BR112020015147B1 - METHOD FOR PREPARING A SOLIDIFIED SURFACTANT COMPOSITION - Google Patents

Abstract

The present invention relates to the solidification of liquid amine oxide, betaine and/or sultaine surfactants with a carrier to form a solidified surfactant composition. In particular, the invention relates to the solidification of liquid surfactants using a drying device (or devices), wherein the feed composition contains at least one liquid surfactant and a carrier to form a solidified surfactant composition. Solidified surfactant compositions may be useful in various cleaning compositions.

Description

CROSS REFERENCE TO RELATED ORDERS

[001] This application claims priority as set forth in USC Title 35 § 119 of Provisional Application Serial Number U.S. 62/622,403 filed January 26, 2018, incorporated herein by reference in its entirety including without limitation, the tables, examples and claims.

[002] This application also refers to Provisional Application Serial Number 62/622,356 filed on January 26, 2018, and U.S. Patent Application No. 16/259,015 [Attorney's Dossier No. P12085US01] filed on January 28 January 2019, in which both are entitled “SOLIDIFYING LIQUID AMINE OXIDE, BETAINE, AND/OR SULTAINE SURFACTANTS WITH A BINDER AND OPTIONAL CARRIER” which is incorporated herein by reference in its entirety including, without limitation, the tables , examples and claims.

FIELD OF TECHNIQUE

[003] The disclosure refers to the solidification of liquid amine oxide, sultaine and/or betaine surfactants with a carrier. In particular, the invention relates to the solidification of liquid amine oxide, betaine and sultaine surfactants with a drying device (or devices), wherein the feed composition contains at least one surfactant and a carrier.

BACKGROUND

[004] Various amine oxide, betaine and sultaine surfactants are available only in liquid form. It is desirable to provide many of these surfactants in solid form in order to produce solid cleaning compositions. As many of these surfactants are only available in liquid form, they cannot be easily incorporated into solid formulations or are limited in the active concentration that can be included in the formulation.

[005] There have been attempts to include certain liquid surfactants in solid form; however, these results were unsuccessful for several reasons. It was not possible to convert liquid amine oxides, betaines and sultaines into solid surfactants and maintain surfactant effectiveness at the same time. This resulted in less desirable performance of the solid cleaning compositions. Another problem is that solidified amine oxide, betaine and sultaine surfactants are often sticky and therefore exhibit clumping, compaction and clumping, which makes it difficult to properly package, store, dose and disperse in a manufacturing process. Additionally, some methods for solidifying liquid amine oxides, betaines, and sultaines have required substantial amounts of binder and/or carrier, thereby reducing the active surfactant concentration in the final product. Other attempts to solidify liquid surfactants have been made using compounds that are not sufficiently soluble in water, for example, with a solubility of about 0.2 g/l or less at 20 °C, such as fumed silica; this is problematic for both the formulation and the end use, which is typically in water. Therefore, there is a need for improvements.

[006] Therefore, it is an object of the claimed invention to develop solidified amine oxide, betaine and/or sultaine compositions from liquid amine oxides, betaines and/or sultaines and methods to produce the same.

[007] Another object of the invention is to provide solidified amine oxide, betaine and/or sultaine compositions that are free-flowing.

[008] Another object of the invention is to provide cleaning compositions that include a solidified amine oxide, betaine and/or sultaine composition.

[009] Other objects, advantages and resources of the present invention will be evident from the following descriptive report, obtained together with the attached drawings.

DETAILED DESCRIPTION OF THE PREFERRED MODE

[0010] The present disclosure relates to the solidification of liquid amine oxide, betaine and/or sultaine surfactants with a carrier to form a solidified surfactant composition. Solidified surfactant compositions have many advantages over existing formulations, including the same surfactants as the surfactants were in liquid form, which made their use difficult or impossible in certain types of solid formulations, including, but not limited to, pressed solids. For example, many amine oxides, betaines, and sultaines are found in liquid form and are currently limited by commercially available solid actives. Converting liquid surfactants to solidified surfactant compositions allows their use at higher concentrations in solid compositions and expands their utility in solid formulations. Unexpectedly, solidification of liquid amine oxide, betaine and sultaine surfactants into solidified surfactant compositions was found to provide substantially similar performance with respect to foam and soil removal properties, which is an indicator of good overall performance of the surfactant. . This demonstrates the utility of solidified surfactant compositions in solid cleaning compositions, including, but not limited to, pressed solids. Additionally, as described herein, it has been found that solidified liquid surfactant compositions can be prepared with only a carrier and without the need for a binder. This may increase the concentration of the liquid surfactant.

[0011] Embodiments are not limited to a particular method and/or product, which may vary and are understood by those skilled in the art. Furthermore, it should be understood that all terminology used herein is intended to describe only particular embodiments and should not limit the scope in any way. For example, as used in this specification and the attached claims, the singular forms “a/a” and “the/a” may include the plural, unless the content clearly indicates otherwise. Furthermore, all units, prefixes and symbols can be represented in their SI-accepted form.

[0012] The numerical ranges recited within the specification include the numbers that define the range and include each integer within the defined range. Throughout this disclosure, various aspects of the present invention are presented in a banner format. It should be understood that the strip format description is for convenience and brevity only and should not be construed as an inflexible limitation on the scope of the invention. Therefore, it must be considered that the description of a range specifically reveals all possible subranges as well as individual numerical values within that range. For example, the description of a range such as 1 to 6 should be considered to have revealed subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6 etc., as well as individual numbers within that range, e.g. 1, 2, 3, 4, 5 and 6, and decimals and fractions, e.g. 1.2, 3.8, 1/ and 4 %. This is applicable regardless of range range.

[0013] So that the present invention can be more easily understood, certain terms are defined first. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by a person skilled in the art to which embodiments of the invention belong. Many methods and materials similar, modified or equivalent to those described herein can be used in the practice of embodiments of the present invention without undue experimentation, preferred materials and methods are described herein. In the description and claims of embodiments of the present invention, the following terminology will be used in accordance with the definitions set forth below.

[0014] The term “about”, as used herein, refers to the variation in numerical quantities that may occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable including, but not limited to , mass, volume, time and distance. Furthermore, given the solid and liquid handling procedures used in the real world, there are certain errors and certain inadvertent variations that are likely through differences in the manufacture, source or purity of the ingredients used to make the compositions or perform the methods and the like. The term "about" also encompasses quantities that are different due to different equilibrium conditions for a composition that result from a particular initial mixture. The term “about” also encompasses these variations. Regardless of whether or not modified by the term “about”, the claims include equivalent amounts.

[0015] The term "actives" or "percentage of actives" or "percentage by weight of actives" or "concentration of actives" is used interchangeably in this document and refers to the concentration of the ingredients involved in cleaning, expressed as a percentage minus inert ingredients such as water or salts.

[0016] As used herein, the term “alkyl” or “alkyl group” refers to a saturated hydrocarbon that has one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl , pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl group (or a “cycloalkyl” or “alicyclic” or “carbocyclic” group) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl , cyclo-octyl etc.), branched-chain alkyl group (e.g. isopropyl, tert-butyl, sec-butyl, isobutyl etc.), and alkyl-substituted alkyl group (e.g. alkyl-substituted cycloalkyl group and alkyl group substituted by cycloalkyl).

[0017] Unless otherwise indicated, the term “alkyl” includes “unsubstituted alkyls” and “substituted alkyls”. As used herein, the term “substituted alkyls” refers to alkyl groups that have substituents that replace one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl or aromatic (including heteroaromatic) groups.

[0018] In some embodiments, substituted alkyls may include a heterocyclic group. As used herein, the term "heterocyclic group" includes closed ring structures analogous to carbocyclic groups in which one or more carbon atoms in the ring is an element other than carbon, for example, nitrogen, sulfur or oxygen. Heterocyclic groups can be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxides, oxiranes), thirane (episulfides), dioxirane, azetidine, oxetane, thiethane, dioxane, dithiethane, dithiodine, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofenan and furan.

[0019] An “anti-redeposition agent” refers to a compound that helps to remain suspended in water, rather than redeposit on the object that is cleaned. Anti-redeposition agents are useful in the present invention to help reduce redeposition of removed dirt on the surface being cleaned.

[0020] As used herein, the term “cleaning” refers to a method used to facilitate or assist the removal of dirt, bleaching, reducing the microbial population and any combination thereof.

[0021] The term “clothes” refers to items or articles that are cleaned in a washing machine. In general, clothing refers to any item or article produced from or including textile materials, woven cloths, non-woven fabrics and knitted cloths. 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, which include mixtures of cotton and polyester. Fibers can be treated or untreated. Exemplary treated fibers include those treated for flame retardancy. It should be understood that the term "linen" is often used to describe certain types of clothing items, including bed sheets, pillowcases, towels, tablecloths, tablecloths, bar mops, and uniforms. The invention further provides a composition and method for treating non-laundry articles and surfaces, including hard surfaces such as plates, glasses and other articles.

[0022] As used herein, the term "polymer" includes generally, but is not limited to, homopolymers, copolymers, such as, for example, block, graft, random and alternating copolymers, terpolymers and higher "x"mers , additionally including its derivatives, combinations and mixtures thereof. Additionally, unless specifically limited otherwise, the term "polymer" will include all possible isomeric 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 include all possible isomeric configurations of the molecule.

[0023] As used herein, the term “dirt” or “stain” refers to a non-polar oily substance that may or may not contain particulate matter, such as mineral clays, sand, natural mineral matter, carbon black, graphite, kaolin, environmental dust etc.

[0024] As used herein, the term "substantially free" refers to compositions that completely lack the component or have such a small amount of the component that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and must be less than 0.5% by weight. In another embodiment, the amount of component is less than 0.1% by weight and in yet another embodiment, the amount of component is less than 0.01% by weight.

[0025] The term "threshold agent" refers to a compound that inhibits the crystallization of water hardness ions from solution, but does not need to form a specific complex with the water hardness ion. Boundary agents include, but are not limited to, a polyacrylate, a polymethacrylate, an olefin/maleic copolymer, and the like.

[0026] As used herein, the term “ware” refers to items such as eating and cooking utensils, dishes and other hard surfaces such as showers, sinks, toilets, bathtubs, countertops, windows, mirrors, vehicles transport and flooring. As used herein, the term “dishwashing” refers to utensils for washing, cleaning or rinsing. Dinnerware also refers to items made from plastic. Types of plastics that can be cleaned with the compositions according to the invention include, but are not limited to, those including polypropylene (PP) polymers, polycarbonate (PC) polymers, melamine formaldehyde resins or melamine resin (melamine). , acrylonitrile-butadiene-styrene (ABS) polymers and polysulfone (PS) polymers. Other exemplary plastics that can be cleaned using the compounds and compositions of the invention include polyethylene terephthalate (PET) polystyrene polyamide.

[0027] The terms "water soluble" and "water miscible", as used herein, mean that the component (e.g. carrier or solvent) is soluble or dispersible in water at about 20 ° C in 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 superior.

[0028] The term "weight percent", "weight percent", "weight percent" and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the substance. composition and multiplied by 100. It is understood, as used herein, that "percentage", "%" and the like shall be synonymous with "percentage by weight", "% by weight”, etc.

[0029] The methods, systems, apparatus and compositions of the present invention may comprise, consist essentially of, or consist of components and ingredients of the present invention, as well as other ingredients described herein. As used herein, "consist essentially of" means that the methods, systems, apparatus and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the methods. , claimed systems, apparatus and compositions.

SURFACTANT SOLIDIFICATION METHODS

[0030] Drying as a function of the process is used to remove liquid from a liquid solid system in order to produce a dry solid. Although the liquid removed is usually water, other organic liquids can be removed through a drying process. Selection of a drying device and/or configuration depends on the condition of the feed stream, desired product shape, sensitivity to feed temperature, as well as general considerations of fluid mechanics, heat and mass transfer, chemical kinetics and interactions between gas and solid. Equipment selection depends on material properties, material drying characteristics, product quality, and dust/solvent recovery.

[0031] Drying devices are typically classified in three ways. First, the operating mode of the drying device/system is classified as batch or continuous drying. Generally, batch drying is employed when required production rates are 500 pounds (226.8 kg) of dry product per hour or less. Continuous drying is favorable when more than 500 pounds (226.8 kg) of dry product is required per hour. Second, drying devices are classified by the mode of heat transfer for moisture removal. Direct heat dryers (also known as adiabatic or convective dryers) contact the material with hot gas that evaporates and removes moisture. When used in a continuous mode of operation, gas flows can be designed to be countercurrent, concurrent, or cross-flow with respect to the material. Indirect heat dryers (also known as nonadiabatic dryers) provide heat by conduction and/or radiation from a hot surface. These dryers can be operated under vacuum to lower the temperature at which moisture is evaporated. Third, dryers can also be classified based on how agitated the material is. The feed can be stationary or fluidized. Successful drying devices provide a transition zone at the inlet for atomizing the fluid or for premixing with recycled solids to improve flow. In the case of the presence of heat-sensitive solids, dryers with precise temperature control and/or vacuum conditions may be favorable. As one skilled in the art would observe, the solidification of surfactants and other useful detergent chemicals needs careful consideration and weighing of processing variables to select the appropriate drying device.

[0032] In one embodiment of the invention, the drying device is, for example, a continuous tunnel dryer, rotary dryer, vacuum dryer, tower constrictor, vibrating carrier constrictor, drum dryer, screw carrier dryer, fluidized bed, spouted bed, pneumatic conveyor, spray dryer or combinations thereof. The drying devices may be placed in parallel or in series, wherein a series includes one or more drying devices. A preferred drying device is a fluidized bed (also called a fluidized bed).

[0033] In one embodiment of the invention, the solidified surfactant compositions contain less than about 10% by weight water, preferably less than about 5% by weight water, more preferably less than about 1% by weight of water and more preferably less than about 0.5% by weight of water.

[0034] In a preferred embodiment of the invention, the methods according to the claimed invention provide a dry composition with at least about 10% by weight of active surfactants, preferably at least about 25% by weight, preferably, at least 40% by weight and, more preferably, at least 50% by weight.

FLUIDIZED BED

[0035] In a preferred embodiment of the invention, the solidification of liquid amine oxide, betaine and sultaine surfactants is carried out using a fluidized bed, in which the free-flowing wet particles are continuously dried by contact with hot gases. Without limiting any particular embodiment or theory of the invention, a fluidized bed dryer comprises a fluidization chamber into which wet particles are fed and fluidized by hot gases blown through a heater and into a plenum chamber below the bed, then through of a distributing plate that fluidizes the particles above.

[0036] The fluidized bed may use an agglomeration process that includes a solid binder and/or carrier or a granulation process that includes only liquid ingredients. The agglomeration process uses a powder feed to coat the drying material. A granulation process differs from an agglomeration process in that no powder feed is required; rather, the granulating process occurs by continuously spraying a liquid coating onto a process seed material to continuously coat and dry the liquid to form solid granules of a desired size. Furthermore, we discovered that the process can be carried out without a seed material or indeed without any material in the bed. In an embodiment where no material is in the bed at the beginning of the process, the process may begin by granulating to form a seed material and then may continue by agglomeration 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 typically is in a range of about 0.0003 to about 304.8 meters per second ( 0.001 to about 1,000 feet per second), preferably, from about 0.003 to about 152.4 meters per second (0.01 to about 500 feet per second), more preferably, from about 0.0305 to 30 .48 meters per second (0.1 to about 100) feet per second and most preferably, from about 0.3048 to about 18.288 meters per second (1 to about 60 feet per second).

[0038] Preferably, the liquid flow rate is between about 0.0005 kg/min/kg (0.001 lb/min/lb) of material in the bed and about 0.068 kg/min/kg (0.15 lb/kg). min/lb) of bed material, more preferably, between about 0.0045 kg/min/kg (0.01 lb/min/lb) of bed material and about 0.0454 kg/min/kg ( 0.10 lb/min/lb) of material in the bed. In one embodiment, when the process begins with no starting material in the bed, including no seed material, it is to be understood that the liquid flow rate at a mass per minute per mass of bed material is initially not calculable, as it is not there is starting material in the bed. However, there is material in the bed almost immediately after the process begins, as material is added to the bed for initial granulation. In such an embodiment, the ratio of added liquid to bed material is initially higher due to the smaller amount of bed material. For example, a preferred liquid flow rate without any starting material in that bed is between about 0.0454 kg/min/kg (0.1 lb/min/lb) of material in the bed and about 0.9072 kg /min/kg (2 lb/min/lb) of bed material, more preferably, between about 0.2268 kg/min/kg (0.5 lb/min/lb) of bed material and about 0 .6804 kg/min/kg (1.5 lb/min/lb) of material in bed.

[0039] The atomization pressure within the fluidized bed can be about 0 to 0.69 MPa (0 to about 100 psig) per nozzle, preferably from about 0.01 to about 0.52 MPa (1 to about 75 psig) per nozzle and, more preferably, from about 0.07 to about 0.41 Mpa (10 to about 60 psig) per nozzle.

SPRAY DRYING

[0040] In a preferred embodiment of the invention, the solidification of liquid amine oxide, betaine and sultaine surfactants is carried out using a spray dryer. Spray dryers are compatible with pastes or solutions and provide desirable evaporation for heat-sensitive materials and light, porous products. Spray dryer configurations may require checking the effects of pressure on the liquid feed and solid product in order for drying to occur without damaging the product. Generally speaking, a liquid or paste is fed to the dryer process unit and is then sprayed as fine droplets into a stream of hot gas. Therefore, the feed composition must be able to withstand the pressures necessary for droplet formation. When in the spray dryer, vaporization of the liquid occurs quickly, while the temperature of the product remains relatively low. Through the selection and design of a process, gas-solid interactions must also be considered. In particular, solid inlet and outlet conditions as well as flow capacity and residence time must be designed with respect to diffusion and heat transfer rates.

[0041] In one embodiment of the invention, the inlet temperature of the inlet feed ranges from about 20°C to about 250°C, preferably from about 100°C to about 250°C, and with more preferably from about 150°C to about 200°C. In another embodiment of the invention, the outlet temperature, aspirator and pump speed depend on the degradation of the surfactant while inside the spray dryer.

[0042] The value of the outlet temperature may vary based on the degradation temperature of the components in the solidified surfactant composition. Therefore, in certain embodiments, the temperature may be higher or lower than those established in this document. 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, more preferably between about 20°C and about of 100°C.

SOLIDIFIED SURFACTANT COMPOSITIONS

[0043] Various amine oxide, betaine and sultaine surfactants are available mainly in liquid form. It is desirable to provide many of these surfactants in solid form. One embodiment of the invention is found in solidified amine oxide, betaine and/or sultaine surfactant compositions. Another embodiment of the invention is found in methods of preparing surfactant compositions of solidified amine oxide, betaine and sultaine surfactants. Solidified surfactant compositions comprise a liquid amine oxide, betaine and/or sultaine surfactant and a carrier and, optionally, a cosurfactant which is preferably in a solid form. Additional components may be present depending on the desired properties of the solidified surfactant composition.

[0044] In one aspect of the invention, a carrier is added to a drying device with a carrier to form a solidified surfactant composition. Liquid compositions supplied to the selected drying device (or devices) of the present invention comprise at least one liquid surfactant and a carrier. In a preferred embodiment, the solidified surfactant compositions are substantially free of a binder, preferably contain less than about 1% by weight of binder, more preferably less than about 0.5% by weight of binder, even more preferably, less than about 0.1% by weight of binder and, more preferably, contain no binder at all.

[0045] The solidified surfactant compositions are preferably a powder. Preferred powder forms include, without limitation, agglomerated solids and granulated solids. Thus, in some embodiments, the solidified surfactant composition is an agglomerated solid or a granulated solid.

CARRIER

[0046] Solidified surfactant compositions may comprise a carrier. Preferably, the carrier is a solid at room temperature. In embodiments that employ a granulation process, the carrier may be in liquid form and therefore may be in dissolved form. Suitable solid carriers include, but are not limited to, powder, granules, spheres 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 more preferred embodiment, the carrier has a water solubility of about 0.2 g/l or more at 20 °C. The carrier can be added to the liquid anionic surfactant alone or with a binder to form solidified surfactant compositions.

[0047] The preferred anionic surfactants, but without limitation, sulfonate surfactants, sulfate surfactants and combinations thereof. In a preferred embodiment, the anionic surfactant carrier is a solid. More preferred anionic surfactants include, but are not limited to, alpha olefin sulfonate, linear alkyl sulfonate, sodium lauryl sulfate, sodium alkyl sulfate and combinations thereof.

[0048] Preferred organic salts include, among others, alkali and alkaline earth metal carbonates (such as sodium carbonate and magnesium carbonate), alkali and alkaline earth metal acetates (such as sodium acetate and magnesium acetate) and combinations thereof. same.

[0049] Preferred inorganic salts include, but are not limited to, alkali and alkaline earth metal sulfates (such as sodium sulfate and magnesium sulfate), sodium chloride and combinations thereof.

[0050] The carrier and liquid surfactant can be added to the drying device in a suitable amount to obtain a solidified surfactant product. The amount of each ingredient may depend on the specific liquid surfactant that is solidified, the carrier used, and any other optional ingredients that may also be included in the solidified surfactant product. Preferably, the carrier and surfactant are in an active amount ratio of between about 5:1 and about 1:30; or between about 2:1 and about 1:30; or between about 1:1 and about 1:25, or between about 1:1 and about 1:20 active.

[0051] Since one of the objectives of the present invention is to be able to incorporate liquid surfactants into solid cleaning compositions in solid form, it is preferred to have a higher concentration or ratio between surfactant and carrier and other ingredients in the solidified surfactant composition. However, this is limited by the desired physical characteristics of the solidified surfactant compositions. For example, in a preferred aspect of the invention, the surfactant is a solidified granule and not a paste. In another preferred aspect of the invention, the solidified surfactant compositions have a reduced viscosity or are non-sticky, so that they flow freely and do not harden, agglomerate or cake when stored.

LIQUID SURFACTANTS

[0052] Various surfactants are available mainly in liquid form. It is desirable to provide many of these surfactants in solid form. In one aspect of the invention, a liquid surfactant is added to a drying device with a carrier to form a solidified surfactant composition. Any suitable liquid surfactants may be included in the solidified surfactant compositions. Preferred liquid surfactants include, but are not limited to, amine oxides, betaines, sultaines and combinations thereof.

[0053] Amine oxides are tertiary amine oxides that correspond to the general formula: wherein the arrow is a conventional representation of a semipolar bond; and R1, R2 and R3 may be aliphatic, aromatic, heterocyclic, alicyclic or combinations thereof. Generally, for amine oxides of detergent interest, R1 is an alkyl radical of about 8 to about 18 carbon atoms; R2 and R3 are alkyl or hydroxyalkyl of 1 to 3 carbon atoms or a mixture thereof; R2 and R3 can be linked to each other, for example, through an oxygen or nitrogen atom, to form a ring structure; R4 is an alkaline group or a hydroxyalkylene containing 2 to 3 carbon atoms; en is in the range of 0 to about 20.

[0054] Suitable amine oxides may include those selected from coconut or dry alkyl di-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylanine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecylbutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl) oxide -3-dodecoxy-1-hydroxypropylamine, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0055] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use in this document. A general formula for these compounds is: wherein R1 contains an alkyl, alkenyl radical or a hydroxyalkyl radical of 8 to 18 carbon atoms that has 0 to 10 chemical moieties of ethylene oxide and 0 to 1 chemical moiety of glyceryl; Y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R2 is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R3 is an alkylene or hydroxy alkylene or hydroxy alkylene of 1 to 4 carbon atoms and Z is a radical selected from the group that It consists of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.

[0056] More specific betaine structures include: wherein R' contains an alkyl, alkenyl or hydroxyalkyl radical of 8 to 18 carbon atoms that has from 0 to 10 chemical moieties of ethylene oxide and from 0 to 1 chemical moiety of glyceryl; R'' is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon atoms; R''' is an alkylene or hydroxy alkylene or hydroxy alkylene of 1 to 4 carbon atoms. These surfactant betaines do not typically exhibit strong cationic or anionic characteristics at extreme pH nor do they show reduced water solubility in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are anionic compatible. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethylbetaine; 4-C14-16 acylmethylamidodiethylammonium-1 carboxybutane; C16-18 acylamidodimethylbetaine; C12-16 acylamidopentanedethylbetaine; and C12-16 acylmethylamidodimethylbetaine.

[0057] Sultaines include those compounds that have the formula (R(R1)2 N+ R2SO3-, in which R is a C6-C18 hydrocarbyl group, each R1 is typically independently C1-C3 alkyl, for example, methyl and R2 is a C1-C6 hydrocarbyl group, for example, a C1-C3 alkylene or hydroxyalkylene group.

WATER AND/OR SOLVENT MISTIBLE WITH WATER

[0058] Many of the liquid surfactants are in an aqueous medium and contain water content. Preferred aqueous media include water, water miscible, hydrogen peroxide and mixtures thereof. In one aspect of the invention, the solidified surfactant compositions contain less than about 20% by weight of added water, preferably less than about 10% by weight of added water, more preferably less than about 5% by weight. weight of added water, even more preferably less than about 1% by weight of added water, and more preferably less than about 0.5% by weight of added water. Added water refers to the amount of water added to the compositions, it does not include the amount of water present in other ingredients, such as sources of alkalinity or surfactants. Preferably, the solidified surfactant compositions contain less than about 20% by weight total water, preferably less than about 10% by weight total water, more preferably less than about 5% by weight water. total, even more preferably less than about 1% by weight total water and more preferably less than about 0.5% by weight total water. Total water refers to the water added to the composition and the water present in other ingredients, such as a source of alkalinity or surfactants. It should be understood that the amount of water added and the total water may depend on the type of solid composition being prepared, as some methods require more water than others.

[0059] In another aspect of the invention, the methods according to the claimed invention provide at least about 30% of the liquid feed, resulting in the solidified surfactant compositions, preferably between at least about 50%, more preferably, at least about 65% and more preferably at least about 85%. Liquid feed is the amount of liquid material added to the bulk drying device.

SOLID CLEANING COMPOSITIONS

[0060] The solidified surfactant compositions of the invention can be included in solid cleaning compositions. Such cleaning compositions may include, but are not limited to, detergent compositions, including, for example, utensil washing compositions and laundry compositions; washing aids; and hard surface cleaning compositions. Exemplary embodiments of these compositions are provided in Tables 1 to 3 below. Such compositions are exemplary and not limiting, for example, other cleaning compositions can be prepared with the solidified surfactant compositions of this disclosure and the cleaning compositions reflected below are offered as examples of preferred formulations. TABLE 1. EXAMPLE MANUAL WASHING COMPOSITION OF UTENSILS TABLE 2. EXAMPLE CLOTHES WASHING COMPOSITION TABLE 3. EXAMPLE HARD SURFACE CLEANING COMPOSITION

[0061] In embodiments of the invention, additional ingredients can be included in solid cleaning compositions. Additional ingredients provide desired properties and functionality to the compositions. For purposes of this application, the term “functional ingredient" includes a material that provides a beneficial property in a particular use. Some particular examples of functional materials are discussed in more detail below, although the specific materials discussed are provided by way of example only. , and that 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, specifically utensil washing applications. However, other embodiments may include functional ingredients for use in cleaning. other applications. Examples of such functional material include chelating/sequestering agents; ; corrosion inhibitors; loads; solidifiers; a hardening agent; solubility modifiers; pH adjusting agents; humectants; hydrotropes; or a wide variety of other functional materials, depending on the desired characteristics and/or functionality of the composition. In the context of some embodiments disclosed herein, functional materials, or ingredients, are optionally included in the solidification matrix for their functional properties. Some more particular examples of functional materials are discussed in greater detail below, but it should be understood by those skilled in the art and others that the particular materials discussed are provided by way of example only and that a wide variety of other functional materials can be used.

[0062] In one aspect of the invention, some of the additional ingredients described below may be included in the solidified surfactant compositions. Preferred additional ingredients that may be incorporated into solidified surfactant compositions include, but are not limited to, a cosurfactant, colorant and/or fragrance (odorant).

ACID SOURCE

[0063] In some embodiments of the invention, a cleaning composition may include an acid source. Suitable acid sources may include organic and/or inorganic acids. Examples of suitable organic acids include carboxylic acids, such as, but not limited to, hydroxyacetic (glycolic) acid, citric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, trichloroacetic acid, urea hydrochloride and benzoic acid among others. Organic dicarboxylic acids, such as oxalic acid, malonic acid, gluconic acid, itaconic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid and terephthalic acid, among others, are also useful according to the invention. Any combination of these organic acids can also be intermixed or with other organic acids that allow the proper formation of the composition of the invention.

[0064] Useful inorganic acids according to the invention include sulfuric acid, sulfamic acid, methylsulfamic acid, hydrochloric acid, hydrobromic acid and nitric acid, among others. These acids can also be used in combination with other inorganic acids or the organic acids mentioned above. In a preferred embodiment, the acid is an inorganic acid.

[0065] In some embodiments of the invention, a cleaning composition may have an acidic pH. In such an embodiment, the pH is preferably between 1 and 7. In another aspect of the invention, the acid source can be included as a pH modifier or neutralizer in a basic composition to achieve the desired pH.

ACTIVATORS

[0066] In some embodiments, a cleaning composition may have enhanced antimicrobial capacity or bleaching activity by adding a material that, when the composition is used, reacts with active oxygen to form an activated component. For example, in some embodiments, a peracid or a peracid salt is formed. For example, in some embodiments, diamine tetraacetylethylene may be included in the composition to react with active oxygen and form a peracid or peracid salt that acts as an antimicrobial agent. Other examples of active oxygen activators include transition metals and their compounds, compounds containing a carboxylic, nitrile or ester moiety, or other such compounds known in the art. In one embodiment, the activator includes diamine tetraacetylethylene; transition metal; compound that includes carboxylic, nitrile, amine or ester chemical moiety; or mixtures thereof.

[0067] In some embodiments, an activating component may include in the range of up to 75% by weight of the composition, in some embodiments in the range of about 0.01 to about 20% by weight, or in some embodiments in the range of about from 0.05 to about 10% by weight of the composition. In some embodiments, an activator for an active oxygen compound combines with the active oxygen to form an antimicrobial agent.

[0068] The activator can be coupled to the solid by any of a variety of methods for coupling one solid cleaning composition to another. For example, the activator may be in the form of a solid that is bonded, affixed, glued, or otherwise adhered to the solid of the cleaning composition. Alternatively, the solid activator can be formed around and surrounding the cleaning composition. By way of further example, the solid activator may be coupled to the cleaning composition by the container or package for the composition, such as by a plastic or shrink wrap or film.

SOURCE OF ALKALINITY

[0069] Cleaning compositions can include an effective amount of one or more sources of alkalinity. An effective amount of one or more alkaline sources should be considered as an amount that provides a composition that has a pH between about 7 and about 14. In a particular embodiment, the cleaning compositions can have a pH between about 7. 5 and about 13.5. During a wash cycle, the use solution may have a pH between about 6 and about 14. In particular embodiments, the use solution may have a pH between about 6 and 14. If the cleaning composition includes a enzymatic, the pH can be modulated to provide the ideal pH range for the effectiveness of the enzyme compositions. In a specific embodiment of the invention that incorporates an enzyme composition into the cleaning composition, the ideal pH is between about 10 and about 11.

[0070] Examples of suitable alkaline sources include, but are not limited to, carbonate-based alkalinity sources, including, for example, an alkali metal carbonate; caustic-based sources of alkalinity, including, for example, alkali metal hydroxides; other suitable alkalinity sources may include metal silicate, metal borate and organic alkalinity sources. Exemplary alkali metal carbonates that may be used include, but are not limited to, sodium carbonate, potassium carbonate, bicarbonate, sesquicarbonate and mixtures thereof. Exemplary alkali metal hydroxides that may be used include, but are not limited to, sodium, lithium, or potassium hydroxide. Exemplary metal silicates that may be used include, but are not limited to, sodium or potassium silicate or metasilicate. Examples of metal borates include, but are not limited to, sodium or potassium borate.

[0071] Organic sources of alkalinity are often strong nitrogenous bases including, for example, ammonia (ammonium hydroxide), amines, alkanolamines and amino alcohols. Typical examples of amines include primary, secondary or tertiary amines and diamines bearing at least one nitrogen-bonded hydrocarbon group, which represents a saturated or unsaturated linear or branched alkyl group having at least 10 carbon atoms and preferably 16 to 24 carbon atoms, or an aryl, aralkyl or alkaryl group containing up to 24 carbon atoms, and in which the other nitrogen-bonded optional groups are formed by optionally substituted alkyl groups, aryl groups or aralkyl groups or polyalkoxy groups. Typical examples of alkanolamines include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, tripropanolamine and the like. Typical examples of amino alcohols include 2-amino-2-methyl-1-propanol, 2-amino-1-butanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1 , 3-propanediol, hydroxymethylaminomethane and the like.

[0072] In general, alkalinity sources are generally available in aqueous or powdered form. Preferably, the source of alkalinity is in solid form. Alkalinity can be added to the composition in any form in the art, including as solid microspheres, granulated or particulate form, dissolved in aqueous solution or a combination thereof.

[0073] In general, cleaning compositions are expected to include the source of alkalinity in an amount between about 0.01% and about 99% by weight. In some embodiments, the source of alkalinity will be between about 35% and about 95% by weight of the total weight of the cleaning composition. When diluted into a solution for use, the compositions of the present invention can include between about 5 ppm and about 25,000 ppm of an alkalinity source.

ANTI-REDEPOSITION AGENTS

[0074] The cleaning composition may optionally include an anti-redeposition agent with the ability to facilitate prolonged suspension of dirt in a rinse solution and prevent removed dirt from being redeposited on the substrate that is rinsed. Some examples of suitable anti-redeposition agents may include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, maleic styrene anhydride copolymers and cellulosic derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and the like. A cleaning composition may include up to about 10% by weight and, in some embodiments, in the range of about 1 to about 5% by weight of an anti-redeposition agent.

BLEACHING AGENTS

[0075] Cleaning compositions may optionally include a bleaching agent. The bleaching agent may be used to lighten or bleach a substrate and may include bleaching compounds having the ability to release an active halogen species, such as Cl2, Br2, -OCl- and/or -OBr-, or the like, under conditions typically encountered during the cleaning process. Suitable bleaching agents for use may include, for example, chlorine-containing compounds, such as a chlorine, a hypochlorite, chloramines and the like. Some examples of halogen-releasing compounds include alkali metal dichloroisocyanurates, chlorinated trisodium phosphate, alkali metal hypochlorites, monochloramine and dichloramine, and the like. Encapsulated chlorine sources can 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). . A whitening agent may also include an agent that contains or acts as a source of active oxygen. The active oxygen compound acts to provide a source of active oxygen, for example it can release active oxygen in aqueous solutions. An active oxygen compound may be inorganic or organic or may be a mixture thereof. Some examples of active oxygen compounds include peroxygen compounds or adducts of peroxygen compounds. Some examples of active oxygen compounds or sources include hydrogen peroxide, perborates, sodium carbonate peroxyhydrate, phosphate peroxyhydrates, potassium permonosulfate, and sodium perborate mono- and tetrahydrate with and without activators, such as tetraacetylethylene diamine and the like. The rinse aid composition may include a minimal but effective amount of a bleaching agent, e.g., in some embodiments range up to about 10% by weight and in some embodiments range up to about 0.1 to about 6% by weight.

CHELATING/SEQUESTRATING AGENTS

[0076] The rinse aid composition may also include effective amounts of chelating/sequestering agents, also referred to as builders. Furthermore, the cleaning compositions may optionally include one or more additional builders as a functional ingredient. Generally speaking, a chelating agent is a molecule with the ability to coordinate (i.e., bind) metal ions commonly found in water supplies to prevent the metal ions from interfering with the action of other ingredients of a rinse aid. or other cleaning composition. The chelating/sequestering agent can also function as a water conditioning agent when included in an effective amount. In some embodiments, a cleaning composition may include a range of up to 70% by weight or a range of about 1 to 60% by weight of a chelating/sequestering agent.

[0077] Often, the cleaning composition is also phosphate-free and/or sulfate-free. In embodiments of the solid cleaning composition that are phosphate-free, additional functional materials, including builders, exclude phosphorus-containing compounds, such as condensed phosphates and phosphonates.

[0078] Suitable additional constructs include aminocarboxylates and polycarboxylates. Some examples of aminocarboxylates useful as chelating/sequestering agents include N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA) and the like. Some examples of polymeric polycarboxylates suitable for use as sequestering agents include those having pendant carboxylate (--CO2) groups and include, for example, polyacrylic acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid, acrylic acid copolymers -methacrylic acid, hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-methacrylonitrile copolymers and the like.

[0079] In embodiments of the solid cleaning composition that are not phosphate-free, the added chelating/sequestering agents may include, for example, a condensed phosphate, a phosphonate and the like. Some examples of condensed phosphates include sodium potassium orthophosphate, sodium potassium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and the like. A condensed phosphate can also assist, to a limited extent, in solidifying the composition by binding the free water present in the composition as water of hydration.

[0080] In embodiments of the solid cleaning composition that are not phosphate-free, the composition may include a phosphonate, such as 1-hydroxyethane-1,1-diphosphonic acid CH3C(OH)[PO(OH)2]2; aminotri(methylenephosphonic acid); aminotri(methylenephosphonate) N[CH2 PO(OH)2]3, sodium salt 2-hydroxyethyliminobis(methylenephosphonic acid) HOCH2 CH2 N[CH2 PO(OH)2]2; diethylenetriaminepenta(methylenephosphonic acid) (HO)2 POCH2 N[CH2 N[CH2 PO(OH)2]2]2; diethylenetriaminepenta(methylenephosphonate), sodium salt C9 H(28-x) N3 NaxO15P5 (x=7); hexamethylenediamine (tetramethylenephosphonate), potassium salt C10 H(28- x)N2KxO12P4 (x=6); bis(hexamethylene)triamine(pentamethylenephosphonic acid) (HO2)POCH2N[(CH2)6 N[CH2 PO(OH)2]2]2; and phosphorous acid H3PO3. In some embodiments, a phosphonate combination, such as ATMP and DTPMP, may be used. A neutralized or alkaline phosphonate or a combination of the phosphonate with an alkaline source before it is added to the mixture so that there is little or no heat or gas generated by a neutralization reaction when the phosphonate is added can be used.

[0081] For further discussion of chelating/sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339 to 366 and volume 23, pages 319 to 320, the disclosure of which is incorporated by reference to this document.

DYES/ODORANTS

[0082] Various dyes, odorants including perfumes and other aesthetic enhancing agents can also be included in the compositions. Dyes may be included to alter the appearance of the composition, for example, FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 ( American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keyston Analine and Chemical), Methanyl Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis ), Sandolan Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy) and the like.

[0083] Fragrances or perfumes that can be included in the compositions include, for example, terpenoids, such as citronellol, aldehydes, such as amyl cinnamaldehyde, a jasmine, such as C1S-jamim or jasmal, vanillin and the like.

LOADS

[0084] Solid cleaning compositions may optionally include a smaller but effective amount of one or more of a filler material. Some examples of suitable fillers may include sodium chloride, starch, sugars, C1-C10 alkylene glycols, such as propylene flicol, sulfate, PEG, urea, sodium acetate, magnesium sulfate, sodium acetate, magnesium sulfate, carbonate sodium and the like. In some embodiments, a filler may be included in an amount in the range of up to about 50% by weight or in some embodiments in the range of about 1 to 15% by weight.

FUNCTIONAL POLYDIMETHYLSILOXANES

[0085] The cleaning composition may also optionally include one or more functional polydimethylsiloxanes. For example, in some embodiments, a polyalkylene oxide-modified polydimethylsiloxane, nonionic surfactant, or a polybetaine-modified polysiloxane amphoteric surfactant may be employed as an additive. The two, in some embodiments, are linear polysiloxane copolymers to which polyethers or polybetaines have been grafted through a hydrosilylation reaction. Some examples of specific siloxane surfactants are known as SILWET® surfactants available from Union Carbide, or ABIL® polybetaine or polyether polysiloxane copolymers available from Goldschmidt Chemical Corp., and described in U.S. Patent No. 4,654,161, in which the patent is incorporated herein by reference. In some embodiments, the particular siloxanes used can be described as having, for example, low surface tension, high wetting capacity, and excellent lubricity. For example, these surfactants are considered to be among the few with the ability to wet polytetrafluoroethylene surfaces. The siloxane surfactant employed as an additive may be used alone or in combination with a fluorochemical surfactant. In some embodiments, the fluorochemical surfactant employed as an additive, optionally in combination with a silane, may be, for example, a fluoro -non-ionic hydrocarbon, for example, fluorinated alkylpolyoxyethylene ethanols, fluorinated alkyl alkoxylate and fluorinated alkyl esters.

[0086] Additional descriptions of such functional polydimethylsiloxones and/or fluorochemical surfactants are described in patents No. 5,880,088; 5,880,089; and 5,603,776, all of which are incorporated herein by reference. It has been found, for example, that the use of certain polysiloxane copolymers in a mixture with hydrocarbon surfactants provides excellent rinsing aids for plastic articles. We also conclude that the combination of certain silicone polysiloxane copolymers and hydrocarbon surfactants with conventional hydrocarbon surfactants also provides excellent rinse aids on plastic articles. This combination was found to be better than the individual components, with the exception of certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine polysiloxane copolymers, where the efficacy is nearly equivalent. Therefore, some embodiments encompass polysiloxane copolymers alone and the combination with the fluorocarbon surfactant may involve polyether polysiloxanes, the non-ionic siloxane surfactants. Amphoteric siloxane surfactants, polybetaine polysiloxane copolymers can be employed alone as the additive in rinse aids to provide the same results.

[0087] In some embodiments, the composition may include functional polydimethylsiloxanes in an amount in the range of about 10% by weight. For example, some embodiments may include in the range of about 0.1 to 10% by weight of a polyalkylene oxide-modified polydimethylsiloxane or a betaine-modified polysiloxane, optionally, in combination with about 0.1 to 10% by weight. of a non-ionic fluorinated hydrocarbon surfactant.

ADDITIONAL HARDENING/SOLIDIFICATION AGENTS/SOLUBILITY MODIFIERS

[0088] In some embodiments, one or more solidifying agents may be included in the rinse aid composition. Examples of hardening agents include urea, an amide, such as stearic monoethanolamide or lauric diethanolamide or an alkylamide and the like; sulfate salts or sulfated surfactants and aromatic sulfonates and the like; a solid polyethylene glycol, or a solid EO/PO block copolymer and the like; starches that have been made water-soluble through an acid or alkaline treatment process; various inorganics that impart solidifying properties to a heated composition upon cooling and the like. Such compounds can also vary the solubility of the composition in an aqueous medium during use, so that the rinse aid and/or other active ingredients can be dispensed from the solid composition over an extended period of time.

[0089] Suitable aromatic sulfonates include, but are not limited to, sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate and/or sodium butyl naphthalene. Preferred aromatic sulfonates include sodium xylene sulfonate and sodium cumene sulfonate.

[0090] The amount of solidifying agent included in a rinse aid composition can be dictated by the desired effect. Generally, an effective amount of solidifying agent is considered to be an amount that acts with or without other materials to solidify the rinse aid composition. Typically, for solid embodiments, the amount of solidifying agent in a rinse aid composition is in a range of about 10 to about 80% by weight of the rinse aid composition, preferably in the range of about 20 to about of 75% by weight, more preferably in the range of about 20 to about 70% by weight of the rinse aid composition. In one aspect of the invention, the solidifying agent is substantially sulfate-free. For example, the rinse aid may have less than 1% by weight sulfate, preferably less than 0.5% by weight, more preferably less than 0.1% by weight. In a preferred embodiment, the cleaning composition is sulfate-free.

[0091] In certain embodiments, it may be desirable to have a secondary solidifying agent. In compositions that contain secondary solidification, the composition may include a secondary solidifying agent in an amount in the range of up to about 50% by weight. In some embodiments, secondary hardening agents are/may be present in an amount in the range of about 5 to about 35% by weight, often in the range of about 10 to about 25% by weight, and sometimes in the range of about 5 to about 15% by weight.

[0092] In some embodiments, one or more additional hardening agents may be included in the rinse aid composition, if desired. Examples of hardening agents include an amide, such as stearic monoethanolamide or lauric diethanolamide or an alkylamide and the like; a solid polyethylene glycol, or a solid EO/PO block copolymer and the like; starches that have been made water-soluble through an acid or alkaline treatment process; various inorganics that impart solidification properties to a heated composition upon cooling and the like. Such compounds can also vary the solubility of the composition in an aqueous medium during use, so that the rinse aid and/or other ingredients can be dispensed from the solid composition over an extended period of time. The composition may include a secondary hardening agent in an amount ranging up to about 30% by weight. In some embodiments, secondary hardening agents may be present in an amount in the range of about 5 to about 25% by weight, often in the range of about 10 to about 25% by weight, and sometimes in the range of about 10 to about 25% by weight. range from about 5 to about 15% by weight.

HUMECTANT

[0093] The cleaning composition may also optionally include one or more humectants. A humectant is a substance that has an affinity for water. The humectant may be provided in an amount sufficient to reduce the visibility of a film on the substrate surface. The visibility of a film on the substrate surface is of particular concern when the rinse water contains in excess of 200 ppm total dissolved solids. Accordingly, in some embodiments, the humectant is provided in an amount sufficient to reduce the visibility of a film on a substrate surface when the rinse water contains in excess of 200 ppm total dissolved solids compared to a degreasing agent composition. rinse that does not contain humectant. The terms "water solids layer" or "layer" refer to the presence of a visible continuous layer of matter on a substrate surface that gives the appearance that the substrate surface is not clean.

[0094] Some example humectants that can be used include those materials that contain more than 5% by weight of water (based on dry humectant) balanced 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 rinse agent composition may include humectant in an amount in the range of up to about 75% based on the total composition and in some embodiments in the range of about 5% by weight to about 75% by weight with based on the weight of the composition.

HYDRATABLE SALT

[0095] The solid cleaning compositions according to the invention may optionally comprise at least one hydratable salt. In one embodiment, the hydratable salt is sodium carbonate (also known as lye or soda) and/or potassium carbonate (also known as potash). In a preferred aspect, the hydratable salt is sodium carbonate and excludes potassium carbonate. The hydratable salt may be provided in the range of between approximately 20% and 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 salt. hydratable, such as sodium carbonate. Those skilled in the art will observe other suitable component concentration ranges to obtain comparable properties of the solidification matrix.

[0096] In other embodiments, the hydratable salt can be combined with other solidifying agents. For example, the hydratable salt can be used with additional solidifying agents that are inorganic in nature and can also optionally act as a source of alkalinity. In certain embodiments, the secondary solidifying agent may include, but is not limited to: additional alkali metal hydroxides, anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous sodium acetate, and other known hydratable compounds or combinations thereof. According to a preferred embodiment, the secondary hydratable salt comprises sodium metasilicate and/or anhydrous sodium metasilicate. The amount of secondary solidifying agent required to achieve solidification depends on several factors, including the exact solidifying agent employed, the amount of water in the composition, and the hydration capacity of the other components of the cleaning composition. In certain embodiments, the secondary solidifying agent may also serve as an additional alkaline source.

POLYMER

[0097] Cleaning compositions may include a polymer or a polymer system comprised of at least one polycarboxylic acid polymer, copolymer and/or terpolymer. Particularly suitable polycarboxylic acid polymers of the present invention include, but are not limited to, polymaleic acid homopolymers, polyacrylic acid copolymers and maleic anhydride/olefin copolymers.

[0098] Polymaleic acid polymers (C4H2O3)x or hydrolyzed polymaleic anhydride or cis-2-butenedioic acid homopolymer have the structural formula: where neither are any integer. Examples of homopolymers, copolymers and/or terpolymers of polymaleic acid (and salts thereof) that can be used for the invention are particularly preferred are those with a molecular weight of about 0 to about 5,000, more preferably between about 200 and around 2,000 (can confirm these MWs). Commercially available polymaleic acid homopolymers include the Belclene 200 series of maleic acid homopolymers from BWATM Water Additives, 979 Lakeside Parkway, Suite 925 Tucker, GA 30084, USA and Aquatreat AR-801, available from AkzoNobel. Polymaleic acid homopolymers, copolymers and/or terpolymers can be present in cleaning compositions from about 0.01% by weight to about 30% by weight.

[0099] The cleaning compositions of the present invention can use polyacrylic acid polymers, copolymers and/or terpolymers. Poly acrylic acids have 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 acids, (C3H4O2)n or 2-Propenoic acid, acrylic acid, polyacrylic acid, propenoic acid .

[00100] In one embodiment of the present invention, particularly suitable acrylic acid polymers, copolymers and/or terpolymers have a molecular weight between about 100 and about 10,000, in a preferred embodiment between about 500 and about 7,000, in in an even more preferred embodiment between about 1,000 and about 5,000, and in a more preferred embodiment between about 1,500 and about 3,500. Examples of polyacrylic acid polymers, copolymers and/or terpolymers (or salts thereof) that can be used for the invention include, but are not limited to, Acusol 448 and Acusol 425 from The Dow Chemical Company, Wilmington Delaware, USA. In particular embodiments, it may be desirable to have acrylic acid polymers (and salts thereof) with molecular weights greater than about 10,000. Examples include, but are not limited to, Acusol 929 (10,000 MW) and Acumer 1510 (60,000 MW), both available from Dow Chemical, AQUATREAT AR-6 (100,000 MW) from AkzoNobel Strawinskylaan 2555 1077 ZZ Amsterdam Postbus 75730 1070 AS Amsterdam. The polyacrylic acid polymer, copolymer and/or terpolymer may be present in the compositions from about 0.01% by weight to about 30% by weight.

[00101] Maleic anhydride/olefin copolymers are copolymers of polymeric anhydrides and olefins. Maleic anhydride (C2H2(CO)2O has the following structure:

[00102] A part of the maleic anhydride can be replaced by maleimide, N-alkyl (Ci-4) maleimides, N-phenyl-maleimide, fumaric acid, itaconic acid, cirtraconic acid, aconitic acid, crotonic acid, cinnamic acid 10, ( Ci—is) alkyl esters of the aforementioned acids, (C3-8) cycloalkyl esters of the aforementioned acids, castor oil sulfate or the like.

[00103] At least 95% by weight of the polymers, copolymers or terpolymers of maleic anhydride have a number average molecular weight in the range between about 700 and about 20,000, preferably between about 1000 and about 100,000.

[00104] A variety of straight and branched chain alpha-olefins can be used for the purposes of the present invention. Particularly useful alpha-olefins are dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene and 2-methyl-1,5-hexadiene; 1-alkenes containing 4 to 8 carbon atoms, preferably C4-10, such as isobutylene, 1-butene, 1-hexene, 1-octene and the like.

[00105] In one embodiment of the present 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 a more preferred embodiment preferred between about 7,500 and about 12,500. Examples of maleic anhydride/olefin copolymers that can be used for the invention include, but are not limited to, Acusol 460N from The Dow Chemical Company, Wilmington Delaware, USA. The maleic anhydride/olefin copolymer may be present in cleaning compositions from about 0.01% by weight to about 30% by weight.

DISINFECTANTS/ANTIMICROBIAL AGENTS

[00106] Cleaning compositions may optionally include a disinfectant agent. Disinfecting agents, also known as antimicrobial agents, are chemical compositions that can be used on a solid functional material to prevent microbial contamination and deterioration of systems, surfaces, etc. In general, these materials fall into specific classes, including phenolics, halogen compounds, quaternary ammonium compounds, metallic derivatives, amines, alkanolamines, nitro derivatives, analides, organosulfur and nitrogen-sulfur compounds, and miscellaneous compounds.

[00107] It should also be understood that active oxygen compounds, such as those discussed above in the bleaching agents section, can also act as antimicrobial agents and can even provide disinfectant activity. Indeed, in some embodiments, the ability of the active oxygen compound to act as an antimicrobial agent reduces the need for additional antimicrobial agents within the composition. For example, percarbonate compositions provide excellent antimicrobial action. However, some modalities incorporate additional antimicrobial agents.

[00108] The given antimicrobial agent, depending on the chemical composition and concentration, may simply further limit the proliferation of microbe numbers or may destroy all or a portion of the microbial population. The terms "microbes" and "microorganisms" typically refer primarily to bacteria, viruses, yeast, fungal spores and microorganisms. In use, antimicrobial agents are typically formed in a solid functional material that when diluted and dispensed, optionally, e.g. , with the use of an aqueous stream forms an aqueous disinfectant or disinfectant composition that can come into contact with a variety of surfaces, resulting in the prevention of growth or the extermination of a portion of the microbial population. A three log reduction of the microbial population results. in a disinfectant composition. The antimicrobial agent may be encapsulated, for example, to improve its stability.

[00109] Some examples of common antimicrobial agents include phenolic antimicrobials, such as pentachlorophenol, orthophenylphenol, a chloro-p-benzylphenol, p-chloro-m-xylenol. Halogen-containing antibacterial agents include sodium trichloroisocyanurate complexes, sodium dichloroisocyanate (anhydrous or dihydrate), iodine-poly(vinylpyrrolidinone), bromine compounds such as 2-bromo-2-nitropropane-1,3-diol and quaternary antimicrobial agents such as benzalkonium chloride, didecyldimethyl ammonium chloride, choline diiodochloride, tetramethyl phosphonium tribromide. Other antimicrobial compositions, such as hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates, such as sodium dimethyldithiocarbamate, and a variety of other materials are known in the art for their antimicrobial properties.

[00110] In embodiments of the solid cleaning composition that are phosphate-free and/or sulfate-free and also include an antimicrobial agent, the antimicrobial is selected to meet these requirements. Embodiments of the rinse aid composition that include only GRAS ingredients may exclude or omit antimicrobial agents described in this section.

[00111] In some embodiments, the rinse aid composition comprises an antimicrobial component in the range of up to 10% by weight of the composition, in some embodiments in the range of about 5% by weight, or in some embodiments in the range of about 0. .01 to about 3% by weight or in the range of 0.05 to 1% by weight of the composition.

ADDITIONAL SURFACTANTS

[00112] Solidified surfactant compositions may include optional cosurfactants. Preferably, a cosurfactant is in solid form. Furthermore, the solidified surfactant compositions of the invention can be incorporated into cleaning compositions. Such cleaning compositions may include, but are not limited to, detergent compositions, utensil washing compositions, laundry compositions, rinse aids, and hard surface cleaning compositions. Surfactants that may be included as a cosurfactant in solidified surfactant compositions and/or as a surfactant in a cleaning composition include nonionic surfactants, semipolar nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures or combinations thereof. .

[00113] When including a cosurfactant carrier in the solidified surfactant compositions of the invention, the cosurfactant is preferably in a weight ratio to the liquid surfactant between about 1:0 and about 0:1. In a further embodiment of the invention, the cosurfactant carrier is present in amounts of from about 20% by weight to about 90% by weight, more preferably from about 30% by weight to about 90% by weight, and with more preferably, from about 40% by weight to about 80% by weight.

NONIONIC SURFACTANTS

[00114] Useful nonionic surfactants are generally characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic hydrophobic, aromatic alkyl or polyoxyalkylene compound with a hydrophilic alkaline oxide chemical moiety which in common practice it is ethylene oxide or a polyhydration product thereof, polyethylene glycol. Virtually any hydrophobic compound that has a hydroxyl, carboxyl, amino or amide group with a reactive hydrogen atom can be condensed with ethylene oxide, or polyhydration adducts thereof or mixtures with alkoxylenes thereof, such as propylene oxide for form a non-ionic surface active agent. The length of the hydrophilic polyoxyalkylene chemical moiety that is condensed with any particular hydrophobic compound can be readily adjusted to generate a water-dispersible or water-soluble compound that has the desired degree of balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

[00115] Polyoxypropylene-polyoxyethylene block polymeric compounds based on propylene glycol, ethylene glycol, glycerol, trimethylolpropane and ethylenediamine as the initiating reactive hydrogen compound. Pluronic® compounds are difunctional compounds (two reactive hydrogens) formed by condensation of ethylene oxide with a hydrophobic base formed by the addition of propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic chemical portion of the molecule weighs from about 1,000 to about 4,000. Ethylene oxide is then added to sandwich this hydrophobe between hydrophilic groups, controlled by length to constitute from about 10% by weight to about 80% by weight of the final molecule. Another class of compounds are tetrafunctional block copolymers derived from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of the propylene oxide hydrotope ranges from about 500 to about 7,000; and hydrophilic ethylene oxide is added to constitute from about 10% by weight to about 80% by weight of the molecule.

[00116] Condensation products of one mole of alkylphenol in which the alkyl chain, of straight-chain or branched-chain configuration or of the single or double alkyl constituent, contains from about 8 to about 18 carbon atoms with about 3 to about 50 moles of ethylene oxide. The alkyl group can, for example, be represented by diisobutylene, diamyl, polymerized propylene, isooctyl, nonyl and dinonyl. These surfactants can be condensates of polyethylene oxide, polypropylene and polybutylene alkylphenols. Examples of commercial compounds of this chemistry are available on the market under the trade names Igepal® manufactured by Rhone-Poulenc and Triton® manufactured by Union Carbide.

[00117] Condensation products of one mole of a straight or branched chain saturated or unsaturated alcohol that has from about 6 to about 24 carbon atoms with about 3 to about 50 moles of ethylene oxide. The alcohol chemical moiety may consist of mixtures of alcohols in the carbon range outlined above or it may consist of an alcohol that has a specific number of carbon atoms within that range. Similar commercial surfactant examples are available under the trade names Neodol™ manufactured by Shell Chemical Co. and Alfonic™ manufactured by Vista Chemical Co.

[00118] Condensation products of one mole of saturated or unsaturated straight or branched chain carboxylic acid having from about 8 to about 18 carbon atoms with from about 6 to about 50 moles of ethylene oxide. The acid moiety may consist of mixtures of acids in the range of carbon atoms defined above or may consist of an acid that has a specific number of carbon atoms within the range. Examples of commercial compounds of this chemistry are available on the market under the trade name LipopegTM manufactured by Lipo Chemicals, Inc.

[00119] In addition to ethoxylated carboxylic acids, commonly called polyethylene glycol esters, other alkanoic acid esters formed by the reaction with glycerides, glycerin and polyhydric alcohols (saccharide or sorbitan/sorbitol) are applicable to this invention for specific embodiments, particularly, indirect food additive applications. All of these ester chemical moieties have one or more reactive hydrogen sites in their molecule that can undergo additional acylation or addition of ethylene oxide (alkoxide) to control the hydrophilicity of these substances.

[00120] Examples of non-ionic low foaming surfactants include: The compounds of (1) which are modified, essentially reversed, by addition of ethylene oxide to ethylene glycol to provide a hydrophile of designated molecular weight; and then add propylene oxide to obtain hydrophobic blocks on the outside (ends) of the molecule. The hydrophobic chemical portion of the molecule weighs from about 1,000 to about 3,100 with the central hydrophile comprising 10% by weight to about 80% by weight of the final molecule. The hydrophobic chemical portion of the molecule weighs from about 2,100 to about 6,700 with the central hydrophile comprising 10% by weight to about 80% by weight of the final molecule.

[00121] Compounds of groups (1), (2), (3) and (4), which are modified by “capping” or “end blocking” of the hydroxy terminal group or groups (of multifunctional chemical moieties) to reduce foaming by reaction with a small hydrophobic molecule, such as propylene oxide, butylene oxide, benzyl chloride; and short-chain fatty acids, alcohols or alkyl halides containing from 1 to about 5 carbon atoms; and mixtures thereof. Also included are reagents such as thionyl chloride, which converts terminal hydroxy groups into a chloride group. Such modifications to the terminal hydroxy group may result in block-only, heteroblock, heteric-block, or heteric-only nonionics.

[00122] Additional examples of effective low-foaming non-ionics include: The alkylphenoxypolyethoxyalkanols of US Patent No. 2,903,486, issued September 8, 1959, to Brown et al. and represented by the formula in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of 3 to 4 carbon atoms, n is an integer from 7 to 16 and m is an integer from 1 to 10.

[00123] The polyalkylene glycol condensates of U.S. Patent No. 3,048,548, issued on August 7, 1962, to Martin et al. which has alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, where the weight of the terminal hydrophobic chains, the weight of the middle hydrophobic unit and the weight of the connecting hydrophilic units each represent about one third of the condensate.

[00124] The non-ionic antifoam surfactants disclosed in U.S. Patent No. 3,382,178, issued on May 7, 1968, by Lissant et al., which has the general formula Z[(OR)nOH]z where Z is material alkoxylatable, R is a radical derived from an alkaline oxide, which can be ethylene and propylene, and n is an integer of, for example, 10 to 2,000 or more, and z is an integer determined by the number of reactive oxyalkylatable groups.

[00125] The conjugated polyoxyalkylene compounds described in U.S. Patent No. 2,677,700, issued on May 4, 1954, to Jackson et al. corresponding to the formula Y(C3H6O)n (C2H4O)mH where Y is the organic compound residue having from about 1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of at least about 6 ,4, as determined by the hydroxyl number and m has a value such that the oxyethylene chemical portion constitutes about 10% to about 90% by weight of the molecule.

[00126] The conjugated polyoxyalkylene compounds described in U.S. Patent No. 2,674,619, issued on April 6, 1954, to Lundsted et al. having the formula Y[(C3H6On (C2H4O)mH]x where Y is the residue of an organic compound having from about 2 to 6 carbon atoms and containing x atoms of reactive hydrogen in which x has a value of at least 2, n has a value such that the molecular weight of the hydrophobic polyoxypropylene base is at least about 900 and m has a value such that the oxyethylene content of the molecule is from about 10% to about 90% by weight. Compounds that fall within the scope of the definition for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, ethylenediamine and the like. The oxypropylene chains optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains. also optionally, but advantageously, contain small amounts of propylene oxide.

[00127] Additional conjugated polyoxyalkylene surface active agents that are advantageously used in the compositions of the present invention correspond to the formula: P[(C3H6O)n (C2H4O)mH]x where P is the residue of an organic compound that must about 8 to 18 carbon atoms and which contains x reactive hydrogen atoms in which x has a value of 1 or 2, n has a value such that the molecular weight of the polyoxypropylene moiety is at least about 44, and m has a value such that the oxypropylene content of the molecule is from about 10% to about 90% by weight. In any case, the oxypropylene chains may optionally, but advantageously, contain small amounts of ethylene oxide and the oxyethylene chains may also optionally, but advantageously, contain small amounts of propylene oxide.

[00128] Polyhydroxy fatty acid amide surfactants suitable for use in the present compositions include those having the structural formula R2CONR1Z in which R1 is H, groups C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof; R2 is a C5-C31 hydrocarbyl that can be straight chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z can be derived from a reducing sugar in a reductive amination reaction; such as a chemical moiety of glycytyl.

[00129] Alkyl ethoxylated condensation products of aliphatic alcohols with about 0 to about 25 moles of ethylene oxide are suitable for use in the present compositions. The alkyl chain of aliphatic alcohol can be linear or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.

[00130] Ethoxylated C6-C18 fatty alcohols and mixed C6-C18 ethoxylated and propoxylated fatty alcohols are suitable surfactants for use in the present compositions, particularly those that are soluble in water. Suitable ethoxylated fatty alcohols include C6-C18 ethoxylated fatty alcohols with a degree of ethoxylation of 3 to 50.

[00131] Suitable nonionic alkyl polysaccharide surfactants particularly for use in the present compositions include those disclosed in U.S. Patent No. 4,565,647, Llenado, issued January 21, 1986. These surfactants include a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide, for example, a polyglycoside, hydrophilic group containing from about 1.3 to about 10 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be used in place of glycosyl moieties. (Optionally, the hydrophobic group is fixed at the 2-, 3-, 4-, etc. positions, thus providing a glucose or galactose, as opposed to a glycoside or galactoside.) The intersaccharide bonds may be, for example, between the a position of the additional saccharide units and the 2-, 3-, 4- and/or 6-positions in the previous saccharide units.

[00132] Fatty acid amide surfactants suitable for use in the present compositions include those having the formula R6CON(R7)2 in which R6 is an alkyl group containing from 7 to 21 carbon atoms and each R7 is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl or -- (C2H4O)XH, where x is in the range 1 to 3.

[00133] A useful class of nonionic surfactants includes the class defined as alkoxylated amines or, more particularly, alkoxylated/amino/alcohol alkoxylated surfactants. These nonionic surfactants can be, at least in part, represented by the general formulas: R20-- (PO)SN--(EO) tH, R20--(PO)SN--(EO) tH(EO)tH and R20 --N(EO) tH; wherein R20 is an alkyl, alkenyl or other aliphatic group or an alkyl aryl group of 8 to 20, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5 and u is 1 to 10, preferably 2 to 5. Other variations in the scope of these compounds can be represented by the alternative formula: R20--(PO)V-- N[(EO ) wH][(EO) zH] in which R20 is as defined above, v is from 1 to 20 (e.g. 1, 2, 3 or 4 (preferably 2)) and w and z are independently from 1 to 10, preferably from 2 to 5. These compounds are represented commercially by a line of products sold by Huntsman Chemicals as nonionic surfactants. A preferred chemical of this class includes Surfonic™ Alkoxylated Amine PEA 25. Preferred nonionic surfactants for the compositions of the invention include alcohol alkoxylates, EO/PO block copolymers, alkylphenol alkoxylates, and the like.

[00134] The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent reference on the wide variety of nonionic compounds generally employed in the practice of the present invention. A typical listing of nonionic classes and species of these surfactants is provided in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are provided in "Surface Active Agents and Detergents" (Volumes I and II by Schwartz, Perry and Berch).

SEMIPOLAR NONIONIC SURFACTANTS

[00135] The semipolar type of nonionic surface active agents is another class of nonionic surfactant useful in the compositions of the present invention. Generally speaking, semipolar nonionics are high foamers and foam stabilizers that can limit their application in CIP systems. However, within compositional embodiments of the present invention designed for high foam cleaning methodology, semipolar nonionics would have immediate utility. Semipolar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.

[00136] Amine oxides are tertiary amine oxides that correspond to the general formula: wherein the arrow is a conventional representation of a semipolar bond; and R1, R2 and R3 can be aliphatic, aromatic, heterocyclic, alicyclic or combinations thereof. Generally, for amine oxides of detergent interest, R1 is an alkyl radical of about 8 to about 24 carbon atoms; R2 and R3 are alkyl or hydroxyalkyl of 1 to 3 carbon atoms or a mixture thereof; R2 and R3 can be linked to each other, for example, through an oxygen or nitrogen atom, to form a ring structure; R4 is an alkaline group or a hydroxyalkylene containing 2 to 3 carbon atoms; en is in the range of 0 to about 20.

[00137] Useful water-soluble amine oxide surfactants are selected from alkyl di-(lower alkyl)amine oxides of coconut or tallow, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tradecyldimethylamine oxide, pentadecyldimethylamine, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2- hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[00138] Useful semipolar nonionic surfactants also include water-soluble phosphine oxides which have the following structure: wherein the arrow is a conventional representation of a semipolar bond; and R1 is an alkyl, alkenyl or hydroxyalkyl chemical moiety that is in the range of 10 to about 24 carbon atoms in chain length; and R2 and R3 are each alkyl moieties separately selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[00139] Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide and bis( hydroxymethyl)tetradecylphosphine.

[00140] Semipolar nonionic surfactants useful herein also include water-soluble sulfoxide compounds that have the structure: wherein the arrow is a conventional representation of a semipolar bond; and R1 is an alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms, from about 0 to about 5 ether bonds and from 0 to about 2 hydroxyl substituents; and R2 is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

[00141] Useful examples of such sulfoxides include dodecyl methyl sulfoxide; 3-hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

[00142] Semipolar nonionic surfactants for the compositions of the invention include dimethylamine oxides, such as lauryldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, combinations thereof and the like. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut or tallow alkyldi-(lower alkyl)amine oxides, examples of which are octyldimethylamine oxide, nonyldimethylamine oxide, decylmethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, isododecyldimethylamine oxide, tridecyldimethylamine oxide, tradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldimethylamine oxide cyldipropylamine, oxide tetradecylbutylamine, octadecylbutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6 oxide ,9-trioctadecyldimethylamine and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[00143] Nonionic surfactants suitable for use with the compositions of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO/PO copolymers, capped EO/PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixtures thereof or the like. Alkoxylated surfactants suitable for use as solvents include EO/PO block copolymers such as Pluronic and reverse Pluronic surfactants; alcohol alkoxylates, such as Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6); and capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11; mixtures of the same or similar ones.

ANIONIC SURFACTANTS

[00144] Also useful in the present invention are surface active substances that are categorized as anionic due to the fact that the charge on the hydrophobe is negative; or surfactants in which the hydrophobic section of the molecule does not carry charge unless the pH is raised to neutrality or higher (e.g., carboxylic acids). Carboxylate, sulfonate, sulfate and phosphate are the polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium and potassium provide solubility in water; ammonium and substituted ammonium ions provide solubility in both water and oil; and calcium, barium and magnesium promote oil solubility. As those skilled in the art understand, anionics are excellent detersive surfactants and are therefore favorable additions to heavy-duty detergent compositions.

[00145] Anionic sulfate surfactants suitable for use in the present compositions include alkyl ether sulfates, alkyl sulfates, primary and secondary linear and branched alkyl sulfates, alkyl ethoxysulfates, fatty glycerol oleyl sulfates, fatty ether sulfates, ethylene oxide phenol alkyl, the glucamine sulfates C5-C17 acyl-N-(C1-C4 alkyl) and -N(C1-C2 hydroxyalkyl) and alkylpolysaccharide sulfates, such as alkylpolyglucoside sulfates and the like. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy sulfates), such as the sulfates or condensation products of ethylene oxide and nonyl phenol (which typically have 1 to 6 oxyethylene groups per molecule). .

[00146] Anionic sulfonate surfactants suitable for use in the present compositions also include alkyl sulfonates, primary and secondary linear and branched alkyl sulfonates, and aromatic sulfonates, with or without substituents.

[00147] Anionic carboxylate surfactants suitable for use in the present compositions include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), carboxylic acid esters (e.g., alkyl succinates), ether carboxylic acids, acids sulfonated fatty acids, such as oleic acid sulfonate, and the like. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxycarboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxylates). Secondary carboxylates useful in the present compositions include those containing a carboxyl moiety attached to a secondary carbon. The secondary carbon may be in a ring structure, for example, as in p-octyl benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. Secondary carboxylate surfactants typically do not contain ether bonds, ester bonds, and hydroxyl groups. Additionally, they typically lack nitrogen atoms in the head group (amphiphilic portion). Suitable secondary soap surfactants typically contain 11 to 13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acylamino acids (and salts) such as acylgluamates, acyl peptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyl taurates and methyl tauride fatty acid amides), and the like.

[00148] Suitable anionic surfactants include alkyl or alkylryl ethoxy carboxylates of the following formula: RO-(CH2CH2O)n(CH2)m-CO2X (3) where R is a C8 to C22 alkyl group or wherein R1 is a C4-C16 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, ammonia, or an amine salt, such as monoethanolamine, diethanolamine, or triethanolamine. In some embodiments, n is an integer from 4 to 10 and m is 1. In some embodiments, R is a C8-C16 alkyl group. In some embodiments, R is a C12-C14 alkyl group, n is 4, m is 1.

[00149] In other embodiments, R is and R1 is a C6-C12 alkyl group. In still other embodiments, R1 is a C9 alkyl group, n is 10 and m is 1.

[00150] Such alkyl and alkylaryl ethoxy carboxylates are commercially available. These ethoxy carboxylates are typically available as the acid forms, which can be readily converted to the anionic or salt form. Commercially available carboxylates include, Neodox 23-4, a C12-13 alkyl polyethoxy carboxylic acid (4) (Shell Chemical) and Emcol CNP-110, a C9 alkylaryl polyethoxy carboxylic acid (10) (Witco Chemical). Carboxylates are also available from Clariant, for example the product Sandopan® DTC, a C13 alkyl polyethoxy carboxylic acid (7).

CATIONIC SURFACTANTS

[00151] Surface active substances are classified as cationic if the charge on the hydrotropic portion of the molecule is positive. Surfactants in which the hydrotrope carries no charge unless the pH is lowered to near neutrality or lower, but which are then cationic (e.g., alkylamines), are also included in this group. In theory, cationic surfactants can be synthesized from any combination of elements containing an RnX+Y-- “onium” structure and could include compounds other than non-nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). . In practice, the cationic surfactant field is dominated by nitrogen-containing compounds, probably due to the fact that the synthetic routes to nitrogenous cations are simple and direct and provide high product yields, which can make them less expensive.

[00152] Cationic surfactants preferably include, but preferably refer to, compounds that contain at least one long carbon chain hydrophobic group and at least one positively charged nitrogen. The long carbon chain group can be attached directly to the nitrogen atom by simple substitution; or more preferably indirectly by a bridging functional group or groups in so-called interrupted alkylamines and starch amines. Such functional groups can make the molecule more hydrophilic and/or more dispersible in water, more easily solubilized in water by mixtures of cosurfactants and/or soluble in water. For high water solubility, additional primary, secondary or tertiary amino groups can be introduced or the amino nitrogen can be quaternized with low molecular weight alkyl groups. Furthermore, nitrogen may be a part of the branched or straight chain chemical moiety of varying degrees of unsaturation or of a saturated or unsaturated heterocyclic ring. Furthermore, cationic surfactants may contain complex bonds that have more than one cationic nitrogen atom.

[00153] Surfactant compounds classified as amine oxides, amphoteric and zwitterionic are themselves typically cationic in near-neutral to acidic pH solutions and may overlap surfactant classifications. Polyoxyethylated cationic surfactants generally behave as nonionic surfactants in alkaline solution and as cationic surfactants in acidic solution.

[00154] The simplest cationic amines, amine salts and quaternary ammonium compounds can be schematically drawn in this way: where R represents an alkyl chain, R', R'' and R''' can be either alkyl chains or aryl groups or hydrogen and X represents an anion. Amine salts and quaternary ammonium compounds are preferred for practical use in this invention because of their high degree of solubility in water.

[00155] Most large volume commercial cationic surfactants can be subdivided into four major classes and additional subgroups known to those skilled in the art and described in "Surfactant Encyclopedia", Cosmetics & Toiletries, Volume 104 (2) 86 to 96 (1989 ). The first class includes alkylamines and their salts. The second class includes the alkyl imidazolines. The third class includes ethoxylated amines. The fourth class includes quaternaries such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, tetraalkylammonium salts and the like. Cationic surfactants are known to have a variety of properties that may be beneficial in the present compositions. Such desirable properties may include detergency in compositions at or below neutral pH, antimicrobial efficacy, thickening or gelling in cooperation with other agents, and the like.

[00156] Cationic surfactants useful in the compositions of the present invention include those having the formula R1mR2xYLZ in which each R1 is an organic group that contains a straight or branched alkyl or alkenyl group optionally substituted by up to three phenyl or hydroxy groups and optionally interrupted by up to four of the following structures: or an isomer or mixture of these structures and containing from about 8 to 22 carbon atoms. The R1 groups may additionally contain up to 12 ethoxy groups. m is a number from 1 to 3. Preferably, not more than one R1 group in a molecule has 16 or more carbon atoms when m is 2 or more than 12 carbon atoms when m is 3. Each R2 is a group alkyl or hydroxyalkyl containing 1 to 4 carbon atoms or a benzyl group having no more than one R2 in a molecule that is benzyl and ex is a number from 0 to 11, preferably from 0 to 6. The remainder of any positions of carbon atom in group Y is filled with hydrogens.

[00157] Y is may be a group that includes, but is not limited to: or a mixture thereof. Preferably, L is 1 or 2, with the Y groups being separated by a chemical moiety selected from analogues of R1 and R2 (preferably, alkylene or alkenylene) that have from 1 to about 22 carbon atoms and two carbon single bonds. free when L is 2. Z is a water-soluble anion, such as a halide, sulfate, methyl sulfate, hydroxide or nitrate anion, in which chloride, bromide, iodide, sulfate or methyl sulfate anions are particularly preferred, in a number to generate electrical neutrality of the cationic component.

AMPHOTERIC SURFACTANTS

[00158] Amphoteric or ampholytic surfactants contain a basic hydrophilic group and an acid and an organic hydrophobic group. These ionic entities can be any of the anionic or cationic groups described herein for other types of surfactants. A basic nitrogen group and an acidic carboxylate group are the typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, sulfonate, sulfate, phosphonate, or phosphate provide the negative charge.

[00159] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical may be straight or branched chain and in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains as anionic water solubilizing group, e.g. carboxy, sulfo, sulfate, phosphate or phosphone. Amphoteric surfactants are subdivided into two main classes known to those skilled in the art and described in "Surfactant Encyclopedia" Cosmetics & Toiletries, Volume 104 (2) 69 to 71 (1989), which is incorporated herein by reference in its entirety. The first class includes acyl/dialkyl ethylenediamine derivatives (e.g., 2-alkyl hydroxyethyl imidazoline derivatives) and salts thereof. The second class includes N-alkylamino acids and their salts. Some amphoteric surfactants can be considered suitable for both classes.

[00160] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized by condensation and ring closure of a long-chain carboxylic acid (or a derivative) with dialkyl ethylenediamine. Commercial amphoteric surfactants are derived by subsequent hydrolysis and ring opening of imidazoline by alkylation - for example, with chloroacetic acid or ethyl acetate. During alkylation, one or two carboxyalkyl groups react to form a tertiary amine and an ether bond with different alkylating agents that produce different tertiary amines. Long-chain imidazole derivatives that have application in the present invention generally have the general formula: where R is an acyclic hydrophobic group containing about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion, usually sodium. Commercially prominent imidazoline-derived amphoterics that can be used in the present compositions include, for example: Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate, Cocoamphocarboxy-glycinate, Cocoamphocarboxy-glycinate, Cocoamphopropylsulfonate and Cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced at from fatty imidazolines in which the dicarboxylic acid functionality of amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

[00161] The carboxymethylated compounds (glycinates) described above in this document are often called betaines. Betaines are a special class of amphoterics discussed below in this document in the section entitled Zwitterionic surfactants.

[00162] Long-chain N-alkylmino acids are easily prepared by reacting RNH2, where R=C8-C18 straight or branched chain alkyl, fatty amines with halogenated carboxylic acids. Alkylation of the primary amino groups of an amino acid generates secondary and tertiary amines. Alkyl substituents may have additional amino groups that provide more than one reactive nitrogen center. Most commercial N-alkylmine acids are alkyl derivatives of beta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercial N-alkylmino ampholyte acids that have application in the present invention include alkyl beta-amino dipropionates, RN(C2H4COOM)2 and RNHC2H4COOM. In one embodiment, R may be an acyclic hydrophobic group containing from about 8 to about 18 carbon atoms, and M is a cation to neutralize the charge of the anion.

[00163] Suitable amphoteric surfactants include those derived from coconut products, such as coconut oil or coconut fatty acid. Additional suitable coconut-derived surfactants include, as part of their structure, an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, for example, glycine, or a combination thereof; and an aliphatic substituent of about 8 to 18 (e.g., 12) carbon atoms. This surfactant can also be considered an alkyl amphodicarboxylic acid. These amphoteric surfactants may include chemical structures represented as: C12-alkyl-C(O)-NH- CH2-CH2-N+(CH2-CH2-CO2Na)2-CH2-CH2-OH or C12-alkyl-C(O)- N(H)- CH2-CH2-N+(CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoampho dipropionate is a suitable amphoteric surfactant and is commercially available under the trade name Miranol™ FBS from Rhodia Inc., Cranbury, NJ. Another suitable coconut-derived amphoteric surfactant with the chemical name cocoampho disodium diacetate is marketed under the trade name Mirataine™ JCHA, also from Rhodia Inc., Cranbury, NJ.

[00164] A typical listing of amphoteric classes and species of these surfactants is provided in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are provided in "Surface Active Agents and detergents" (Volumes I and II by Schwartz, Perry and Berch). Each such reference is incorporated herein by reference in its entirety.

ZWITTERIONIC SURFACTANTS

[00165] Zwitterionic surfactants can be considered a subset of amphoteric surfactants and can include an anionic charge. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of secondary and tertiary heterocyclic amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, a zwitterionic surfactant includes a positively charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion; a negatively charged carboxyl group; and an alkyl group. Zwitterionics generally contain cationic and anionic groups that ionize to an almost equal degree in the isoelectric region of the molecule and that can develop strong "internal salt" attraction between the positive-negative charge centers. Examples of such synthetic zwitterionic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic radicals may be straight or branched chain and in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains as solubilizing group in anionic water, e.g. carboxy, sulfonate, sulfate, phosphate or phosphonate.

[00166] Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use in this document. A general formula for these compounds is: wherein R1 contains an alkyl, alkenyl radical or a hydroxyalkyl radical of 8 to 18 carbon atoms that has 0 to 10 chemical moieties of ethylene oxide and 0 to 1 chemical moiety of glyceryl; Y is selected from the group consisting of nitrogen, phosphorus and sulfur atoms; R2 is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R3 is an alkylene or hydroxy alkylene or hydroxy alkylene of 1 to 4 carbon atoms and Z is a radical selected from the group that consists of carboxylate, sulfonate, sulfate, phosphonate and phosphate groups.

[00167] Examples of zwitterionic surfactants with the structures listed above include: 4-[N, N-di(2-hydroxyethyl)-N-octadecylammonium]-butane-1-carboxylate; 5-[S-3-hydroxypropyl-S-hexadecylsulfonium]-3-hydroxypentane-1-sulfate; 3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonium]-2-hydroxypropane-1-phosphate; 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate; 3-(N,N-dimethyl-N-hexadecylammonium)-propane-1-sulfonate; 3-(N,N-dimethyl-N-hexadecylammonium)-2-hydroxy-propane-1-sulfonate; 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonium]-butane-1-carboxylate; 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonium ]-propane-1-phosphate; 3-[P, P-dimethyl-P-dodecylphosphonium]-propane-1-phosphonate; -pentane-1-sulfate. The alkyl groups contained in said detergent surfactants can be linear or branched and saturated or unsaturated.

[00168] The zwitterionic surfactant suitable for use in the present compositions includes a betaine of the general structure:

[00169] These betaine surfactants typically do not exhibit strong cationic or anionic characters at extreme pH nor do they show reduced solubility in water in their isoelectric range. Unlike "external" quaternary ammonium salts, betaines are anionic compatible. Examples of suitable betaines include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethylbetaine; 4-C14-16 acylmethylamidodiethylammonium-1-carboxybutane; C16-18 acylamidodimethylbetaine; C12-16 acylamidopentanedethylbetaine; and C12-16 acylmethylamidodimethylbetaine.

[00170] Sultaines useful in the present invention include those compounds having the formula (R(R1)2 N+ R2SO3-, in which R is a C6-C18 hydrocarbyl group, each R1 is typically independently C1-C3 alkyl, e.g. methyl and R2 is a C1-C6 hydrocarbyl group, for example, a C1-C3 alkylene or hydroxyalkylene group.

[00171] A typical listing of zwitterionic classes and species of these surfactants is provided in U.S. Patent No. 3,929,678, issued to Laughlin and Heuring on December 30, 1975. Additional examples are provided in "Surface Active Agents and detergents" (Volumes I and II by Schwartz, Perry and Berch). Each such reference is incorporated herein in its entirety.

METHODS OF MANUFACTURING CLEANING COMPOSITIONS

[00172] The solidified surfactant compositions of the invention can be included in various cleaning compositions. Preferably, the cleaning compositions are solid compositions. Suitable solid cleaning compositions include, but are not limited to, granular and granulated solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block composition, pressed solid compositions, and the like. Preferably, the cleaning compositions are pressed solids.

[00173] Solid particle cleaning compositions can be made simply by mixing the dry solid ingredients formed according to the invention in appropriate proportions or by agglomerating the materials in appropriate agglomeration systems. Pelleted materials can be manufactured by compressing the granular materials or solid agglomerates in appropriate pelletizing equipment to result in pelletized materials of suitable size. Solid block and molten solid block materials can be produced by introducing into a container a pre-hardened block of material or a molten liquid that hardens into a solid block within a container. Preferred containers include disposable plastic containers or water-soluble film containers. Other packaging suitable for compounding includes flexible bags, bundles, shrink wrap, and water-soluble film such as polyvinyl alcohol.

[00174] Solid detergent compositions can be formed using a batch or continuous mixing system. In an exemplary embodiment, a single or twin screw extruder may be used to combine and mix one or more component agents under high shear to form a homogeneous mixture. In some embodiments, the processing temperature is equal to or lower than the melting temperature of the components. The processed mixture may be dispensed from the mixer by forming, melting or other suitable means, whereby the cleaning composition hardens into a solid form. The matrix structure can be characterized according to its hardness, melting point, material distribution, crystalline structure and other similar properties according to methods known in the art. In general, a solid composition processed in accordance with the method of the invention is substantially homogeneous with respect to the distribution of ingredients throughout its mass and is stable in size.

[00175] In an extrusion process, liquid and solid components are introduced into the final mixing system and are continuously mixed until the components form a substantially homogeneous semisolid mixture in which the components are distributed throughout its 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 an exemplary embodiment, the formed composition begins to harden between approximately 1 minute and approximately 3 hours. Particularly, the formed composition begins to harden between approximately 1 minute and approximately 2 hours. More particularly, the formed composition begins to harden between approximately 1 minute and approximately 20 minutes.

[00176] In a fusion process, liquid and solid components are introduced into the final mixing system and are continuously mixed until the components form a substantially homogeneous liquid mixture in which the components are distributed throughout its mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once mixing is complete, the product is transferred to a packaging container where solidification occurs. In an exemplary embodiment, the molten composition begins to harden between approximately 1 minute and approximately 3 hours. In particular, the molten composition begins to harden between approximately 1 minute and approximately 2 hours. More particularly, the molten composition begins to harden between approximately 1 minute and approximately 20 minutes.

[00177] In a pressed solid process, a fluid solid, such as granular solids or other particulate solids including binding agents, are combined under pressure. In a pressed solid process, the flowable solids of the compositions are placed in a form (e.g., a mold or container). The method may include gently pressing the flowable solid into the form to produce the solid cleaning composition. Pressure can be applied by a block machine or a rotary press, or something similar. Pressure can be applied at about 0.01 to about 20.68 MPa (1 to about 3,000 psi), about 0.03 to about 17.24 MPa (5 to about 2,500 psi), or about 0.07 to about 13.79 MPa (10 psi to about 2,000 psi). As used herein, the term “MPa (psi)” or “megapascal (pounds per square inch)” refers to the actual pressure applied to the flowable solid that is pressed and does not refer to the gauge or hydraulic pressure measured at a point in the device that creates pressure. The method may additionally include a curing step to produce the solid cleaning composition. As referred to herein, an uncured composition that includes the flowable solid is compressed to provide sufficient surface contact between the particles constituting the flowable solid that the uncured composition will solidify into a composition of stable solid cleaning. A sufficient amount of particles (e.g., granules) in contact with each other provides effective binding of particles to each other to produce a stable solid composition. Inclusion of a curing step may include allowing the pressed solid to solidify for a period of time, such as a few hours or about 1 day (or longer). In further aspects, the methods may include vibrating the solid with the ability to flow into the form or mold, such as the methods disclosed in U.S. Patent No. 8,889,048, which is incorporated herein by reference in its entirety.

[00178] The use of pressed solids provides numerous benefits over conventional solid block or tablet compositions that require high pressure in a tablet press or foundry that requires the melting of a composition consuming significant amounts of energy and/or by extrusion that requires expensive equipment and advanced technical knowledge. Pressed solids overcome these various limitations of other solid formulations for which there is a need to produce solid cleaning compositions. Furthermore, pressed solid compositions maintain their shape under conditions in which the composition may be stored or handled.

[00179] By the term "solid", it is meant that the hardened composition will not flow and will substantially maintain its shape under moderate tension or pressure or mere gravity. A solid may be in various forms, such as a powder, a flake, a granule, a pellet, a tablet, a lozenge, a disk, a briquette, a brick, a solid block, a unit dose, or other solid form known to people skilled in the technique. The degree of hardness of the solid cast composition and/or a solid pressed composition may vary from a solid cast product that is relatively dense and hard, for example, like concrete, to a consistency characterized as being a hardened paste. Furthermore, the term "solid" refers to the state of the composition under the expected conditions of storage and use of the solid cleaning composition. Generally, the cleaning composition is expected to remain in solid form when exposed to temperatures of up to approximately 37.78 °C (100 °F) and particularly up to approximately 48.89 °C (120 °F).

[00180] The resulting solid composition can take forms that include, but are not limited to: a pellet, block, tablet, powder, granule, extruded, molded or formed solid flakes; or the solid formed may thereafter be ground or formed into a powder, granule or flake. In an exemplary embodiment, extruded pellet materials formed by the solidification matrix have a weight of between approximately 50 grams and approximately 250 grams, extruded solids formed by the composition have a weight of approximately 100 grams or more, and solid block detergents formed by the composition have a mass between approximately 1 and approximately 10 kilograms. Solid compositions provide a stabilized source of functional materials. In some embodiments, the solid composition may be dissolved, for example, in an aqueous medium or other medium, to create a concentrated solution and/or use. The solution can be directed to a storage reservoir for later use and/or dilution or can be applied directly to a point of use.

[00181] The following patents disclose various combinations of solidifying, binding and/or hardening agents that can be used in the solid compositions of the present invention. The following U.S. patents are incorporated herein by reference: U.S. Patent No. 7,153,820; 7,094,746; 7,087,569; 7,037,886; 6,831,054; 6,730,653; 6,660,707; 6,653,266; 6,583,094; 6,410,495; 6,258,765; 6,177,392; 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.

[00182] Liquid compositions can typically be made by forming the ingredients in a liquid aqueous system or in an aqueous liquid solvent. Such systems are typically produced by dissolving or suspending the active ingredients in water or a compatible solvent and then diluting the product to an appropriate concentration to form a concentrate or solution for use thereof. Gelled compositions can be produced in a similar manner by dissolving or suspending the active ingredients in an aqueous system, compatible aqueous liquid or in a mixed aqueous organic system, including a gelling agent in an appropriate concentration. All publications and patent applications in the present specification are indicative of the level of common skill in the art to which this invention belongs. All publications and patent applications are incorporated herein by reference to the same extent as if each individual publication or patent application were specifically and individually indicated as incorporated by reference. EXAMPLES

[00183] Embodiments of the present invention are further defined in the following non-limiting Examples. It should be understood that these examples, although they indicate certain embodiments of the invention, are provided by way of illustration only. From the above discussion and these Examples, a person skilled in the art can ascertain the essential features of the present invention and, without departing from the spirit and scope thereof, can apply various changes and modifications of the embodiments of the invention to adapt it to various uses and conditions. Thus, various modifications of embodiments of the invention, in addition to those shown and described herein, will be apparent to persons skilled in the art from the foregoing description. Such modifications should also fall within the scope of the attached claims.

[00184] The materials used in the following examples are provided here: Ammonyx LO (30%), a lauramine oxide available from Stepan Co.

[00185] Amphosol CG, a cocamidopropyl betaine available from Stepan Co.

[00186] Barlox 12, a cocoamine oxide available from Lonza.

[00187] Mackam CB35, a cocobetaine available from Solvay.

[00188] Mackam LSB50, a lauramidopropyl hydroxysultaine available from Rhodia.

[00189] Mackam 50SB, a cocamidopropyl hydroxysultaine available from Rhodia.

[00190] Additional ingredients used available from various commercial sources include: sodium alpha olefin sulfate, sodium chloride, sodium sulfate, sodium acetate and magnesium sulfate.

EXAMPLE 1 SOLIDIFIED LIQUID SURFACTANTS WITH A CARRIER

[00191] Examples of liquid amine oxide surfactants, betaine and sultaine were solidified with various exemplary solid carriers in accordance with the methods described herein. These formulations are shown in Table 4. TABLE 4

[00192] Table 4 demonstrates that liquid surfactants can be solidified with a carrier.

[00193] The features disclosed in the preceding description or in the following claims, expressed in their specific forms or in terms of a means for performing the disclosed function or a method or process for achieving the disclosed result, as appropriate, may, separately or in any combination of such characteristics, be used to carry out the invention in various forms thereof. With the invention thus described, it will be obvious that it can be varied in various ways. Such variations should not be considered as a departure from the spirit and scope of the invention and all such modifications should be included within the scope of the following claims. The above specification provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention is described in the claims.

Claims (20)

1. Method for preparing a solidified surfactant composition, characterized in that it comprises: adding a liquid surfactant comprising one or more of an amine oxide, a betaine, and a sultain and a solid carrier comprising an anionic surfactant, an organic salt , an inorganic salt, or a combination thereof for a drying device, in which the carrier and liquid surfactant are in a ratio of between 5:1 to 1:30 active; drying the liquid surfactant and carrier to form a solidified surfactant composition, wherein the solidified surfactant composition is a free-flowing granule; wherein the liquid surfactant is solidified in the solidified surfactant composition and wherein the solidified surfactant composition has less than 5% by weight water; wherein the anionic surfactant is an alpha olefin sulfonate, a linear alkyl sulfonate, a sodium lauryl sulfate, a sodium alkyl sulfate or a combination thereof; wherein the organic salt is an alkali metal carbonate, an alkaline earth metal carbonate, an alkali salt acetate, an alkaline earth salt acetate, or a combination thereof; wherein the inorganic salt is an alkali metal sulfate, an alkaline earth metal sulfate, or a combination thereof; and wherein the solidified surfactant composition is free of a binder. 2. The solidified surfactant method of claim 1, wherein the drying device is a continuous tunnel dryer, rotary dryer, vacuum dryer, tower constrictor, vibrating conveyor constrictor, drum dryer, dryer screw conveyor, fluidized bed, spouted bed, pneumatic conveyor, spray dryer or a combination thereof. 3. Method according to claim 1 or 2, characterized by the fact that there are at least two drying devices placed in series or in parallel. 4. Method according to any one of claims 1 to 3, characterized in that the drying process is carried out in a batch system or a continuous system. 5. Method according to any one of claims 1 to 4, characterized in that the drying device comprises a fluidized bed; wherein the fluidized bed has a liquid flow rate between 0.001 to 0.000008 kg/s (0.001 and 0.15 lb/min) pounds of bed material an atomizing air pressure between 0 to 0.69 MPa (0 psig and 100 psig) per nozzle, and an air speed between 0.3048 meters per second (1 foot per second) and 30.48 meters per second (100 feet per second). 6. Method according to claim 5, characterized by the fact that the method employs an agglomeration process. 7. Method according to claim 5, characterized by the fact that the method employs a granulation process. 8. Method according to any one of claims 1 to 7 characterized by the fact that the carrier and the surfactant in the solidified surfactant composition are in a ratio of between 2:1 and 1:25 active. 9. Method according to any one of claims 1 to 8 characterized by the fact that the liquid surfactant is one or more of the following: dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecylbutylamine oxide, octadecylbutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy oxide -1-hydroxypropylamine, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide. 10. Method according to any one of claims 1 to 8 characterized by the fact that the liquid surfactant is one or more of the following: coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine, C12-14 acylamidopropylbetaine, C8-14 acylamidohexyldiethyl betaine, C16-18 acylamidodimethylbetaine, C12-16 acylamidopentanedethylbetaine, C12-16 acylmethylamidodimethylbetaine or a combination thereof. 11. Method according to any one of claims 1 to 8 characterized by the fact that the liquid surfactant is a compound having the formula (R(R1)2 N+ R2SO3-, where R is a C6—C18 hydrocarbyl group, wherein R1 is a C1-C3 alkyl and wherein R2 is a C1-C6 hydrocarbyl group. 12. Method according to any one of claims 1 to 11 characterized by the fact that the carrier is an alpha olefin sulfonate, a linear alkyl sulfonate, a sodium lauryl sulfonate, a sodium alkyl sulfate or a combination thereof. 13. Method according to any one of claims 1 to 11 characterized by the fact that the carrier is an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal acetate, an alkaline earth metal acetate, a sulfate of alkali metal, an alkaline earth metal sulfate, sodium chloride or a combination thereof. 14. Method according to any one of claims 1 to 11 characterized by the fact that the carrier is sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium acetate or a combination thereof . 15. Method according to any one of claims 1 to 14 characterized by the fact that the carrier is a powder. 16. Method according to any one of claims 1 to 15 characterized by the fact that the carrier has a water solubility of 0.2 g/L or more at 20 ° C. 17. Method according to any one of claims 1 to 16 characterized by the fact that the solidified surfactant composition has less than 5% by weight of water. 18. Method according to any one of claims 1 to 17 characterized by the fact that the solidified surfactant composition contains at least 10% by weight of active surfactants. 19. Method according to any one of claims 1 to 18 characterized by the fact that the solidified surfactant composition contains at least 25% by weight of active surfactants. 20. Method according to any one of claims 1 to 19 characterized by the fact that the solidified surfactant composition contains at least 50% by weight of active surfactants.