a range of up to about 75% by weight of the cleaning composition, in some embodiments in a range of about 0.01% by weight to about 20% by weight, or in some embodiments in a range of about 0.05% by weight to 10% by weight of the cleaning composition. In some embodiments, the activator for reactive oxygen species is combined with reactive oxygen species to form an antimicrobial agent.

[0080] An activator can be attached to a solid cleaning composition by any of a variety of methods used to attach one solid cleaning composition to another. For example, the activator can be in a solid form that is bonded, adhered, glued, or otherwise bonded to the solid cleaning composition. Alternatively, a solid activator can be formed around and encapsulate the solid cleaning composition. As another example, the solid activator can be attached to the solid cleaning composition via a container or packaging for the composition, such as through plastic or shrink wrap or film.

[0081] Alkalinity source The cleaning composition may include an effective amount of one or more alkalinity sources. The effective amount of one or more alkalinity sources should be considered as the amount that provides a composition with a pH between about 7 and about 14. In one particular embodiment, the pH of the cleaning composition may be between about 7.5 and about 13.5. During a washing cycle, the pH of the solution used may be between about 6 and about 14. In one particular embodiment, the solution used may have a pH between about 6 and 14. If the cleaning composition includes an enzyme composition, then the pH may be adjusted to provide an optimal pH range for the effectiveness of the enzyme composition. In a particular embodiment of the invention, the enzyme composition is incorporated into the cleaning composition, with an optimal pH between about 10 and about 11.

[0082] Examples of suitable alkalinity sources for the cleaning composition include, but are not limited to, carbonate-based alkalinity sources, including, for example, carbonates, such as alkali metal carbonates; caustic base-based alkalinity sources, including, for example, alkali metal hydroxides; other suitable alkalinity sources may include metal silicates, metal borates, and organic alkalinity sources. Exemplary alkali metal carbonates that may be used include, but are not limited to, sodium carbonate, potassium carbonate, bicarbonate, sodium sesquicarbonate, and mixtures thereof. Exemplary alkali metal hydroxides that may be used include, but are not limited to, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Exemplary metal silicates that may be used include, but are not limited to, sodium silicate or potassium silicate or sodium metasilicate or potassium metasilicate. Exemplary metal borates include, but are not limited to, sodium borate or potassium borate.

[0083] Organic basicity sources are typically strong nitrogen bases, including, for example, ammonia (ammonium hydroxide), amines, alkanolamines, and amino alcohols. Typical examples of amines include primary, secondary, or tertiary amines and diamines with at least one nitrogen-linked hydrocarbon group, wherein the hydrocarbon group represents a saturated or unsaturated straight-chain or branched alkyl group having at least 10 carbon atoms, and preferably 16-24 carbon atoms, or an aryl, aralkyl, or alkylaryl group containing up to 24 carbon atoms, wherein optionally other nitrogen-linked groups are formed from optionally substituted alkyl, aryl, or aralkyl or polyalkoxy groups. Typical examples of alkanolamines include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine, etc. 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, etc.

[0084] Generally, alkalinity sources are available in aqueous or powder form. Preferably, the alkalinity source is in solid form. Alkalinity can be added to the composition in any form known in the art, including solid beads, granulated or particulate forms, or combinations thereof dissolved in aqueous solution.

[0085] Generally, the cleaning composition is expected to include an alkalinity source in amounts between about 0.01% by weight and about 99% by weight. In some embodiments, the alkalinity source will be between about 35% by weight and about 95% by weight of the total weight of the cleaning composition. When diluted to a working solution, the compositions of the present invention may include an alkalinity source of about 5 ppm to about 25,000 ppm.

[0086] Anti-redeposition agent The cleaning composition may optionally include an anti-redeposition agent that promotes the sustained suspension of contaminants in the cleaning or rinsing solution and prevents the removed contaminants from redepositing onto the substrate being cleaned 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, etc. The cleaning composition may contain up to about 10% by weight, and in some embodiments, from about 1% by weight to about 5% by weight of the anti-redeposition agent.

[0087] bleach The cleaning composition may optionally include a bleaching agent. The bleaching agent can be used to brighten or whiten a substrate and may include bleaching compounds capable of releasing active halogen substances (such as Cl2, Br2, -OCl- and / or -OBr-, etc.) under conditions typically encountered during the cleaning process. Suitable bleaching agents may include, for example, chlorine-containing compounds such as chlorine, hypochlorite, chloramine, etc. Some examples of halogen-releasing compounds include alkali metal dichloroisocyanurate, trisodium chloride phosphate, alkali metal hypochlorite, monochloramine, and dichloramine, etc. Encapsulated chlorine sources may also be used to enhance the stability of the chlorine source in the composition (see, for example, U.S. Patent Nos. 4,618,914 and 4,830,773, the disclosures of which are incorporated herein by reference). The bleaching agent may also include a reagent containing or acting as a source of active oxygen. Active oxygen compounds are used to provide a source of active oxygen, for example, by releasing active oxygen in aqueous solutions. Active oxygen compounds may be inorganic or organic, or mixtures thereof. Some examples of reactive oxygen species (ROS) include peroxides or peroxide adducts. Some examples of ROS or ROS sources, with or without activators such as tetraacetylethylenediamine, include hydrogen peroxide, perborate, sodium carbonate peroxide hydrate, phosphate peroxide hydrate, potassium persulfate, and sodium perborate monohydrate and tetrahydrate. Cleaning compositions may include trace but effective amounts of bleach, for example, in some embodiments up to about 10% by weight, and in some embodiments from about 0.1% to about 6% by weight.

[0088] Chelating agents / multivalent chelating agents The cleaning composition may also include an effective amount of a chelating agent / polyvalent chelating agent, also known as a synergist. Additionally, the cleaning composition may optionally include one or more additional builder agents as functional ingredients. Generally, a chelating agent is a molecule capable of coordinating (i.e., binding) with metal ions normally present in water sources to prevent the metal ions from interfering with the action of rinsing aids or other components of the cleaning composition. When included in an effective amount, the chelating agent / polyvalent chelating agent may also function as a water conditioner. In some embodiments, the cleaning composition may include up to about 70% by weight or about 1-60% by weight of a chelating agent / polyvalent chelating agent.

[0089] Typically, cleaning compositions are also free of phosphonates and / or sulfates. In embodiments of phosphonate-free solid cleaning compositions, additional functional materials (including builders) do not include phosphorus-containing compounds such as condensed phosphates and phosphonates.

[0090] Suitable additional detergent builders include aminocarboxylates and polycarboxylates. Some examples of aminocarboxylates suitable as chelating agents / multivalent chelating agents include N-hydroxyethyliminodiacetic acid, hyponitrotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), glutamic acid-N,N-diacetic acid (GLDA), N-hydroxyethylethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA), methyl-glycine-diacetic acid (MGDA), etc. Some examples of polymeric polycarboxylates suitable as multivalent chelating agents include those having side-attached carboxylic ester (--CO2) groups, and include, for example, polyacrylic acid, maleic acid / olefin copolymers, acrylic acid / 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, etc.

[0091] In embodiments of solid cleaning compositions that are not phosphate-free, the added chelating agents / polyvalent chelating agents may include, for example, condensed phosphates, phosphonates, etc. Some examples of condensed phosphates include sodium orthophosphate and potassium orthophosphate, sodium pyrophosphate and potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, etc. Condensed phosphates can also assist the curing of the composition to a limited extent by fixing free water present in the composition into hydrated water.

[0092] In embodiments of phosphonate-free solid cleaning compositions, the composition may include phosphonates such as 1-hydroxyethane-1,1-diphosphonic acid CH3C(OH)[PO(OH)2]2; aminotris(methylenephosphonic acid) N[CH2PO(OH)2]3; or aminotris(methylenephosphonate) sodium salt. 2-Hydroxyethyliminobis(methylenephosphonic acid)HOCH2CH2N[CH2PO(OH)2]2; Diethylenetriaminepenta(methylenephosphonic acid)(HO)2POCH2N[CH2N[CH2PO(OH)2]2]2; Sodium diethylenetriaminepenta(methylenephosphonate)C9H (28-x) N3Na x O 15 P5 (x=7); Potassium salt of hexamethylenediamine (tetramethylenephosphonate) C 10 H (28-x) N2K x O 12P4 (x=6); bis(hexamethylene)triamine(pentamethylenephosphonic acid)(HO2)POCH2N[(CH2)6N[CH2PO(OH)2]2]2; and phosphoric acid H3PO3. In some embodiments, combinations of phosphonates, such as ATMP and DTPMP, may be used. When adding phosphonates, neutralized or basic phosphonates, or combinations of phosphonates with alkali metal sources, may be used prior to addition to the mixture, such that the heat or gas generated by the neutralization reaction is minimal or nonexistent.

[0093] For further discussion on chelating agents / polyvalent chelating agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 5, pp. 339-366, and Volume 23, pp. 319-320, the contents of which are incorporated herein by reference.

[0094] Dyes / Flavors Various dyes, flavorings (including fragrances), and other beautifying and enhancing agents may also be included in solid cleaning compositions. Dyes may be included to alter the appearance of the composition, such as 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 (Keyston Analine and Chemical), 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.

[0095] Fragrances or flavorings that may be included in solid cleaning compositions include, for example, terpenoids (such as citronellol), aldehydes (such as pentylcinnamaldehyde), jasmine (such as C1S-jasmine or benzoyl acetate), vanillin, etc.

[0096] filler Solid cleaning compositions may optionally include trace but effective amounts of one or more fillers. Some examples of suitable fillers may include sodium chloride, starch, sugar, C1-C 10 Alkyl glycols (such as propylene glycol, sulfates, PEG, urea, sodium acetate, magnesium sulfate, sodium acetate, magnesium sulfate, sodium carbonate, etc.). In some embodiments, the filler may be included in an amount ranging from up to about 50% by weight, and in some embodiments, it may be included in an amount ranging from about 1 to 15% by weight.

[0097] Functional polydimethylsiloxane Solid cleaning compositions may optionally include one or more functional polydimethylsiloxanes. For example, in some embodiments, polyalkylene oxide-modified polydimethylsiloxanes, nonionic surfactants, or polybetaine-modified polysiloxane amphoteric surfactants may be used as additives. In some embodiments, both are linear polysiloxane copolymers grafted with polyethers or polybetaines via hydrosilylation. Some examples of specific siloxane surfactants are known, such as SILWET, available from Union Carbide. ® Surfactants, or ABIL, can be purchased from Goldschmidt Chemical Corp. ® Polyether or polybetaine polysiloxane copolymers, and described in U.S. Patent No. 4,654,161, which is incorporated herein by reference. In some embodiments, the particular siloxane used can be described as having, for example, low surface tension, high wetting ability, and excellent lubricity. For example, these surfactants are said to be some of a few surfactants capable of wetting polytetrafluoroethylene surfaces. Siloxane surfactants used as additives can be used alone or in combination with fluorochemical surfactants. In some embodiments, fluorochemical surfactants optionally combined with silanes as additives can be, for example, nonionic fluorinated hydrocarbons, such as fluorinated alkyl polyoxyethylene alcohols, fluorinated alkyl alkoxylates, and fluorinated alkyl esters.

[0098] Further descriptions of such functional polydimethylsiloxane and / or fluorochemical surfactants are described 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, we have found that the use of certain polysiloxane copolymers in mixtures containing hydrocarbon surfactants yields excellent rinsing aids for plastic appliances. We have also found that combinations of certain silicone polysiloxane copolymers and fluorocarbon surfactants with conventional hydrocarbon surfactants also yield excellent rinsing aids for plastic appliances. Such combinations have been found to be better than the individual components, with the exception of certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine polysiloxane copolymers, in which the effectiveness is substantially equivalent. Therefore, some embodiments cover individual polysiloxane copolymers, and combinations with fluorocarbon surfactants may involve nonionic siloxane surfactants such as polyether polysiloxanes. Amphoteric siloxane surfactants, such as polybetaine polysiloxane copolymers, can be used alone as additives in cleaning compositions to provide the same results.

[0099] In some embodiments, the composition may include an amount of functional polydimethylsiloxane in the range of up to about 10% by weight. For example, some embodiments may include about 0.1 to 10% by weight of polyalkylene oxide-modified polydimethylsiloxane or polybetaine-modified polysiloxane, optionally combined with about 0.1 to 10% by weight of a fluorinated hydrocarbon nonionic surfactant.

[0100] Hardener / curing agent / solubility modifier In some embodiments, the cleaning composition may include one or more curing agents. Examples of curing agents include urea; amides, such as stearic acid monoethanolamide or laurate diethanolamide or alkylamides; sulfates or sulfated surfactants and aromatic sulfonates; solid polyethylene glycol or solid EO / PO block copolymers; starches that have been made water-soluble through acid or alkali treatment processes; and various inorganic substances that impart the property of curing upon cooling to the heated composition. Such compounds can also alter the solubility of the composition in an aqueous medium during use, allowing the active ingredient to be dispensed from the solid composition over a prolonged period.

[0101] Suitable aromatic sulfonates include, but are not limited to, sodium xylenesulfonate, sodium toluenesulfonate, sodium cumenesulfonate, potassium toluenesulfonate, ammonium xylenesulfonate, calcium xylenesulfonate, sodium alkylnaphthalenesulfonate, and / or sodium butylnaphthalene. Preferred aromatic sulfonates include sodium xylenesulfonate and sodium cumenesulfonate.

[0102] The amount of curing agent included in the cleaning composition can be specified by the desired effect. Generally, the effective amount of curing agent is considered as the amount that acts with or without other materials to cure the cleaning composition. Typically, for solid embodiments, the amount of curing agent in the cleaning composition ranges from about 10% by weight to about 80% by weight of the cleaning composition, preferably from about 20% by weight to about 75% by weight, and more preferably from about 20% by weight to about 70% by weight. In one aspect of the invention, the curing agent is substantially sulfate-free. For example, the cleaning composition may 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.

[0103] In some embodiments, it may be desirable to have a second curing agent. In a composition containing a second curing agent, the composition may include an amount of the second curing agent in the range of up to about 50% by weight. In some embodiments, the amount of the second curing agent present may range from about 5% by weight to about 35% by weight, typically from about 10% by weight to about 25% by weight, and sometimes from about 5% by weight to about 15% by weight.

[0104] In some embodiments, one or more additional hardeners may be included in the solid cleaning composition, if necessary. Examples of hardeners include amides, such as stearic acid monoethanolamide or lauric acid diethanolamide or alkylamides; solid polyethylene glycol or solid EO / PO block copolymers; starches that have been made water-soluble by acid or alkali treatment processes; and various inorganic substances that impart the property of curing upon cooling to the heated composition. Such compounds may also alter the solubility of the composition in an aqueous medium during use, allowing for dispensing of the components from the solid composition over an extended period of time. The composition may include a second hardener in an amount ranging from up to about 30% by weight. In some embodiments, the amount of the second hardener present may range from about 5% by weight to about 25% by weight, often from about 10% by weight to about 25% by weight, and sometimes from about 5% by weight to about 15% by weight.

[0105] Moisturizer Solid cleaning compositions may optionally include one or more humectants. Humectants are substances with an affinity for water. The humectant may be provided in an amount sufficient to help reduce the visibility of the film on the substrate surface. The visibility of the film on the substrate surface is a particular concern when the rinse water contains more than 200 ppm of total dissolved solids. Therefore, in some embodiments, the humectant is provided in an amount sufficient to reduce the visibility of the film on the substrate surface when the rinse water contains more than 200 ppm of total dissolved solids, compared to a rinse composition without a humectant. The terms "aqueous solids film formation" or "film formation" refer to the presence of a distinct, continuous layer of material on the substrate surface that makes the substrate surface appear unclean.

[0106] Some exemplary humectants that may be used include those containing more than 5% by weight of water (on a dry humectant basis) at 50% relative humidity and room temperature. Exemplary humectants that may be used include glycerin, propylene glycol, sorbitol, alkyl polyglycosides, polybetaine, polysiloxanes, and mixtures thereof. In some embodiments, the rinsing composition may include a humectant in an amount ranging from up to about 75% by weight of the composition, and in some embodiments, a humectant in an amount ranging from about 5% to about 75% by weight of the composition.

[0107] Hydrated salts The solid cleaning compositions according to the invention may optionally contain at least one hydrateable salt. In one embodiment, the hydrateable salt is sodium carbonate (also known as soda ash or ash) and / or potassium carbonate (also known as potassium carbonate). In a preferred aspect, the hydrateable salt is sodium carbonate and does not include potassium carbonate. The hydrateable salt may be provided in the range of approximately 20% to approximately 90% by weight, preferably between approximately 25% and approximately 90% by weight, and more preferably between approximately 30% and approximately 70% by weight of the hydrateable salt (such as sodium carbonate). Those skilled in the art will appreciate other suitable concentration ranges of components for obtaining comparable cured matrix properties.

[0108] In other embodiments, the hydrateable salt may be combined with other curing agents. For example, the hydrateable salt may be used with additional curing agents that are inherently inorganic, and may also optionally act as an alkalinity source. In some embodiments, the second curing agent may include, but is not limited to: additional alkali metal hydroxides, anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous sodium acetate, and other known hydrateable compounds, or combinations thereof. According to a preferred embodiment, the second hydrateable salt comprises sodium metasilicate and / or anhydrous sodium metasilicate. The amount of the second curing agent necessary to achieve curing depends on several factors, including the exact curing agent used, the amount of water in the composition, and the hydration capacity of other clean composition components. In some embodiments, the second curing agent may also act as an additional alkalinity source.

[0109] polymer Cleaning compositions may include polymers or polymer systems comprising 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.

[0110] Polymaleic acid (C4H2O3)x or hydrolyzed polymaleic anhydride or maleic-2-butenedioic acid homopolymers have the following structural formulas: Where n and m are any integers. Examples of polymaleic acid homopolymers, copolymers, and / or terpolymers (and their salts) that can be used in this invention are particularly preferred, having molecular weights of about 0 and about 5000, more preferably between about 200 and about 2000 (could you please confirm these MW values?). Commercially available polymaleic acid homopolymers include those from BWA. TM The water additive (979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA) contains Belclene 200 series maleic acid homopolymers and Aquatreat AR-801, available from AkzoNobel. The polymaleic acid homopolymer, copolymer, and / or terpolymer may be present in the cleaning composition at about 0.01% by weight to about 30% by weight.

[0111] The cleaning compositions of the present invention may use polyacrylic acid polymers, copolymers, and / or terpolymers. Polyacrylic acid has the following structural formula: Where n is any integer. Examples of suitable polyacrylic acid polymers, copolymers, and / or terpolymers include, but are not limited to, polymers, copolymers, and / or terpolymers of polyacrylic acid, (C3H4O2). n Or 2-propanoic acid, acrylic acid, polyacrylic acid, or propenoic acid.

[0112] In one embodiment of the invention, particularly suitable acrylic polymers, copolymers, and / or terpolymers have molecular weights between about 100 and about 10,000, in preferred embodiments between about 500 and about 7,000, in even more preferred embodiments between about 1,000 and about 5,000, and in most preferred embodiments between about 1,500 and about 3,500. Examples of polyacrylic 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 Dow Chemical Company, Wilmington, Delaware, USA. In certain embodiments, acrylic polymers (and their salts) having molecular weights greater than about 10,000 may be required. Examples include, but are not limited to, Acusol 929 (10,000 MW) and Acumer 1510 (60,000 MW), both available from Dow Chemical Company; and AQUATREAT AR-6 (100,000 MW), available from AkzoNobel (Strawinskylaan 2555 1077 ZZ Amsterdam Postbus 75730 1070 AS Amsterdam). Polyacrylic acid polymers, copolymers, and / or terpolymers may be present in the clean composition from about 0.01% by weight to about 30% by weight.

[0113] Maleic anhydride / olefin copolymers are copolymers of polymaleic anhydride and olefins. Maleic anhydride (C2H2(CO)2O) has the following structure: Maleic anhydride can be partially replaced by the following: maleimide, N-alkyl (C 1-4 Maleimide, N-phenyl-maleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, cinnamic acid, and alkyl groups of the aforementioned acids (C 1-18 )ester, The aforementioned acid's cycloalkyl (C 3-8 Esters, sulfated castor oil, etc.

[0114] At least 95% by weight of the maleic anhydride polymer, copolymer or terpolymer has a number average molecular weight between about 700 and about 20,000, preferably between about 1,000 and about 100,000.

[0115] For the purposes of this invention, a variety of straight-chain and branched α-olefins can be used. Particularly suitable α-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-1,5-hexadiene; and 1-olefins containing 4 to 8 carbon atoms, preferably C4-. 4-10 Examples include isobutylene, 1-butene, 1-hexene, and 1-octene.

[0116] In one embodiment of the invention, particularly suitable maleic anhydride / olefin copolymers have a molecular weight between about 1,000 and about 50,000, in a preferred embodiment between about 5,000 and about 20,000, and in the most preferred embodiment between about 7,500 and 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 Dow Chemical Company, Wilmington, Delaware, USA. The maleic anhydride / olefin copolymer may be present in the cleaning composition in amounts from about 0.01% by weight to about 30% by weight.

[0117] preservative Solid cleaning compositions may also contain an effective amount of preservatives. Preferred preservatives for use in solid cleaning compositions include, but are not limited to, methylchloroisothiazolinone, methylisothiazolinone, pyridinethione derivatives and salts, glutaraldehyde, or mixtures thereof. A preferred blend of methylchloroisothiazolinone and methylisothiazolinone may be marketed under the brand name KATHON. TM CG was purchased from Dow Chemical. The preferred pyridinethione salt is sodium pyridinethione.

[0118] When a preservative is included in a solid cleaning composition, the preservative may be present in an amount of about 0.01% by weight to about 5% by weight; preferably about 0.01% by weight to about 3% by weight; more preferably about 0.05% by weight to about 2% by weight; and even more preferably about 0.05% by weight to about 1% by weight.

[0119] Disinfectant / Antimicrobial Agent The cleaning composition may optionally include a disinfectant. Disinfectants, also known as antimicrobial agents, are chemical compositions that can be used in solid functional materials to prevent microbial contamination and degradation of material systems, surfaces, etc. Generally, these materials belong to specific categories, including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, anilines, organosulfur and sulfur-nitrogen compounds, and hybrid compounds.

[0120] It should also be understood that reactive oxygen species (such as those discussed above in the bleach section) can also act as antimicrobial agents and can even provide disinfecting activity. In fact, in some embodiments, the ability of reactive oxygen species to act as antimicrobial agents reduces the need for additional antimicrobial agents in the composition. For example, percarbonate compositions have been shown to have excellent antimicrobial activity. Nevertheless, some embodiments still incorporate additional antimicrobial agents.

[0121] Depending on their chemical composition and concentration, antimicrobial agents may limit the further proliferation of only a few microorganisms or may destroy all or a portion of a microbial community. The terms "microbe" and "microorganism" generally refer primarily to bacteria, viruses, yeasts, spores, and fungi. In use, antimicrobial agents are typically formed as solid functional materials that, when optionally diluted and dispensed, for example, using a stream of water, form an aqueous bactericide or disinfectant composition that can contact a variety of surfaces, thereby preventing the growth of a microbial community or killing a portion of the microbial community. This results in a disinfectant composition that reduces the microbial community by three log units. Antimicrobial agents may be encapsulated to, for example, improve their stability.

[0122] Some examples of common antimicrobial agents include phenolic antimicrobial agents such as pentachlorophenol, o-phenylphenol, chloro-p-benzylphenol, and p-chloro-m-xylenol. Halogen-containing antibacterial agents include sodium trichloroisocyanurate; sodium dichloroisocyanurate (anhydrous or dihydrate); iodine-poly(vinylpyrrolidone) complexes; bromine compounds such as 2-bromo-2-nitropropane-1,3-diol; and quaternary antimicrobial agents such as benzalkonium chloride, dialcyldimethylammonium chloride, diiodocholine chloride, and tetramethylphosphonium tribromide. Other antimicrobial compositions are well-known in the art for their antimicrobial properties, such as hexahydro-1,3,5-tris(2-hydroxyethyl)-triazine; dithiocarbamates such as sodium dimethyl dithiocarbamate; and various other materials.

[0123] In embodiments of solid cleaning compositions that are free of phosphonates and / or sulfates and also include antimicrobial agents, the antimicrobial agents are selected to meet those requirements. Embodiments of solid cleaning compositions that include only GRAS components may omit or exclude the antimicrobial agents described in this section.

[0124] In some embodiments, the cleaning composition comprises an antimicrobial component in a range of up to about 10% by weight of the composition, in some embodiments in a range of up to about 5% by weight, or in some embodiments in a range of about 0.01% by weight to about 3% by weight, or in a range of 0.05% by weight to 1% by weight.

[0125] Additional surfactants The cured surfactant composition may optionally contain a co-surfactant. Preferably, the co-surfactant is in solid form. Furthermore, the cured surfactant compositions of the present invention may be incorporated into cleaning compositions. These cleaning compositions may include, but are not limited to, detergent compositions, appliance cleaning compositions, laundry compositions, rinsing aids, and hard surface cleaning compositions. Surfactants that can be included as co-surfactants in the cured surfactant composition and / or as surfactants in the cleaning composition include nonionic surfactants, semi-polar nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, and mixtures or combinations thereof.

[0126] When a co-surfactant carrier is included in the curing surfactant composition of the present invention, the weight ratio of the co-surfactant to the liquid surfactant is preferably between about 1:0 and about 0:1. In another embodiment 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 even more preferably about 40% to about 80% by weight.

[0127] Nonionic surfactants Solid cleaning compositions may optionally contain one or more additional nonionic surfactants. Suitable additional nonionic surfactants may include, but are not limited to: The condensation product of one mole of alkylphenol with about 3 to about 50 moles of ethylene oxide, wherein the alkyl chain, whether straight-chain or branched, or of monoalkyl or dialkyl composition, contains about 8 to about 18 carbon atoms. The alkyl group can be represented, for example, by diisobutylene, dipentyl, polypropylene, isooctyl, nonyl, and dinonyl. These surfactants can be polyoxyethylene, polyoxypropylene, and polyoxybutylene condensates of alkylphenols. Examples of commercial compounds having this chemical substance are available on the market under the trademarks Igepal® (manufactured by Solvay) and Triton® (manufactured by Dow).

[0128] The condensation product of one mole of a saturated or unsaturated, straight-chain or branched carboxylic acid having about 8 to about 18 carbon atoms and about 6 to about 50 moles of ethylene oxide. The acid moiety may consist of a mixture of acids within the carbon atom range defined above, or may consist of acids having a specific number of carbon atoms within the said range. Examples of commercially available compounds with this chemical property are traded under the name Nopalcol. TM (Manufactured by Henkel Corporation) and Lipopeg TM (Obtained by Lipo Chemicals, Inc.)

[0129] Compounds from groups (1), (2), (3), and (4) are modified by "end-capping" or "terminal blocking" one or more terminal hydroxyl groups (of the multifunctional moiety) to reduce foaming, by reacting with hydrophobic small molecules such as propylene oxide, butane oxide, and benzyl chloride; and short-chain fatty acids, alcohols, or alkyl halides containing one to about five carbon atoms; and mixtures thereof. Reactants such as thionyl chloride are also included, which convert terminal hydroxyl groups to chlorinated groups. Such modification of terminal hydroxyl groups can produce fully block, intercalated, intercalated, or fully mixed nonionic surfactants.

[0130] Alkylphenoxy polyethoxyalkanols, of which U.S. Patent No. 2,903,486 was granted to Brown et al. on September 8, 1959, are represented by the following formula: Where R is an alkyl group with 8 to 9 carbon atoms, A is an alkylene chain with 3 to 4 carbon atoms, n is an integer from 7 to 16, and m is an integer from 1 to 10.

[0131] The polyalkylene glycol condensate granted to Martin et al. on August 7, 1962, has alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, wherein the weight of the hydrophobic end chain, the weight of the hydrophobic intermediate unit, and the weight of the hydrophilic linking unit are each approximately one-third of the condensate.

[0132] The defoaming nonionic surfactant disclosed in U.S. Patent No. 3,382,178 to Lissant et al., granted on May 7, 1968, has the general formula Z[(OR)]. n OH] z , where Z is an alkoxylated material, R is a free radical derived from an olefin oxide, which may be ethylene or propylene, and n is, for example, an integer from 10 to 2,000 or greater, and z is an integer determined by the number of reactive alkoxylated groups.

[0133] The conjugated polyoxyethylene compound described in U.S. Patent No. 2,677,700 to Jackson et al., issued on May 4, 1954, corresponds to the formula Y(C3H6O). n (C2H4O) m H, where Y is a residue of an organic compound having about 1 to 6 carbon atoms and one reactive hydrogen atom, as determined by the number of hydroxyl groups, n has an average value of at least about 6.4, and m has a value such that the oxyethylene moiety constitutes about 10% to about 90% by weight of the molecule.

[0134] The conjugated polyoxyalkylene compound described in U.S. Patent No. 2,674,619 to Lundsted et al., issued on April 6, 1954, has the formula Y[(C3H6O n (C2H4O) m H] x In this formula, Y is a residue of an organic compound having about 2 to 6 carbon atoms and containing x reactive hydrogen atoms, wherein the value of x is at least about 2, the value of n is such that the molecular weight of the hydrophobic polyoxypropylene matrix is ​​at least about 900, and the value of m is such that the ethylene oxide content of the molecule is from about 10% by weight to about 90% by weight. Compounds falling within the definition of Y include, for example, propylene glycol, glycerol, pentaerythritol, trimethylolpropane, ethylenediamine, etc. The propylene oxide chain optionally but advantageously contains a small amount of ethylene oxide, and the ethylene oxide chain also optionally but advantageously contains a small amount of propylene oxide.

[0135] The additional conjugated polyoxyethylene surfactant advantageously used in the compositions of this invention corresponds to the formula: P[(C3H6O)] n (C2H4O) m H] x , wherein P is a residue of an organic compound having about 8 to 18 carbon atoms and containing x reactive hydrogen atoms, wherein the value of x is 1 or 2, the value of n is such that the molecular weight of the polyethylene oxide moiety is at least about 44, and the value of m is such that the propylene oxide content of the molecule is from about 10% by weight to about 90% by weight. In either case, the propylene oxide chain may optionally but advantageously contain a small amount of ethylene oxide, and the ethylene oxide chain may also optionally but advantageously contain a small amount of propylene oxide.

[0136] Anionic surfactants Also applicable to the present invention are surfactants classified as anionic surfactants, because the hydrophobic component has a negative charge; or surfactants in which the hydrophobic portion of the molecule is uncharged unless the pH is raised to electrically neutral or higher (e.g., carboxylic acids). Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) solubilizing groups found in anionic surfactants. Among 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 will be understood by those skilled in the art, anionic surfactants are excellent detergent surfactants and are therefore suitable for addition to heavy-duty detergent compositions.

[0137] Suitable anionic sulfate surfactants for use in the compositions of this invention include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oil alkenylglycerol sulfates, alkylphenol ethylene oxide ether sulfates, and C5-C... 17Acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) reduced glucosamine sulfates and sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides. Also included are alkyl sulfates, alkyl poly(ethylene oxy) ether sulfates, and aromatic poly(ethylene oxy) sulfates, such as sulfates or condensation products of ethylene oxide and nonylphenol (typically having 1 to 6 vinyl oxide groups per molecule).

[0138] The anionic sulfonate surfactants suitable for use in the compositions of the present invention also include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0139] Suitable anionic carboxylate surfactants for use in the compositions of the present invention include carboxylic acids (and salts) such as alkyl acids (and alkylates), carboxylic acid esters (e.g., alkyl succinate esters), carboxylic acid ethers, sulfonated fatty acids such as sulfonated oleic acid, etc. These carboxylate salts include alkyl ethoxycarboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxy polycarboxylates surfactants, and soaps (e.g., alkyl carboxylates). Secondary carboxylate surfactants suitable for use in the compositions of the present invention include those containing a carboxyl unit linked to a secondary carbon. The secondary carbon can be in a cyclic structure, such as in p-octylbenzoic acid, or as in alkyl-substituted cyclohexylcarboxylates. Secondary carboxylate surfactants generally do not contain ether bonds, ester bonds, or hydroxyl groups. Furthermore, they typically lack a nitrogen atom in the head group (amphiphilic moiety). Suitable secondary soap surfactants typically contain a total of 11 to 13 carbon atoms, but more carbon atoms (e.g., up to 16) can be present. Suitable carboxylates also include acyl amino acids (and salts), such as acylglutamate, acyl peptides, sarcosinates (e.g., N-acylsarcosinate), taurates (e.g., fatty acid amides of N-acyltaurate and methyltaurine), etc.

[0140] Suitable anionic surfactants comprise alkyl or alkylaryl ethoxycarboxylate salts having the following formula: RO-(CH2CH2O) n (CH2) m -CO2X (3) Where R is C8 to C 22 alkyl or , where R 1 It is C4-C 16 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 C8-C. 16 Alkyl group. In some embodiments, R is C. 12 -C 14Alkyl group, n is 4, and m is 1.

[0141] In other embodiments, R is... And R 1 It is C6-C 12 Alkyl group. In yet other embodiments, R 1 It is a C9 alkyl group, n is 10 and m is 1.

[0142] These alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically obtained in acid form, which can be readily converted to anionic or salt forms. Commercially available carboxylates include Neodox 23-4, which is C10. 12-13 Alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP-110, which is C9 alkyl aryl polyethoxy(10) carboxylic acid (Witco Chemical). Carboxylates are also available from Clariant, for example, the product Sandopan. ® DTC, C 13 Alkyl polyethoxy (7) carboxylic acid.

[0143] cationic surfactants If the charge on the co-aqueous solvent portion of the molecule is positive, then the surfactant is classified as cationic. This group also includes surfactants in which the co-aqueous solvent is uncharged unless the pH is lowered to near neutral or lower, but which are then cationic (e.g., alkylamines). Theoretically, cationic surfactants can be synthesized from any combination of elements containing the “onium” structure RnX+Y-- and can include non-nitrogen (ammonium) compounds such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, nitrogen-containing compounds dominate the field of cationic surfactants, likely because the synthetic routes for nitrogen-containing cationic surfactants are simple and direct, and the resulting products are produced in high yields, making them relatively inexpensive.

[0144] Cationic surfactants preferably include, and more preferably, compounds containing at least one long-chain hydrophobic group and at least one positively charged nitrogen atom. The long-chain group can be directly attached to the nitrogen atom by simple substitution; or, more preferably, indirectly attached to the nitrogen atom by a bridging functional group in so-called interrupted alkylamines and amide amines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, more readily soluble in water by co-surfactant mixtures, and / or water-soluble. To improve water solubility, additional primary, secondary, or tertiary amino groups can be introduced, or the amino nitrogen can be quaternized using low molecular weight alkyl groups. Furthermore, the nitrogen can be part of a branched or straight-chain portion of an unsaturated or saturated or unsaturated heterocycle to varying degrees. Additionally, cationic surfactants can contain complex bonds having more than one cationic nitrogen atom.

[0145] Surfactant compounds classified as amine oxides, amphoteric surfactants, and zwitterionic surfactants are typically cationic in near-neutral to acidic pH solutions and may overlap with surfactant classifications. Polyoxyethylated cationic surfactants generally behave similarly to nonionic surfactants in alkaline solutions and similarly to cationic surfactants in acidic solutions.

[0146] The simplest cationic amines, amine salts, and quaternary ammonium compounds can be schematically described as follows: Wherein, R represents an alkyl chain, R', R'', and R''' can be alkyl chains, aryl groups, or hydrogen groups, and X represents an anion. For practical use in this invention, amine salts and quaternary ammonium compounds are preferred because of their high water solubility.

[0147] Most commercially available cationic surfactants can be subdivided into four main categories and additional subgroups, as are known to those skilled in the art and described in the "Surfactant Encyclopedia". Cosmetics & Toiletries In Volume 104(2) 86-96 (1989). Class I includes alkylamines and their salts. Class II includes alkylimidazolines. Class III includes ethoxylated amines. Class IV includes quaternary ammonium salts, such as alkylbenzyl dimethyl ammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkyl ammonium salts, etc. Cationic surfactants are known to possess a variety of properties that can be beneficial in the compositions of the present invention. These desired properties may include detergency in compositions at or below neutral pH, antimicrobial efficacy, thickening or gelling in conjunction with other reagents, etc.

[0148] Cationic surfactants that can be used in the compositions of the present invention include those having the formula R 1 m R 2x Y L Those of Z, where each of R 1 It contains a straight-chain or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxyl groups, and optionally with up to four cleaved organic groups from the following structures: Or isomers or mixtures of these structures, and they contain approximately 8 to 22 carbon atoms. R 1 The group may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, when m is 2, there is no more than one R in the molecule. 1 The group has 16 or more carbon atoms, or more than 12 carbon atoms when m is 3. Each R 2 It is an alkyl, hydroxyalkyl, or benzyl group containing 1 to 4 carbon atoms, wherein there is no more than one R in the molecule. 2 It is benzyl, and x is 0 to 11, preferably 0 to 6. Any remaining carbon atom positions on the Y group are filled with hydrogen. Y can be, but is not limited to, the following groups: Or a mixture thereof. Preferably, LS is 1 or 2, wherein when L is 2, the Y-based group is composed of R atoms having 1 to about 22 carbon atoms and two free carbon single bonds. 1 and R 2 The analogues (preferably alkylene or alkenylene) are separated. Z is a water-soluble anion, such as a halide, sulfate, methyl sulfate, hydroxide, or nitrate anion, particularly preferably a chloride, bromide, iodide, sulfate, or methyl sulfate anion, in an amount that makes it electrically neutral with the cationic component.

[0149] Amphoteric surfactants Amphoteric or amphipathic surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. Basic nitrogen and acidic carboxylic acid ester groups are typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, sulfonate, sulfate, phosphonate, or phosphate groups provide a negative charge.

[0150] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, wherein the aliphatic group can be linear or branched and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water-coating group, such as a carboxyl, sulfonic acid, sulfate, phosphate, or phosphonoyl group. Amphoteric surfactants are subdivided into two main categories, which are known to those skilled in the art and described in “The Complete Guide to Surfactants,” Cosmetics and Toiletries, Vol. 104(2) 69-71 (1989), which is incorporated herein by reference in its entirety. The first category includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second category includes N-alkyl amino acids and their salts. Some amphoteric surfactants may be considered to fall into either of these categories.

[0151] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethyl imidazoline is synthesized via the condensation and ring-closure of a long-chain carboxylic acid (or derivative) with a dialkylethylenediamine. Commercially available amphoteric surfactants are derivatized by alkylation, for example, using chloroacetic acid or ethyl acetate, which causes sequential hydrolysis and ring-opening of the imidazoline ring. During alkylation, one or both carboxyl-alkyl groups react with different alkylating agents to form tertiary amines and ether linkages, producing different tertiary amines.

[0152] The long-chain imidazole derivatives used in this invention generally have the following general formula: (Single) Acetate (II) Propionate neutral pH zwitterions Amphoteric sulfonates Wherein R is a noncyclic hydrophobic group containing about 8 to 18 carbon atoms, and M is a cation used to neutralize anions, typically sodium. Commercially known imidazoline-derived amphoteric surfactants that can be used in the compositions of this invention include, for example, cocoamphopropionate, cocoamphocarboxypropionate, cocoamphoglycinate, cocoamphocarboxyglycinate, cocoamphopropylsulfonate, and cocoamphocarboxypropionic acid. The amphoteric carboxylic acid can be generated from aliphatic imidazolines, wherein the dicarboxylic acid functional group of the amphoteric dicarboxylic acid is diacetic acid and / or dipropionic acid.

[0153] The carboxymethylated compounds (glycine salts) described above are often referred to as betaine. Betaine is a special class of amphoteric surfactants discussed below in the section entitled "Amphoteric Surfactants".

[0154] Long-chain N-alkyl amino acids readily pass through RNH2 (where R=C8-C).18 It is prepared by reacting straight-chain or branched alkyl groups, aliphatic amines, and halocarboxylic acids. Alkylation of the primary amino group of an amino acid yields secondary and tertiary amines. The alkyl substituent may have additional amino groups providing more than one reactive nitrogen center. Most commercial N-alkylamino acids are alkyl derivatives of β-alanine or β-N(2-carboxyethyl)alanine. Examples of commercial N-alkyl amino acid amphoteric electrolytes used in this invention include alkyl β-amino dipropionates, RN(C2H4COOM)2, and RNHC2H4COOM. In one embodiment, R may be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation used to neutralize the charge of the anion.

[0155] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include ethylenediamine moieties, alkanolamide moieties, amino acid moieties (e.g., glycine), or combinations thereof as part of their structure; and aliphatic substituents of about 8 to 18 (e.g., 12) carbon atoms. Such surfactants can also be considered alkyl amphoteric dicarboxylic acids. These amphoteric surfactants can contain chemical structures represented as follows: 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 + (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is a suitable amphoteric surfactant and is available under the trademark Miranol™ FBS from Rhodia Inc., Cranbury, NJ. Another suitable coconut-derived chemical name for this amphoteric surfactant is disodium cocoamphodiacetate, sold under the trademark Mirataine™ JCHA, also from Rhodia Inc., Cranbury, NJ.

[0156] A typical list of the amphoteric classes and species of these surfactants is given in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are given in *Surface Active Agents and Detergents* (Volumes I and II, by Schwartz, Perry, and Berch). These references are each incorporated herein by reference in their entirety.

[0157] zwitterionic surfactants Zwitterionic surfactants can be considered a subgroup of amphoteric surfactants and can include anionic charges. Broadly, zwitterionic surfactants can be described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants include positively charged quaternary ammonium ions, or in some cases, sulfonium or phosphonium ions; negatively charged carboxyl groups; and alkyl groups. Zwitterionic surfactants generally contain cationic and anionic groups that are ionized to nearly equal degree in the isoelectric region of the molecule and can generate a strong “internal salt” attraction between the positive and negative charge centers. Examples of such synthetic zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, wherein the aliphatic groups can be straight-chain or branched, and wherein one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains anionic water-solubilizing groups, such as carboxyl, sulfonate, sulfate, phosphate, or phosphonate groups.

[0158] Betaine surfactants and sulfobetaine surfactants are exemplary zwitterionic surfactants used in this paper. The general formula for these compounds is: Where R 1 Contains an alkyl, alkenyl, or hydroxyalkyl group having 8 to 18 carbon atoms, having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moieties; Y is selected from the group consisting of nitrogen, phosphorus, and sulfur atoms; R 2 It is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; when Y is a sulfur atom, x is 1, and when Y is a nitrogen or phosphorus atom, x is 2, R 3 Z is an alkylene or hydroxyalkylene or a hydroxyalkylene having one to four carbon atoms, and Z is a group selected from the group consisting of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.

[0159] Examples of zwitterionic surfactants having the structures listed above include: 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonium]-but-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonium]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosylphosphine]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl-ammonium]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulfonate; -N-hexadecylammonium)-2-hydroxy-propane-1-sulfonate; 4-[N,N-bis(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonium]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecyloxy-2-hydroxypropyl)sulfonium]-propane-1-phosphate; 3-[P,P-dimethyl-P-dodecylphosphino]-propane-1-phosphonate; and S[N,N-bis(3-hydroxypropyl)-N-hexadecylammonium]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in the detergent surfactant can be straight-chain or branched and can be saturated or unsaturated.

[0160] The zwitterionic surfactants suitable for the compositions of the present invention include betaine having the following general formula: These surfactants, betaines, typically do not exhibit strong cationic or anionic characteristics at extreme pH values, nor do they show a decrease in water solubility over their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are compatible with anionic surfactants. Suitable examples of betaines include cocoylamidopropyl dimethyl betaine; hexadecyl dimethyl betaine; C 12-14 Acylamidopropyl betaine; C 8-14 Acylamidohexyldiethylbetaine; 4-C 14-16 Acylmethylamidodiethylammonium-1-carboxybutane; C 16-18 Acylamidodimethylbetaine; C 12-16 Acylamidopentanediethyl betaine; and C 12-16 Acylmethylamidodimethylbetaine.

[0161] The sulfobetaines suitable for use in this invention include those having the formula (R(R)). 1 )2 N + R 2 SO 3- Those compounds in which R is C6-C 18 Hydrocarbon group, each R 1 Typically, it is independently a C1-C3 alkyl group, such as methyl, and R2 It is a C1-C6 hydrocarbon group, such as a C1-C3 alkylene group or a hydroxyalkylene group.

[0162] A typical list of zwitterionic classes and substances of these surfactants is given in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Further examples are given in *Surface Active Agents and Detergents* (Volumes I and II, by Schwartz, Perry, and Berch). These references are each incorporated herein in full.

[0163] Method for manufacturing cleaning compositions The cured 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.

[0164] Solid particulate cleaning compositions can be prepared by blending dry solid components formed according to the invention in appropriate proportions or by agglomerating materials in a suitable coalescence system. Granulated materials can be manufactured by compressing solid granules or agglomerated materials in a suitable granulation apparatus to produce granulated materials of appropriate size. Solid block and cast solid block materials are prepared by introducing pre-hardened material blocks or castable liquids hardened into solid blocks within a container into a container. Preferred containers include disposable plastic containers or water-soluble film containers. Other suitable packaging for the compositions includes flexible bags, pouches, shrink wraps, and water-soluble films such as polyvinyl alcohol.

[0165] Solid cleaning compositions can be formed using batch or continuous mixing systems. 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 at or below the melting temperature of the components. The processed mixture can be dispensed from the mixer by forming, casting, or other suitable means, thereby hardening the cleaning composition into a solid form. The structure of the matrix can be characterized according to methods known in the art based on the matrix's hardness, melting point, material distribution, crystal structure, and other similar properties. Generally, solid cleaning compositions processed according to the method of the invention are substantially homogeneous in compositional distribution throughout their entire mass and are dimensionally stable.

[0166] In an 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 forming means. The product is then packaged. In one exemplary embodiment, the forming composition begins to harden into a solid form between approximately 1 minute and approximately 3 hours. Specifically, the forming composition begins to harden into a solid form between approximately 1 minute and approximately 2 hours. More specifically, the forming composition begins to harden into a solid form between approximately 1 minute and approximately 20 minutes.

[0167] In the casting process, liquid and solid components are introduced into a final mixing system and continuously mixed until the components form a generally homogeneous liquid mixture in which the components are distributed throughout the entire mass. In one exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once mixing is complete, the product can be transferred to a packaging container therein for curing. In one exemplary embodiment, the casting composition begins to harden into a solid form between approximately 1 minute and approximately 3 hours. Specifically, the casting composition begins to harden into a solid form between approximately 1 minute and approximately 2 hours. More specifically, the casting composition begins to harden into a solid form between approximately 1 minute and approximately 20 minutes.

[0168] In a pressed solids method, flowable solids (such as granular solids or other particulate solids) are combined under pressure. In a pressed solids method, the flowable solids of the composition are placed in a molded part (e.g., a mold or container). The method may include gently pressing the flowable solids in the molded part to produce a solid cleaning composition. Pressure may be applied using a block machine or a rotary press. Pressures of about 1 psi to about 3000 psi, about 5 psi to about 2500 psi, or about 10 psi to about 2000 psi may be applied. As used herein, the term “psi” or “pounds per square inch” refers to the actual pressure applied to the pressed flowable solids and not to gauge or hydraulic pressure measured at a point in the equipment where the pressing is performed. The method may include a curing step to produce a solid cleaning composition. As mentioned herein, an uncured composition comprising flowable solids is compressed to provide sufficient surface contact between the particles constituting the flowable solids, such that the uncured composition cures into a stable solid cleaning composition. Sufficient contact between a sufficient number of particles (e.g., fine particles) provides effective particle-to-particle bonding for the preparation of a stable solid composition. Optional curing steps may include allowing the pressed solid to cure for a period of time, such as several hours or about one day (or longer). In an additional aspect, the method may include a vibratory form or a flowable solid in a mold, as disclosed in U.S. Patent No. 8,889,048, which is incorporated herein by reference in its entirety.

[0169] Compared to conventional solid block or tablet compositions that require high pressure in a tableting machine, or casting that requires melting the composition and consumes significant amounts of energy, and / or extrusion that requires expensive equipment and advanced technical knowledge, the use of compressed solids offers numerous advantages. Compressed solids overcome many of the limitations of other solid formulations required to produce solid, clean compositions. Furthermore, compressed solid compositions retain their shape under conditions where the composition can be stored or disposed of.

[0170] The term "solid" refers to a hardened composition that does not flow and will substantially retain its shape under moderate stress or pressure or gravity alone. Solids can be in a variety of forms, such as powder, flakes, granules, pellets, tablets, rhomboid flakes, ice-ball-shaped lumps, clumps, bricks, solid blocks, unit doses, or another solid form known to those skilled in the art. The hardness of solid casting compositions and / or pressed solid compositions can range from the hardness of a relatively dense and hard molten solid product (e.g., like concrete) to the consistency characterized as a hardened paste. Additionally, the term "solid" refers to the state of a cleaning composition under the intended conditions for storage and use. Generally, a cleaning composition is expected to remain in solid form when exposed to temperatures of at most approximately 100℉, and more precisely at most approximately 120℉.

[0171] The resulting solid cleaning compositions can take, but are not limited to, the following forms: cast solid products; extruded, molded, or shaped solid pellets, blocks, tablets, powders, granules, flakes; pressed solids; or subsequently, the shaped solids can be ground or shaped into powders, granules, or flakes. In exemplary embodiments, the extruded pellet material formed from the solidified matrix has a weight between approximately 50 grams and approximately 250 grams, the extruded solid formed from the composition has a weight of approximately 100 grams or more, and the solid block detergent formed from the composition has a mass between approximately 1 and approximately 10 kilograms. The solid compositions provide a stable source of functional materials. In some embodiments, the solid compositions can be dissolved in, for example, an aqueous solution or other medium to produce concentrated solutions and / or use solutions. The solutions can be directed to storage containers for subsequent use and / or dilution, or they can be applied directly to the point of use.

[0172] The following patents disclose various combinations of solidifying, binding, and / or hardening agents that can be used in the solid cleaning compositions of the present invention. The following U.S. patents are incorporated herein by reference: 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; and 6,410,495. Nos. 6,258,765; 6,177,392; 6,156,715; 5,858,299; 5,316,688; 5,234,615; 5,198,198; 5,078,301; 4,595,520; 4,680,134; RE32,763; and RE32818.

[0173] Liquid compositions are typically prepared by forming the components in an aqueous liquid or aqueous liquid solvent system. Such systems are typically prepared by dissolving or suspending the active ingredient in water or a compatible solvent, and then diluting the product to an appropriate concentration to form a concentrate or a solution for use. Gelation compositions can similarly be prepared by dissolving or suspending the active ingredient in a compatible aqueous (aqueous liquid or mixed aqueous) organic system comprising an appropriate concentration of a gelling agent. All disclosures and patent applications in this specification indicate the level of skill of one ordinary person in the art to which this invention pertains. All disclosures and patent applications are incorporated herein by reference to the extent that each individual disclosure or patent application is expressly and individually indicated to be incorporated by reference.

[0174] Example The embodiments of the present invention are further limited to the following non-limiting examples. It should be understood that although these examples illustrate certain implementations of the invention, they are merely illustrative and non-limiting. From the foregoing discussion and these examples, those skilled in the art can recognize the essential characteristics of the invention, and various changes and modifications can be made to the embodiments of the invention to adapt them to various uses and conditions without departing from its spirit and scope. Therefore, in addition to what is described herein, various modifications to the embodiments of the invention will be apparent to those skilled in the art based on the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

[0175] Materials used: BIO-TERGE® AS-90: 90% active spray-dried sodium C14-C16 alpha olefin sulfonate available from Stepan.

[0176] DEHYPON® LS 54: Available from BASF for low-foaming fatty alcohols and ethylene oxide / propylene oxide derivatives.

[0177] DEQUEST® 2016D: A hydroxyethylidene-based scale inhibitor available from Italmatch Chemicals.

[0178] GLUCOPON® 625 UP: Available from BASF as an alkyl polyglucoside.

[0179] LUTENSOL® TDA-3: Available from BASF as a tridecyl alcohol ethoxylate.

[0180] LUTENSOL® XL 40: A branched Guerbet nonionic alkylene oxide product available from BASF.

[0181] LUTENSOL® XP 50: A branched Guerbet nonionic ethylene oxide product available from BASF.

[0182] PLURAFAC® LF 221: A fatty alcohol alkoxylate available from BASF.

[0183] PLURAFAC® RA 300: A fatty alcohol alkoxylate available from BASF.

[0184] PLUAFAC® SLF-180: A fatty alcohol alkoxylate available from BASF.

[0185] PLURONIC® 25R2: Propanolated polyoxyethylene available from BASF.

[0186] PLURONIC® F68: A bifunctional block copolymer with terminal primary hydroxyl groups available from BASF.

[0187] PLURONIC® L61: A bifunctional block copolymer with terminal primary hydroxyl groups available from BASF.

[0188] SURFONIC® L24-7: A linear C-type ... 12-16 Alcohol ethoxylates.

[0189] TETRONIC® 1301: A tetrafunctional block copolymer available from BASF.

[0190] TETRONIC® 150R1: A reverse tetrafunctional block copolymer available from BASF.

[0191] TOMADOL® 91-6: Available from Evonik (C) 9-11 Ethoxylated alcohols.

[0192] The additional ingredients used, which are available from multiple commercial sources, include anhydrous citric acid, polyethylene glycol (PEG8000), sodium carbonate, sodium chloride (NaCl), anhydrous sodium sulfate, sodium xylenesulfonate (SXS), and urea.

[0193] Example 1 Nonionic surfactants in the curing liquid of a spray dryer The exemplary liquid nonionic surfactant was cured using a spray drying device.

[0194] Tests were performed to evaluate the curing of the liquid nonionic surfactant with the binder. Table 2 provides the prepared compositions and notes on the powder flow characteristics of the resulting cured surfactant compositions. The weight of the components in each prepared composition represents the liquid composition before curing.

[0195] Table 2 As can be seen in Table 2, when a spray dryer is used to combine curing with an adhesive, the liquid nonionic surfactant can be cured in powder form with good flow properties.

[0196] Example 2 Solidification of liquid nonionic surfactants in a fluidized bed The exemplary liquid nonionic surfactant was cured using a fluidized bed. Tests were performed to evaluate the curing of the liquid nonionic surfactant with the binder. Table 3 provides the prepared compositions and notes on the powder flow characteristics of the resulting cured surfactant compositions.

[0197] Table 3 As can be seen in Table 3, when a fluidized bed is used in combination with a binder for curing, liquid nonionic surfactants can be cured in powder form with good flow properties.

[0198] The liquid nonionic surfactant compositions cured using a fluidized bed were further compared with those cured using a conventional conical mixer. Table 4 provides the prepared compositions and the methods used to cure them.

[0199] Table 4 After the liquid surfactant compositions are cured, compositions A and B, cured via a fluidized bed, produce free-flowing powders with a non-sticky consistency and easily broken lumps (if present). In contrast, composition C, cured by a conventional conical mixer, produces unfavorable powder flow, where the powder is both sticky and agglomerated. Furthermore, the powder of composition C is non-flowing. Therefore, the results show that the curing method employed in this invention is capable of forming flowable powders compared to conventional curing methods using mixers and agitators that fail to produce free-flowing powders.

[0200] Example 3 Curing nonionic surfactants without processing steps The curing of the exemplary liquid nonionic surfactant was evaluated without any processing steps. Tests were performed to assess the curing of the liquid nonionic surfactant with the binder. Table 5 provides the prepared compositions and notes on the powder flow characteristics of the resulting cured surfactant compositions. The compositions were prepared using a conventional conical mixer or conventional ribbon mixer, rather than by spray drying or fluidized bed curing as described herein. Milled urea and fine SXS powder were used to increase the surface area.

[0201] Table 5 As can be seen in Table 5, conventional mixing methods do not produce flowable powder. The results indicate that, without a drying process, simply mixing liquid surfactants and binders or carriers does not result in a free-flowing powder. These results further distinguish the curing method of this invention for forming flowable powders from the simple mixing of surfactant and binder components.

[0202] Example 4 Pressed solids were prepared using nonionic surfactant powder. A premixed composition of liquid nonionic surfactant and SXS was formulated into a flowable powder for evaluation of its use in rinsing aid formulations. Table 6 provides premixed compositions containing nonionic surfactant and SXS before curing. The compositions were dried in a fluidized bed to form a dry, flowable powder. The liquid flow rate for each premixed composition was maintained at 30 g / min, with a process air volume of 90 m³.3 / hr and the inlet air temperature is 120°C to maintain a bed temperature of 70°C. The percentage of powdered, dried surfactant is also listed in Table 6.

[0203] Table 6 The free-flowing powder premixed compositions from Table 6 were incorporated into the rinsing aid formulation and pressed into pressed solids. Table 7 provides pressed rinsing aid compositions used to evaluate the ability to form pressed solids using nonionic surfactants and SXS premixed compositions. The components of the cured rinsing aid composition were combined in a ribbon mixer and slowly mixed for approximately 30 seconds. The dye was slowly poured on top and mixed for one minute. Each block weighed approximately 0.91 kg and pressed into a pressed solid. In addition to the flow index and particle size distribution of the cured rinsing aid composition, the percentage of total surfactant in the cured rinsing aid composition is further listed below.

[0204] Table 7 As shown in Table 7, the incorporation of the premixed composition of nonionic surfactant and SXS blended well with the additional rinsing aid components. Although the batches exhibited uneven dye dispersion, all cured rinsing aid compositions were well pressed and showed little or no accumulation on the contact surfaces.

[0205] The features disclosed in the foregoing description or the appended claims are expressed in their particular form or according to the manner in which the functions of this disclosure are performed or the method or process for achieving the results of this disclosure (which may, where appropriate, be alone or in any combination of such features) for implementing the invention in its various forms.

[0206] The invention has thus been described, and it will be apparent that it can be varied in many ways. Such variations will not be considered as departing 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 foregoing description provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be carried out without departing from the spirit and scope of the invention, the invention is attributed to the claims.

[0207] The present invention also relates to embodiments numbered as follows: 1. A curable liquid surfactant composition, said curable liquid surfactant composition comprising: Liquid nonionic surfactants; and A solid adhesive comprising a natural polymer, urea, urea derivatives, polyacrylate, chelating agent, PEG, inorganic acid and / or its salt, organic salt and / or its salt, aromatic sulfonate or combinations thereof; wherein the ratio of the solid adhesive to the liquid surfactant is between about 4:1 and about 1:60 based on the active substance. The composition is solid and the liquid surfactant is cured in the composition.

[0208] 2. The curing surfactant composition according to Embodiment 1, wherein the ratio of the solid binder to the liquid surfactant is between about 3:1 and about 1:50 of the active substances.

[0209] 3. The cured surfactant composition according to any one of Embodiments 1-2, 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 amide alkoxylate, a alkyl ester, and combinations thereof.

[0210] 4. The cured surfactant composition according to any one of embodiments 1-3, wherein the cured surfactant composition is a flowable powder.

[0211] 5. The curing surfactant composition according to any one of embodiments 1-4, wherein the binder is urea, urea derivatives, or a combination thereof.

[0212] 6. The curing surfactant composition according to any one of embodiments 1-4, wherein the binder is sodium acetate, sodium chloride, sodium sulfate, magnesium sulfate, sodium xylenesulfonate, alkali metal carbonate, PEG with a melting point of at least about 40°C, or a combination thereof.

[0213] 7. The curing surfactant composition according to any one of embodiments 1-4, wherein the binder is a gum, cellulose, cellulose ester, chitin, chitosan, starch, chemically modified starch, protein, lignin, natural rubber, or a combination thereof.

[0214] 8. The curing surfactant composition according to any one of embodiments 1-7, wherein the adhesive comprises a chelating agent; and wherein the chelating agent is an aminocarboxylate.

[0215] 9. The curing surfactant composition according to any one of embodiments 6-8, wherein the binder is PEG 1450, PEG 3350, PEG 4000, PEG 4600, PEG 8000, or a combination thereof.

[0216] 10. The cured surfactant composition according to any one of embodiments 1-9, wherein the cured surfactant composition further comprises a carrier.

[0217] 11. The curing surfactant composition according to embodiment 10, wherein the adhesive and the carrier have a water solubility of about 0.2 g / L or greater at 20°C.

[0218] 12. The cured surfactant composition according to any one of embodiments 10-11, wherein the carrier is an anionic surfactant, an organic salt, an inorganic salt, or a combination thereof.

[0219] 13. The curing surfactant composition according to any one of embodiments 10-12, wherein the carrier comprises α-olefin sulfonate, linear alkyl sulfonate, sodium lauryl sulfate, sodium alkyl sulfate, sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium sulfate, sodium chloride, or combinations thereof.

[0220] 14. The curing surfactant composition according to any one of embodiments 1-13, wherein the carrier is a solid.

[0221] 15. The cured surfactant composition according to any one of embodiments 1-14, wherein the cured surfactant composition has less than about 12% by weight of water.

[0222] 16. The cured surfactant composition according to any one of embodiments 1-15, wherein the cured surfactant composition has less than about 10% by weight of water.

[0223] 17. A curable liquid surfactant composition, said curable liquid surfactant composition comprising: Liquid nonionic surfactants; and The carrier comprises anionic surfactant, inorganic acid and / or its salt, organic salt and / or its salt, or combinations thereof; wherein the ratio of the carrier to the liquid surfactant is between about 5:1 and about 1:30 based on the active substance. The composition is a solid and the liquid surfactant is cured in the composition, and the cured surfactant composition is wherein.

[0224] 18. The curing surfactant composition according to embodiment 17, wherein the ratio of the carrier to the liquid surfactant is between about 2:1 and about 1:20 of active substances.

[0225] 19. The cured surfactant composition according to any one of embodiments 17-18, 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 amide alkoxylate, a alkyl ester, and combinations thereof.

[0226] 20. The cured surfactant composition according to any one of embodiments 17-19, wherein the cured surfactant composition is a flowable powder.

[0227] 21. The curing surfactant composition according to any one of embodiments 17-20, wherein the carrier comprises an anionic surfactant; wherein the anionic surfactant is a sulfonate, a sulfate, or a combination thereof.

[0228] 22. The curing surfactant composition according to any one of embodiments 17-21, wherein the carrier is an α-olefin sulfonate, a linear alkyl sulfonate, sodium lauryl sulfate, sodium alkyl sulfate, or a combination thereof.

[0229] 23. The cured surfactant composition according to any one of embodiments 17-20, wherein the carrier is an alkali metal carbonate, an alkaline metal carbonate, an alkali metal acetate, an alkaline metal acetate, an alkali metal sulfate, an alkaline metal sulfate, sodium chloride, or a combination thereof.

[0230] 24. The cured surfactant composition according to any one of embodiments 17-20 or 23, wherein the carrier is sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium acetate, or a combination thereof.

[0231] 25. The curing surfactant composition according to any one of embodiments 17-24, wherein the carrier is a solid.

[0232] 26. The cured surfactant composition according to any one of embodiments 17-25, wherein the carrier is a powder.

[0233] 27. The curing surfactant composition according to any one of embodiments 17-24, wherein the carrier is a liquid.

[0234] 28. The cured surfactant composition according to any one of embodiments 17-27, wherein the carrier has a water solubility of about 0.2 g / L or greater at 20°C.

[0235] 29. The cured surfactant composition according to any one of embodiments 17-28, wherein the cured surfactant composition has less than about 5% by weight of water.

[0236] 30. The curing surfactant composition according to any one of embodiments 1-29, wherein the curing surfactant composition contains at least about 10% by weight of an active surfactant.

[0237] 31. The curing surfactant composition according to any one of embodiments 1-30, wherein the curing surfactant composition contains at least about 25% by weight of an active surfactant.

[0238] 32. The curing surfactant composition according to any one of embodiments 1-31, wherein the curing surfactant composition contains at least about 50% by weight of an active surfactant.

[0239] 33. A method for preparing a cured surfactant composition according to any one of embodiments 1-32, the method comprising: The liquid nonionic surfactant, the adhesive, the carrier, or a combination of adhesive and carrier are added to the drying device; The liquid surfactant, water, and binder, carrier, or combination of binder and carrier are dried to form a cured surfactant composition; The liquid surfactant is cured in the cured surfactant composition.

[0240] 34. The method for curing surfactant according to embodiment 33, wherein the drying apparatus is a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower shrinker, a vibrating conveyor shrinker, a drum dryer, a screw conveyor dryer, a fluidized bed, a jet bed, a pneumatic conveyor, a spray dryer, or a combination thereof.

[0241] 35. The method according to any one of embodiments 33-34, wherein at least two drying devices are arranged in series or in parallel.

[0242] 36. The method according to any one of embodiments 33-35, wherein the drying process is performed in a batch system or a continuous system.

[0243] 37. The method according to any one of embodiments 33-36, wherein the weight ratio of the liquid nonionic surfactant to water added to the drying apparatus is between about 1:1 and about 1:20.

[0244] 38. The method according to any one of embodiments 33-37, wherein the drying apparatus comprises a fluidized bed.

[0245] 39. The method according to embodiment 38, wherein the air velocity in the fluidized bed is between about 1 foot / second and about 100 feet / second.

[0246] 40. The method according to any one of embodiments 38-39, wherein the liquid flow rate of the fluidized bed is between about 0.001 and about 0.15 lb / min of bed material.

[0247] 41. The method according to any one of embodiments 38-40, wherein the fluidized bed has an atomizing pressure between about 0 psig and about 100 psig per nozzle.

[0248] 42. The method according to any one of embodiments 38-41, wherein the method employs a coalescence process and the carrier is a solid.

[0249] 43. The method according to any one of embodiments 38-41, wherein the method employs a granulation process and the carrier is a liquid.

[0250] 44. The method according to any one of embodiments 33-37, wherein the drying apparatus includes a spray dryer.

[0251] 45. The method according to embodiment 44, wherein the spray dryer has an inlet and an outlet; wherein the inlet temperature is between about 20°C and about 250°C; and wherein the outlet temperature is less than about 150°C.

[0252] 46. ​​The method according to any one of embodiments 44-45, wherein the inlet temperature is between about 100°C and about 250°C; and wherein the outlet temperature is between about 20°C and about 100°C.

[0253] 47. A solid cleaning composition, said solid cleaning composition comprising: The cured surfactant composition according to any one of embodiments 1-32; and Curing agent.

[0254] 48. The cleaning composition according to embodiment 47, wherein the cleaning composition is an appliance washing composition, a rinsing aid composition, a laundry composition, or a hard surface composition.

[0255] 49. The cleaning composition according to any one of embodiments 47-48, wherein the cleaning composition further comprises an alkalinity source selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, metal silicates, metal borates, alkanolamines, and combinations thereof.

[0256] 50. The cleaning composition according to embodiment 49, wherein the amount of the alkalinity source is between about 0.01% by weight and about 99% by weight of the cleaning composition.

[0257] 51. The cleaning composition according to any one of embodiments 49-50, wherein the amount of the alkalinity source is sufficient to provide a pH between about 7 and about 14 in the solution of use.

[0258] 52. The cleaning composition according to any one of embodiments 47-50, wherein the cleaning composition provides a pH between about 1 and about 7 in the use solution.

[0259] 53. The cleaning composition according to any one of embodiments 47-52, wherein the cleaning composition further comprises an additional surfactant selected from the group consisting of: nonionic surfactants, cationic surfactants, anionic surfactants, semipolar nonionic surfactants, amphoteric surfactants, amphoteric surfactants, and combinations thereof.

[0260] 54. The cleaning composition according to any one of embodiments 47-53, wherein the cleaning composition is a granular solid, a granulated solid, a cast solid, an extruded solid block, or a pressed solid.

[0261] 55. The cleaning composition according to embodiment 54, wherein the cleaning composition is a pressed solid.

[0262] 56. The cleaning composition according to any one of embodiments 47-55, wherein the cleaning composition further comprises 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, a flavoring agent, a filler, a functional polydimethylsiloxane, a hardener, a hydrateable salt, a polymer, or a disinfectant.

[0263] 57. A method for cleaning a surface, the method comprising: The surface is brought into contact with the cleaning composition according to any one of embodiments 47-56.

[0264] 58. The method according to embodiment 57, wherein the surface includes a hard surface, an appliance, or clothing.

[0265] 59. The method according to any one of embodiments 57-58, the method further comprising rinsing the surface with water.

[0266] 60. The method according to any one of embodiments 57-59, wherein the cleaning composition provides foaming properties substantially similar to those of a cleaning composition having the same composition, except that the cured surfactant composition is a liquid surfactant.

[0267] 61. The method according to any one of embodiments 57-60, wherein the cleaning composition is a rinsing aid and reduces the redeposition of dirt on the surface.

Claims

1. A curable liquid surfactant composition, said curable liquid surfactant composition comprising: Liquid nonionic surfactants; and A solid adhesive comprising a natural polymer, urea, urea derivatives, polyacrylate, chelating agent, PEG, inorganic acid and / or its salt, organic salt and / or its salt, aromatic sulfonate or combinations thereof; wherein the ratio of the solid adhesive to the liquid surfactant is between about 4:1 and about 1:60 based on the active substance. The composition is solid and the liquid surfactant is cured in the composition.

2. The curing surfactant composition according to claim 1, wherein the ratio of the solid binder to the liquid surfactant is between about 3:1 and about 1:50 of the active substances.

3. The cured surfactant composition according to any one of claims 1-2, 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 amide alkoxylate, a alkyl ester, and combinations thereof.

4. The cured surfactant composition according to any one of claims 1-3, wherein the cured surfactant composition is a flowable powder.

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

6. The curing surfactant composition according to any one of claims 1-4, wherein the binder is sodium acetate, sodium chloride, sodium sulfate, magnesium sulfate, sodium xylenesulfonate, alkali metal carbonate, PEG with a melting point of at least about 40°C, or a combination thereof.

7. The curing surfactant composition according to any one of claims 1-4, 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 curing surfactant composition according to any one of claims 1-7, wherein the adhesive comprises a chelating agent; and wherein the chelating agent is an aminocarboxylate.

9. The curing surfactant composition according to any one of claims 6-8, wherein the binder is PEG1450, PEG3350, PEG4000, PEG4600, PEG8000, or a combination thereof.

10. The curing surfactant composition according to any one of claims 1-9, wherein the curing surfactant composition further comprises a carrier.

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