Solidification of liquid amine oxides, betaines, and / or sultaine surfactants using a carrier.

Abstract

To provide techniques for solidification of liquid amine oxide, betaine, and / or sultaine surfactants with a carrier to form a solidified surfactant composition.SOLUTION: In particular, the invention relates to solidification of liquid surfactants utilizing one or more drying devices, wherein the feed composition contains at least one liquid surfactant and a carrier to form a solidified surfactant composition. The solidified surfactant compositions can be useful in various cleaning compositions.SELECTED DRAWING: None

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority under § 119 of the United States Patent Act to Provisional Application U.S. No. 62 / 622,403 filed January 26, 2018, which, without limitation, includes tables, examples, and claims in their entirety and is incorporated herein by reference.

[0002] This application is further related to Provisional Application U.S. No. 62 / 622,356 filed on 26 January 2018 and U.S. Patent Application No. 16 / 259,015 [Agent Reference Number P12085US01] filed on 28 January 2019, both of which are titled “SOLIDIFYING LIQUID AMINE OXIDE, BETAINE, AND / OR SULTAINE SURFACTANTS WITH A BINDER AND OPTIONAL CARRIER” and are incorporated herein by reference in their entirety, including but not limited to tables, examples, and claims.

[0003] This disclosure relates to the solidification of liquid amine oxide, sultaine, and / or betaine surfactants using a carrier. Specifically, the present invention relates to the solidification of liquid amine oxide, betaine, and sultaine surfactants using a drying device(s), wherein the supply composition contains at least one surfactant and a carrier. [Background technology]

[0004] Many amine oxide, betaine, and sultaine surfactants are available only in liquid form. For the preparation of solid cleaning compositions, it is desirable that many such surfactants be supplied in solid form. Since many of these surfactants are only available in liquid form, they cannot be easily incorporated into solid formulations, or the active concentrations that can be included in formulations are limited. [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Attempts have been made in the past to include certain liquid surfactants in solid form, however, these have largely been unsuccessful for a variety of reasons. It has been impossible to convert liquid amine oxides, betaines, and sultaines into solid surfactants while maintaining their efficacy. Such conversion results in less desirable performance in solid cleaning compositions. Another problem is that solidified amine oxide, betaine, and sultaine surfactants are often sticky, and therefore suffer from caking, compression, and aggregation, making packaging, storage, proper dosing, and dispersion difficult during the manufacturing process. In addition, several methods for solidifying liquid amine oxides, betaine, and sultaine require substantial amounts of binders and / or carriers, thereby reducing the active concentration of the surfactant in the final product. Other efforts to solidify liquid surfactants involve the use of poorly water-soluble compounds, such as fumed silica, which have a solubility of approximately 0.2 g / L or less at 20°C, which is problematic in both formulation and the final end-use, typically in water. Therefore, improvement is needed.

[0006] Therefore, the claimed object of the present invention is to develop solidified amine oxide, betaine, and / or sultaine compositions from liquid amine oxide, betaine, and / or sultaine, as well as methods for producing them.

[0007] A further object of the present invention is to provide a free-flowing solidified amine oxide, betaine, and / or sultaine composition.

[0008] A further object of the present invention is to provide a cleaning composition comprising a solidified amine oxide, betaine, and / or sultaine composition.

[0009] Other objects, advantages, and features of the present invention will become apparent from the following specification in conjunction with the accompanying drawings. [Modes for carrying out the invention]

[0010] This disclosure relates to solidifying liquid amine oxide, betaine, and / or sultaine surfactants on a carrier to form solidified surfactant compositions. Solidified surfactant compositions have many advantages over existing formulations, including those containing the same surfactants as surfactants that are in liquid form but whose use in certain types of solid formulations is hindered or obstructed, including but not limited to pressed solids. For example, many amine oxides, betaines, and sultaines are found in liquid form, and there are currently limitations on commercially available solid active materials. The conversion of liquid surfactants to solidified surfactant compositions allows for their use at higher concentrations in solid compositions and expands their utility in solid formulations. Unexpectedly, the solidification of liquid amine oxide, betaine, and sultaine surfactants in solidified surfactant compositions has been found to provide substantially similar performance with respect to foaming and stain-removing properties, which are indicators of good overall surfactant performance. This demonstrates the utility of solidified surfactant compositions in solid cleaning compositions, including but not limited to pressed solids. In addition, as described herein, solidified liquid surfactant compositions have been found to be able to be prepared on a carrier alone, without the need for a binder. This allows for an increase in the concentration of the liquid surfactant.

[0011] Embodiments may vary and are not limited to specific methods and / or products as understood by those skilled in the art. It should be further understood that all technical terms used herein are solely for the purpose of describing specific embodiments and are not intended to be limiting in any form or scope. For example, as used herein and in the appended claims, the singular forms "a," "an," and "the" may refer to multiple subjects unless otherwise clearly indicated. Furthermore, all units, prefixes, and symbols may be represented in their SI certified form.

[0012] Numerical ranges described herein include the digit defining the range and each integer within the defined range. Throughout this disclosure, various aspects of the invention are presented in range form. It should be understood that descriptions in range form are merely for convenience and brevity and should not be interpreted as a rigid limitation to the scope of the invention. Accordingly, a description of a range should be considered to specifically disclose all possible subranges, fractions, and individual digits within that range. For example, a description of a range such as 1–6 should be considered to specifically disclose subranges such as 1–3, 1–4, 1–5, 2–4, 2–6, 3–6, etc., as well as individual digits within that range, e.g., 1, 2, 3, 4, 5, and 6, and decimals and fractions, e.g., 1.2, 3.8, 1 and 1 / 2, and 4 and 3 / 4. This applies regardless of the breadth of the range.

[0013] Certain terms are defined first so that the present invention may be more easily understood. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to whom embodiments of the present invention relate. Many methods and materials similar, modified, or equivalent to those described herein can be used in carrying out embodiments of the present invention without excessive experimentation, and preferred materials and methods are described herein. In describing embodiments of the present invention and in claiming them, the following technical terms are used according to the definitions set forth below.

[0014] As used herein, the term “approximately” refers to variations of a quantity that can be made, 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, considering the handling procedures of solids and liquids used in the real world, there are likely to be certain careless errors and variations resulting from differences in the manufacture, source, or purity of the components used to prepare a composition or to carry out a method, etc. The term “approximately” also encompasses different quantities resulting from different equilibrium conditions for a composition arising from a particular initial mixture. The term “approximately” also encompasses variations of these. Whether modified by the term “approximately” or not, the claims include equivalents to that quantity.

[0015] The terms “active substance,” “percent active substance,” “weight percent active substance,” or “active substance concentration” are used interchangeably herein and refer to the concentration of the cleaning component expressed as a percentage after subtracting inert components such as water or salt.

[0016] As used herein, the terms "alkyl" or "alkyl group" refer to saturated hydrocarbons having one or more carbon atoms, and include linear alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cyclic alkyl groups (or "cycloalkyl," "alicyclic," or "carbocyclic" groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

[0017] Unless otherwise specified, the term “alkyl” includes both “unsubstituted alkyl” and “substituted alkyl.” As used herein, the term “substituted alkyl” refers to an alkyl group having substituents that substitute one or more hydrogens of one or more carbons in a hydrocarbon skeleton. Such substituents include, for example, alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinato, shea The following groups may be present: no, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkylaryl, or aromatic (including heteroaromatic) groups.

[0018] In some embodiments, the substituted alkyl group may include a heterocyclic group. As used herein, the term “heterocyclic group” includes a ring-closed structure similar to a carbocyclic group in which one or more carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur, or oxygen. The heterocyclic group may be saturated or unsaturated. Examples of heterocyclic groups, but not limited to these, include aziridine, ethylene oxide (epoxide, oxirane), thiirane (episulfide), dioxirane, azetidine, oxetane, thiethane, dioxetane, dithiethane, dithiethone, azolidine, pyrrolidine, pyrroline, oxolane, dihydrofuran, and furan.

[0019] A "redeposition inhibitor" refers to a compound that helps remain suspended in water instead of redepositing on the object being cleaned. Redeposition inhibitors are useful in this invention to help reduce the redeposit of removed dirt on the surface being cleaned.

[0020] As used herein, the term “cleaning” refers to methods used to promote or assist in the removal of dirt, bleaching, reduction of microbial communities, and any combination thereof.

[0021] The term “laundry” refers to items or articles that are washed in a washing machine. Generally, laundry refers to any item or article made from, or containing, woven materials, fabrics, nonwovens, and knitted fabrics. Woven materials may include natural or synthetic fibers such as silk fibers, linen fibers, cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylic fibers, acetate fibers, and blends thereof, including cotton and polyester blends. Fibers may be treated or untreated. An example of treated fibers is flame-retardant treated fibers. The term “linen” should be understood as often being used to describe specific types of laundry items, including bed sheets, pillowcases, towels, table linens, tablecloths, bar mops, and uniforms. The present invention additionally provides compositions and methods for treating non-laundry items and surfaces, including hard surfaces such as dishes, glass, and other products.

[0022] As used herein, the term “polymer” generally includes, but is not limited to, homopolymers, copolymers, terpolymers such as block, graft, random, and alternating copolymers, and higher-order “x”mers, and further includes their derivatives, combinations, and blends. Furthermore, unless otherwise specifically limited, the term “polymer” includes, but is not limited to, all possible isomeric configurations of a molecule, including isotactic, syndiotactic, and random symmetry, and combinations thereof. Furthermore, unless otherwise specifically limited, the term “polymer” includes all possible geometric configurations of a molecule.

[0023] As used herein, the terms “dirt” or “stain” refer to non-polar oily substances which may or may not include certain substances such as mineral clay, sand, natural minerals, carbon black, graphite, kaolin, and environmental dust.

[0024] As used herein, the term “substantially absent” means a composition that either completely lacks the component or contains such a small amount of the component that it does not affect the performance of the composition. The component may be present as an impurity or contaminant and must be less than 0.5% by weight. In another embodiment, the amount of the component is less than 0.1% by weight, and in yet another embodiment, the amount of the component is less than 0.01% by weight.

[0025] The term "threshold agent" refers to a compound that inhibits the crystallization of hard water ions originating from a solution, but does not require the formation of a specific complex with those hard water ions. Examples of threshold agents, though not limited to them, include polyacrylates, polymethacrylates, and olefin / maleic acid copolymers.

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

[0027] As used herein, the terms “water-soluble” and “water-miscible” mean that a component (e.g., a carrier or solvent) is soluble or dispersible in water at a concentration of about 0.2 g / L, preferably about 1 g / L or more, more preferably 10 g / L or more, and most preferably about 50 g / L or more, at about 20°C.

[0028] The terms "weight percent," "wt-%," "percent by weight," and "% by weight," and their variations, as used herein, refer to the concentration of a substance obtained by dividing its weight by the total weight of the composition and multiplying by 100. As used herein, "percent," "%," etc., are intended to be synonymous with "weight percent," "wt-%," etc.

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

[0030] Method for solidifying surfactants Drying as a process function is used to remove liquid from a liquid-solid system to produce a dry solid. The liquid removed is generally water, but other organic liquids may be removed through the drying process. The selection of drying devices and / or configurations depends on the state of the feed stream, the desired form of the product, and the temperature sensitivity of the feed, in addition to general considerations of fluid dynamics, heat and mass transfer, chemical reaction rates, and gas-solid interactions. The selection of equipment depends on the material properties, the drying characteristics of the material, the product quality, and the recovery of dust / solvents.

[0031] Drying devices are typically classified into three types. Firstly, the operating mode of the drying device / system is classified into batch drying or continuous drying. Generally, batch drying is employed when the required production rate is 500 pounds or less of dried product per hour. Continuous drying is preferred when more than 500 pounds of dried product per hour is required. Secondly, drying devices are classified by the mode of heat transfer for moisture removal. Direct heating dryers (also known as adiabatic or convection dryers) bring the material into contact with a hot gas to evaporate and remove moisture. When used in continuous operation mode, the airflow can be designed to be counterflowing, parallel, or direct alternating current relative to the material. Indirect heating dryers (also known as non-adiabatic dryers) provide heat through conduction and / or radiation from a hot surface. These dryers can be operated under vacuum to lower the temperature at which moisture evaporates. Thirdly, dryers can also be classified based on the degree of agitation of the material. The feed can be either static or fluidized. A good drying device provides a transition zone at the inlet to atomize the fluid or pre-mix the fluid with the recycled solid to improve flow. When heat-sensitive solids are present, a dryer with precise temperature control and / or vacuum conditions may be preferable. As those skilled in the art will understand, selecting a suitable drying device for the solidification of surfactants and other useful detergent chemicals requires careful consideration and weighing of process variables.

[0032] In one embodiment of the present invention, the drying device is, for example, a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower shrinker, a vibrating conveyor shrinker, a drum dryer, a screw conveyor dryer, a fluidized bed, a jet bed, a pneumatic conveyor, a spray dryer, or a combination thereof. The drying devices may be arranged in parallel or in series, and one series may contain one or more drying devices. A preferred drying device is a fluidized bed (also referred to as a fluid bed).

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

[0034] In a preferred embodiment of the present invention, the claimed method provides a dry composition comprising at least about 10% by weight, preferably at least about 25% by weight, preferably at least 40% by weight, and more preferably at least 50% by weight of an active surfactant.

[0035] fluidized bed In a preferred embodiment of the present invention, the solidification of liquid amine oxides, betaines, and sultaine surfactants is carried out using a fluidized bed, in which freely flowing wet particles are continuously dried through contact with a hot gas. Although not intended to be limited by any particular configuration or theory of the present invention, the fluidized bed dryer comprises a fluidization chamber in which wet particles are supplied and fluidized by a hot gas blown through a heater into a plenum chamber below the floor, and then passed through a distribution plate that fluidizes the particles above.

[0036] The fluidized bed can be used with a coagulation process that includes a solid binder and / or carrier, or a granulation process that includes only liquid components. In the coagulation process, a powder feed is used to coat the dry material. The granulation process differs from the coagulation process in that it does not require a powder feed; rather, the granulation process is carried out by continuously spraying a liquid coating onto a seed material from the process, continuously coating and drying the liquid to form solid granules of the desired size. Furthermore, it has been found that this process can be carried out without seed material, or even without material in the bed in practice. In one embodiment, where no material is present in the bed at the start of the process, the process may begin by granulating to form seed material, and then be continued by coagulation or further granulation.

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

[0038] Preferably, the liquid flow rate is about 0.001 lb / min / lb of bed material to about 0.15 lb / min / lb of bed material, more preferably about 0.01 lb / min / lb of bed material to about 0.10 lb / min / lb of bed material. In one embodiment where there is no seed material and the process is started without starting material in the bed, it should be understood that the liquid flow rate per minute per mass of bed material is initially uncalcible because there is zero starting bed material. However, since material is added to the bed for the initial granulation, bed material is present almost immediately after the process starts. In such an embodiment, the ratio of liquid added to the bed material is initially higher due to the small amount of bed material. For example, a preferred liquid flow rate when there is no starting material in the bed is about 0.1 lb / min / lb of bed material to about 2 lb / min / lb of bed material, more preferably about 0.5 lb / min / lb of bed material to about 1.5 lb / min / lb of bed material.

[0039] The atomizing air pressure in the fluidized bed may be about 0 to about 100 psig per nozzle, preferably about 1 to about 75 psig per nozzle, and more preferably about 10 to about 60 psig per nozzle.

[0040] spray drying In a preferred embodiment of the present invention, the solidification of liquid amine oxides, betaines, and sultaine surfactants is carried out using a spray dryer. The spray dryer is suitable for slurry or solution feeds and provides desirable evaporation for heat-sensitive materials and lightweight, porous products. In the configuration of the spray dryer, it may be necessary to consider the pressure effect on the liquid feed and the solid product to ensure drying without damaging the product. Generally, the liquid or slurry is fed into the process unit of the dryer and then sprayed as fine droplets into a high-temperature airflow. Therefore, the feed composition must be able to withstand the pressure required for droplet formation. Upon entering the spray dryer, evaporation of the liquid occurs rapidly, while the product temperature remains relatively low. Process selection and design also require consideration of gas-solid interactions. Specifically, the inlet and outlet conditions of the solid, as well as the flow rate and residence time, should be designed considering diffusivity and heat transfer coefficient.

[0041] In one embodiment of the present invention, the inlet temperature of the inlet supply is in the range of about 20°C to about 250°C, preferably about 100°C to about 250°C, and more preferably about 150°C to about 200°C. In a further embodiment of the present invention, the outlet temperature, aspirator, and pump speed depend on the decomposition of the surfactant while inside the spray dryer.

[0042] The outlet temperature can vary based on the decomposition temperature of the components in the solidified surfactant composition. Therefore, in certain embodiments, the temperature may be higher or lower than that described herein. However, in one embodiment of the present invention, the outlet temperature is less than about 150°C, more preferably about 0°C to about 120°C, and most preferably about 20°C to about 100°C.

[0043] Solidifying surfactant composition Many amine oxide, betaine, and sultaine surfactants are available primarily in liquid form. Many such surfactants are preferable to be provided in solid form. One embodiment of the present invention is found in a solidified amine oxide, betaine, and / or sultaine surfactant composition. Another embodiment of the present invention is found in a method for preparing a solidified amine oxide, betaine, and sultaine surfactant composition. The solidified surfactant composition comprises a liquid amine oxide, betaine, and / or sultaine surfactant, and a carrier, as well as optionally, a co-surfactant, preferably in solid form. Depending on the desired properties of the solidified surfactant composition, additional components may be present.

[0044] In one aspect of the present invention, the carrier is added to a drying device together with the carrier to form a solidified surfactant composition. The liquid composition supplied to the selected drying device(s) of the present invention comprises at least one liquid surfactant and a carrier. In one preferred embodiment, the solidified surfactant composition is substantially free of binders, preferably less than about 1% by weight of a binder, more preferably less than about 0.5% by weight of a binder, even more preferably less than about 0.1% by weight of a binder, and most preferably free of binders.

[0045] The solidifying surfactant composition is preferably in powder form. Preferred powder forms include, but are not limited to, agglomerated solids and granulated solids. Therefore, in some embodiments, the solidifying surfactant composition is an agglomerated solid or a granulated solid.

[0046] Carrier The solidifying surfactant composition may contain a carrier. Preferably, the carrier is solid at room temperature. In embodiments employing a granulation process, the carrier may be in liquid form, and therefore in a dissolved form. Suitable solid carriers include, but are not limited to, powder, granule, bead, and flake forms. Suitable carriers include, but are not limited to, anionic surfactants, organic salts, and inorganic salts. Preferably, the carrier is water-soluble. In the most preferred embodiment, the carrier has a water solubility of about 0.2 g / L or more at 20°C. The carrier can be added to a liquid anionic surfactant alone or together with a binder to form the solidifying surfactant composition.

[0047] Preferred anionic surfactants include, but are not limited to, sulfonate surfactants, sulfate surfactants, and combinations thereof. In one preferred embodiment, the anionic surfactant support is solid. Most preferred anionic surfactants include, but are not limited to, alpha-olefin sulfonates, linear alkyl sulfonates, sodium lauryl sulfate, sodium alkyl sulfate, and combinations thereof.

[0048] Preferred organic salts include, but are not limited to, alkali carbonates and alkali metal carbonates (such as sodium carbonate and magnesium carbonate), alkali acetates and alkali metal acetates (such as sodium acetate and magnesium acetate), and combinations thereof.

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

[0050] A solidified surfactant product can be achieved by adding a carrier and a liquid surfactant in suitable amounts to a drying device. The amount of each component may depend on the specific liquid surfactant to be solidified, the carrier used, and any other optional components that may also be included in the solidified surfactant product. Preferably, the carrier and surfactant have an active substance ratio of about 5:1 to about 1:30, or about 2:1 to about 1:30, or about 1:1 to about 1:25, or about 1:1 to 1:20.

[0051] One of the ultimate goals of the present invention is to enable the incorporation of liquid surfactants into solid cleaning compositions in solid form; therefore, it is preferable that the surfactant in the solidified surfactant composition has a high concentration or ratio relative to the carrier and other components. However, this is limited by the desired physical characteristics of the solidified surfactant composition. For example, in one preferred embodiment of the present invention, the surfactant is solidified granules, not a paste. In another preferred embodiment of the present invention, the solidified surfactant compositions have reduced tackiness or are not tacky, so that they are free-flowing and do not caking, and do not aggregate or caking during storage.

[0052] Liquid surfactant Many surfactants are available primarily in liquid form. Many such surfactants are preferably provided in solid form. In one aspect of the present invention, a liquid surfactant is added to a drying device together with a carrier to form a solidified surfactant composition. Any suitable liquid surfactant can be included in the solidified surfactant composition. Preferred liquid surfactants include, but are not limited to, amine oxides, betaines, sultaines, and combinations thereof.

[0053] Amine oxides are tertiary amine oxides corresponding to the general formula, [ka] In the formula, the arrow is the conventional representation of a semipolar bond, R 1 , R 2 , and R 3can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Generally, for detergent-related amine oxides, R 1 is an alkyl radical having from about 8 to about 18 carbon atoms, R 2 and R 3 are alkyl or hydroxyalkyl having 1 to 3 carbon atoms, or a mixture thereof, R 2 and R 3 can be bonded to each other through, for example, an oxygen or nitrogen atom to form a ring structure, R 4 is alkaline or a hydroxyalkylene group containing 2 to 3 carbon atoms, and n ranges from 0 to about 20.

[0054] Suitable amine oxides include those selected from coconut or tallow alkyldi-(lower alkyl) amine oxides, specific examples of which are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, 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 oxide, 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 examples of zwitterionic surfactants for use herein. The general formula of these compounds is as follows,

Chemical formula

[0056] A more specific structure of betaine includes the following: [ka] In the formula, R ’ However, it contains an alkyl, alkenyl, or hydroxyalkyl radical of 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety, where R'' is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms, and R''' is an alkylene or hydroxyalkylene or hydroxyalkylene containing 1 to 4 carbon atoms. These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH, nor do they show reduced water solubility within their isoelectric range. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyldimethyl betaine, C12-14 acylamidopropyl betaine, C 8-14 Acylamidehexyldiethylbetaine, 4-C 14-16 Acylmethylamide diethylammonio-1-carboxybutane, C 16-18 Acylamide dimethyl betaine, C 12-16 Acylamidopentanediethylbetaine, and C 12-16Acylmethylamide dimethylbetaine is one example.

[0057] A suitable sultaine is given by formula (R(R 1 )2N + R 2 SO 3- The compound may contain a compound having the formula, where R is C6-C 18 It is a hydrocarbyl group, and each R 1 However, typically independently, they are C1-C3 alkyl groups, such as methyl, and R 2 However, these are C1-C6 hydrocarbyl groups, such as C1-C3 alkylene or hydroxyalkylene groups.

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

[0059] In another aspect of the present invention, the claimed method according to the present invention provides a liquid feed comprising at least about 30%, preferably at least about 50%, more preferably at least about 65%, and most preferably at least about 85% of a solidifying surfactant composition. The liquid feed is an amount by mass of the liquid material added to the drying device.

[0060] Solid cleaning composition The solidified surfactant compositions of the present invention can be included in solid cleaning compositions. These cleaning compositions, though not limited to those described above, include, for example, detergent compositions including utensil cleaning compositions and laundry compositions, rinsing aids, and hard surface cleaning compositions. Exemplary embodiments of these compositions are provided in Tables 1-3 below. Such compositions are illustrative 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 provided as examples of preferred formulations. [Table 1] [Table 2] [Table 3]

[0061] In embodiments of the present invention, additional components may be included in the solid cleaning composition. These additional components provide the composition with desired properties and functionality. For the purposes of this application, the term “functional component” includes materials that provide beneficial properties in a particular use. Some specific examples of functional materials are discussed in more detail below, but the specific materials discussed are merely examples, and a variety of other functional components may be used. For example, many of the functional materials discussed below relate to materials used in cleaning, specifically in product cleaning applications. However, other embodiments may include functional components for use in other applications. Examples of such functional materials, depending on the desired properties and / or functionality of the composition, include chelating agents / metal ion sequestering agents, bleaching agents or activators, bactericides / antimicrobial agents, activators, builders or fillers, anti-redeposition agents, optical glossing agents, dyes, deodorants or fragrances, preservatives, stabilizers, processing aids, corrosion inhibitors, fillers, solidifying agents, curing agents, solubility modifiers, pH adjusters, humectants, hydrotropes, or a wide range of other functional materials. In the context of some embodiments disclosed herein, functional materials or components are optionally included in solid cleaning compositions for their functional properties. Some more specific examples of functional materials are discussed in further detail below, but the specific materials discussed are given merely as examples, and it should be understood by those skilled in the art and others that a wide variety of other functional materials may be used.

[0062] In one aspect of the present invention, some of the additional components described below may be included in the solidifying surfactant composition. Preferred additional components that can be incorporated into the solidifying surfactant composition include, but are not limited to, co-surfactants, dyes, and / or fragrances (deodorants).

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

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

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

[0066] Activating agent In some embodiments, the composition may have improved antimicrobial or bleaching properties by adding materials that react with reactive oxygen species to form activated components. For example, in some embodiments, peracids or perate salts are formed. For example, in some embodiments, tetraacetylethylenediamine may be included in the composition to react with reactive oxygen species to form peracids or perate salts that perform antimicrobial functions. Other examples of reactive oxygen species activators include transition metals and compounds thereof, compounds containing carboxyl moieties, nitrile moieties, or ester moieties, or other such compounds known in the art. In one embodiment, the activator includes tetraacetylethylenediamine; transition metals; compounds containing carboxyl moieties, nitrile moieties, amine moieties, or ester moieties; or mixtures thereof.

[0067] In some embodiments, the activating agent component may be included in a range of up to about 75% by weight of the cleaning composition, in some embodiments in a range of about 0.01 to about 20% by weight, or in some embodiments in a range of about 0.05 to 10% by weight of the cleaning composition. In some embodiments, the activating agent of the reactive oxygen species compound combines with reactive oxygen species to form an antimicrobial agent.

[0068] The activator may be attached to the solid cleaning composition by any of the various methods for attaching one solid cleaning composition to another. For example, the activator may be in solid form, bonded, fixed, glued, or adhered to the solid cleaning composition. Alternatively, the solid activator may be formed around the solid cleaning composition and encompass the solid cleaning composition. As a further example, the solid activator may be attached to the solid cleaning composition by a container or packaging for the composition, such as plastic or shrink wrap or film.

[0069] Alkaline source The cleaning composition may contain one or more effective amounts of alkali sources. One or more effective amounts of alkali sources should be considered as an amount that provides a composition having a pH of about 7 to about 14. In certain embodiments, the cleaning composition may have a pH of about 7.5 to about 13.5. During the cleaning cycle, the solution used may have a pH of about 6 to about 14. In certain embodiments, the solution used may have a pH of about 6 to about 14. If the cleaning composition contains an enzyme composition, the pH may be adjusted to provide an optimal pH range for the effectiveness of the enzyme composition. In a particular embodiment of the present invention in which an enzyme composition is incorporated into the cleaning composition, the optimal pH is about 10 to about 11.

[0070] Examples of suitable alkali sources for cleaning compositions include, but are not limited to, carbonate-based alkali sources containing carbonates such as alkali metal carbonates, and caustic-based alkali sources containing alkali metal hydroxides. Other suitable alkali sources include metal silicates, metal borates, and organic alkali sources. Exemplary alkali metal carbonates that can be used include, but are not limited to, sodium carbonate, potassium carbonate, bicarbonates, sesquicarbonates, and mixtures thereof. Exemplary alkali metal hydroxides that can be used include, but are not limited to, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Exemplary metal silicates that can be used include, but are not limited to, sodium silicate or potassium silicate or sodium metasilicate or potassium metasilicate. Exemplary metal borates include, but are not limited to, sodium borate or potassium borate.

[0071] Organic alkali sources often include strong nitrogen bases, such as ammonia (ammonium hydroxide), amines, alkanolamines, and amino alcohols. Typical examples of amines include primary, secondary, or tertiary amines and diamines that support at least one nitrogen-bonded hydrocarbon group, which represents a saturated or unsaturated linear or branched alkyl group having at least 10 carbon atoms, preferably 16 to 24 carbon atoms, or an aryl, aralkyl, or alkaryl group containing up to 24 carbon atoms, and any other nitrogen-bonded group is formed by optionally substituted alkyl, aryl, or aralkyl or polyalkoxy groups. Typical examples of alkanolamines include monoethanolamine, monopropanolamine, diethanolamine, dipropanolamine, triethanolamine, and tripropanolamine. 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, and hydroxymethylaminomethane.

[0072] Generally, alkali sources are usually available in either aqueous or powder form. Preferably, the alkali source is in solid form. Alkalinity can be added to compositions in any form known in the art, including solid beads, granules, or particulate matter, or combinations thereof, dissolved in an aqueous solution.

[0073] Generally, the cleaning composition is expected to contain an amount of alkali source ranging from about 0.01% to about 99% by weight. In some embodiments, the alkali source may be about 35% to about 95% by weight of the total weight of the cleaning composition. When diluted in a working solution, the composition of the present invention may contain about 5 ppm to about 25,000 ppm of alkali source.

[0074] Anti-re-adhesion agent The cleaning composition may optionally contain an anti-redeposition agent capable of promoting the sustained suspension of dirt in the cleaning or rinsing solution and preventing the removed dirt from reattaching to the cleaned and / or rinsed material. Some examples of suitable anti-redeposition agents may include fatty acid amides, fluorocarbon surfactants, complex phosphate esters, styrene maleic anhydride copolymers, and cellulose derivatives such as hydroxyethylcellulose and hydroxypropylcellulose. The cleaning composition may contain an anti-redeposition agent in a range of up to about 10% by weight, and in some embodiments, about 1 to about 5% by weight.

[0075] bleach The cleaning composition may optionally contain a bleaching agent. The bleaching agent may be used to lighten or whiten the substrate and is typically found under conditions encountered during the cleaning process, such as Cl2, Br2, and -OCl. - , and / or -OBr -The bleaching agent may contain bleaching compounds that can release active halogen species such as chlorine, hypochlorite, and chloramine. Suitable bleaching agents may contain, for example, chlorine-containing compounds such as chlorine, hypochlorite, and chloramine. Some examples of halogen-releasing compounds include alkali metal dichloroisocyanurate, trisodium chlorinated phosphate, alkali metal hypochlorite, monochloramine, and dichloramine. Encapsulated chlorine sources may also be used to improve the stability of the chlorine source in the composition (see, for example, U.S. Patents 4,618,914 and 4,830,773, whose disclosures are incorporated herein by reference). The bleaching agent may also contain or function as an active oxygen source. Active oxygen compounds function to provide an active oxygen source and may release active oxygen into an aqueous solution, for example. Active oxygen compounds may be inorganic or organic, or mixtures thereof. Some examples of active oxygen compounds include peroxygen compounds or peroxygen compound additives. Some examples of reactive oxygen species compounds or sources of reactive oxygen species include hydrogen peroxide, perboric acid, sodium carbonate hydride, phosphate peroxyhydrate, potassium peroxymonosulfate, and sodium perborate monohydrate and sodium perborate tetrahydrate, with or without activators such as tetraacetylethylenediamine. The cleaning composition may contain a small but effective amount of bleach, for example, in some embodiments ranging from up to about 10% by weight, and in some embodiments ranging from about 0.1% to about 6% by weight.

[0076] Chelating agents / metal ion sequestering agents The cleaning composition may also contain an effective amount of chelating agents / metal ion sequestering agents, also referred to as builders. In addition, the cleaning composition may optionally contain one or more additional builders as functional ingredients. Generally, chelating agents are molecules that can coordinate (i.e., bind) metal ions commonly found in water sources to prevent them from interfering with the action of other compositions of rinsing aids or other cleaning compositions. When included in effective amounts, chelating agents / metal ion sequestering agents may also function as water conditioners. In some embodiments, the cleaning composition may contain chelating agents / metal ion sequestering agents in the range of up to about 70% by weight, or in the range of about 1 to 60% by weight.

[0077] In many cases, cleaning compositions also do not contain phosphates and / or sulfates. In embodiments of phosphate-free solid cleaning compositions, additional functional materials, including builders, do not contain phosphorus-containing compounds such as condensed phosphates and phosphonates.

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

[0079] In embodiments of phosphate-free solid cleaning compositions, additional chelating agents / metal ion sequestering agents may include, for example, condensation phosphates and phosphonates. Some examples of condensation phosphates include sodium orthophosphate and potassium orthophosphate, sodium pyrophosphate and potassium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate. Condensation phosphates can also assist in the solidification of the composition to a limited extent by fixing the free water present in the composition as hydration water.

[0080] In embodiments of phosphate-free solid cleaning compositions, the composition includes 1-hydroxyethane-1,1-diphosphonic acid CH3C(OH)[PO(OH)2]2, aminotri(methylenephosphonic acid)N[CH2]PO(OH) 23 , aminotri(methylenephosphonate), sodium salt [ka] 2-Hydroxyethyliminobis(methylenephosphonic acid) HOCH2CH2N\[CH2PO(OH)2] 2、 Diethylenetriaminepenta(methylenephosphonic acid)(HO)2POCH2N\[CH2N\[CH2PO(OH)2]2] 2、 Diethylenetriaminepenta(methylenephosphonate), sodium salt C9H (28-x) N3Na x O 15 P5 (x=7), hexamethylenediamine (tetramethylenephosphonate), potassium salt C 10 H (28-x) N2K x O 12The mixture may contain phosphonates such as P4(x=6), bis(hexamethylene)triamine(pentamethylenephosphonic acid)(HO2)POCH2N[(CH2)6N[CH2PO(OH)2]2]2, and phosphorus-containing acids H3PO3. In some embodiments, combinations of phosphonates such as ATMP and DTPMP may be used. Neutralized or alkaline phosphonates, or a mixture of phosphonates and an alkali source before being added to the mixture, may be used so that little or no heat or gas is generated by the neutralization reaction when the phosphonate is added.

[0081] For further consideration of chelating / sequestering agents, see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd edition, Vol. 5, pp. 339-366 and Vol. 23, pp. 319-320, whose disclosures are incorporated herein by reference.

[0082] Dyes / Deodorizers Various dyes, fragrances, odorants, and other cosmetic enhancers may also be included in the solid cleaning composition. Dyes may be included to alter the appearance of the composition, such as FD&C Blue 1 (Sigma Chemical), FD&C Yellow 5 (Sigma Chemical), Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10 (Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical), Sap Green (Keystone Analine and Chemical), Metalil Yellow (Keystone Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan Blue / Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25 (Ciba-Geigy), etc.

[0083] Examples of fragrances or scents that may be included in the solid cleaning composition include terpenoids such as citronellol, aldehydes such as amyl cinnamaldehyde, jasmine such as C1S-jasmine or jasmal, and vanillin.

[0084] Filler The solid cleaning composition may optionally contain one or more fillers in small but effective amounts. Some examples of suitable fillers include C1-C such as sodium chloride, starch, sugars, and propylene glycol. 10Examples include alkylene glycols, sulfates, PEG, urea, sodium acetate, magnesium sulfate, sodium carbonate, and the like. In some embodiments, the filler may be included in an amount ranging from about 50% by weight to a maximum, and in some embodiments, in an amount ranging from about 1 to 15% by weight.

[0085] Functional polydimethylsiloxane The solid cleaning composition may also optionally contain one or more functional polydimethylsiloxanes. For example, in some embodiments, polyalkylene oxide-modified polydimethylsiloxanes, nonionic surfactants, or polybetaine-modified polysiloxane amphoteric surfactants may be used as additives. Both are linear polysiloxane copolymers to which a polyether or polybetaine is grafted via a hydrosilylation reaction, in some embodiments. Some examples of specific siloxane surfactants are known as SILWET® surfactants, available from Union Carbide, or ABIL® polyether or polybetaine polysiloxane copolymers, available from Goldschmidt Chemical Corp., and are described in U.S. Patent No. 4,654,161, whose patent is incorporated herein by reference. In some embodiments, the specific siloxanes used may be described as having, for example, low surface tension, high wetting ability, and excellent lubricity. For example, these surfactants are said to be among the few surfactants capable of wetting polytetrafluoroethylene surfaces. Siloxane surfactants used as additives can be used alone or in combination with fluorinated surfactants. In some embodiments, fluorinated surfactants used as additives in combination with silanes as optional may be, for example, nonionic fluorohydrocarbons, such as fluorinated alkyl polyoxyethylene ethanol, fluorinated alkyl alkoxylates, and fluorinated alkyl esters.

[0086] Further descriptions of such functional polydimethylsiloxanes and / or fluorinated surfactants are found in U.S. Patents 5,880,088, 5,880,089, and 5,603,776, all of which are incorporated herein by reference. We have found, for example, that the use of certain polysiloxane copolymers in mixtures together with hydrocarbon surfactants results in excellent rinsing aids for plasticware. We have also found that combinations of certain silicone polysiloxane copolymers and fluorinated surfactants with conventional hydrocarbon surfactants also result in excellent rinsing aids for plasticware. This combination has been found to be superior to the individual components, except for the use of certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine polysiloxane copolymers, which have nearly equivalent efficacy. Thus, some embodiments may include polysiloxane copolymers alone, while combinations with fluorinated surfactants may involve polyether polysiloxanes, which are nonionic siloxane surfactants. Polybetaine polysiloxane copolymers, which are amphoteric siloxane surfactants, can be used alone as additives in cleaning compositions to provide the same results.

[0087] In some embodiments, the composition may contain a functional polydimethylsiloxane in an amount ranging from up to about 10% by weight. For example, some embodiments may optionally contain a polyalkylene oxide-modified polydimethylsiloxane or polybetaine-modified polysiloxane in a range of about 0.1 to 10% by weight, in combination with a fluorinated hydrocarbon nonionic surfactant.

[0088] Hardening / Solidifying agent / Solubility modifier In some embodiments, one or more solidifying agents may be included in the cleaning composition. Examples of solidifying agents include urea, amides such as stearate monoethanolamide or laurate diethanolamide or alkylamide; sulfates or sulfated surfactants, and aromatic sulfonates; solid polyethylene glycol or solid EO / PO block copolymers; starch made water-soluble by an acid or alkali treatment process; and various inorganic substances that impart solidifying properties to the heated composition upon cooling. Such compounds can also vary the solubility of the composition in aqueous media during use, so that the active ingredients can be distributed from the solid composition over a long period of time.

[0089] Suitable aromatic sulfonates include, but are not limited to, sodium xylenesulfonate, sodium toluenesulfonate, sodium cumenesulfonate, potassium toluenesulfonate, ammonium xylenesulfonate, calcium xylenesulfonate, sodium alkylnaphthalenesulfonate, and / or sodium butylnaphthalenesulfonate. Preferred aromatic sulfonates include sodium xylenesulfonate and sodium cumenesulfonate.

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

[0091] In certain embodiments, it may be desirable to have a secondary curing agent. In compositions containing a secondary curing agent, the composition may contain the secondary curing agent in an amount ranging from up to about 50% by weight. In some embodiments, the secondary curing agent may be present in an amount ranging from about 5% to about 35% by weight, often in the range of about 10% to about 25% by weight, and occasionally in the range of about 5% to about 15% by weight.

[0092] In some embodiments, one or more additional curing agents may be included in the solid cleaning composition if desired. Examples of curing agents include amides, such as monoethanolamide stearate or diethanolamide laurate or alkylamide; solid polyethylene glycol or solid EO / PO block copolymer; starch made water-soluble by an acid or alkali treatment process; and various inorganic substances that, upon cooling, impart solidifying properties to the heated composition. Such compounds can also vary the solubility of the composition in aqueous media during use, so that components can be distributed from the solid composition over a long period of time. The composition may contain a secondary curing agent in an amount ranging from up to about 30% by weight. In some embodiments, the secondary curing agent may be present in an amount ranging from about 5 to about 25% by weight, often in the range of about 10 to about 25% by weight, and occasionally in the range of about 5 to about 15% by weight.

[0093] Moisturizer The solid cleaning composition may also optionally contain one or more humectants. A humectant is a substance having an affinity for water. The humectant may be provided in an amount sufficient to help reduce the visibility of the film on the substrate surface. The visibility of the film on the substrate surface is of particular concern when the rinse water contains more than 200 ppm of total dissolved solids. Therefore, in some embodiments, the humectant is provided in an amount sufficient to reduce the visibility of the film on the substrate surface when the rinse water contains more than 200 ppm of total dissolved solids, compared to a rinsing composition that does not contain a humectant. The terms “water-solid film formation” or “film formation” refer to the presence of a visible, continuous layer of substance on the substrate surface that gives the substrate surface the appearance of not being cleaned.

[0094] Some exemplary humectants that may be used include materials containing more than 5% by weight of water (based on a dry humectant) at equilibrated at 50% relative humidity and room temperature. Examples of humectants that may be used include glycerin, propylene glycol, sorbitol, alkyl polyglycosides, polybetaine polysiloxanes, and mixtures thereof. In some embodiments, the rinsing agent composition may contain the humectant in an amount ranging from up to about 75% by weight of the total composition, and in some embodiments, in an amount ranging from about 5% to about 75% by weight of the composition.

[0095] Hydrated salt The solid cleaning composition according to the present invention may optionally contain at least one hydrateable salt. In one embodiment, the hydrateable salt is sodium carbonate (also known as soda ash or ash) and / or potassium carbonate (also known as potassium). In a preferred embodiment, the hydrateable salt is sodium carbonate and does not contain potassium carbonate. The hydrateable salt may be provided in the range of approximately 20% to approximately 90% by weight, preferably approximately 25% to approximately 90% by weight, and more preferably approximately 30% to approximately 70% by weight, such as sodium carbonate. Those skilled in the art will understand other preferred component concentration ranges for obtaining equivalent properties of the solidification matrix.

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

[0097] polymer Cleaning compositions include polymers, or polymer systems comprising at least one polycarboxylic acid polymer, copolymer, and / or terpolymer. Particularly preferred 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 (C4H2O3)x, or hydrolyzed polymaleic anhydride, or cis-2-butenidioic acid homopolymer has the following structural formula: [ka] In the formula, n and m are any integers. Examples of polymaleic acid homopolymers, copolymers, and / or terpolymers (and their salts) that may be used in the present invention are specific and preferably have molecular weights of about 0 to about 5000, more preferably about 200 to about 2000 (these MW may be confirmed). Examples of commercially available polymaleic acid homopolymers include the Belclene 200 series maleic acid homopolymer from BWA® 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 may be present in the cleaning composition in amounts of about 0.01% to about 30% by weight.

[0099] The cleaning composition of the present invention may use polyacrylic acid polymers, copolymers, and / or terpolymers. Polyacrylic acid has the following structural formula: [ka] In the formula, n is any integer. Suitable examples of polyacrylic acid polymers, copolymers, and / or terpolymers include, but are not limited to, polyacrylic acid, (C3H4O2) n Examples include 2-propenoic acid, acrylic acid, polyacrylic acid, polymers, copolymers, and / or terpolymers of propenoic acid.

[0100] In one embodiment of the present invention, particularly preferred acrylic acid polymers, copolymers, and / or terpolymers have a molecular weight of about 100 to about 10,000, in one preferred embodiment about 500 to about 7,000, in one more preferred embodiment 1,000 to about 5,000, and in one most preferred embodiment about 1,500 to about 3,500. Examples of polyacrylic acid polymers, copolymers, and / or terpolymers (or salts thereof) that may be used in the present invention include, but are not limited to, Acusol 448 and Acusol 425 from The Dow Chemical Company (Wilmington, Delaware, USA). In certain embodiments, it may be desirable to have acrylic acid polymers (and salts thereof) having a molecular weight greater than about 10,000. Examples include, but are not limited to, both Acusol 929 (10,000 MW) and Acumer 1510 (60,000 MW) available from Dow Chemical, and AQUATREAT AR-6 (100,000 MW) from Akzo Nobel (Strawinskylaan 2555 1077 ZZ Amsterdam Postbus 75730 1070 AS Amsterdam). Approximately 0.01% to 30% by weight of polyacrylic acid polymers, copolymers, and / or terpolymers may be present in the composition, and approximately may be present in the cleaning composition.

[0101] Maleic anhydride / olefin copolymer is a copolymer of polymaleic anhydride and an olefin. Maleic anhydride ((C2H2(CO)2O) has the following structure: [ka] Some of the maleic anhydride is maleimide, N-alkyl(C) 1-4 ) Maleimide, N-phenylmaleimide, fumaric acid, itaconic acid, citraconic acid, aconitic acid, crotonic acid, cinnamic acid 10, alkyl(C) of the aforementioned acids 1-18 )ester, The aforementioned cycloalkyl(C) acid 3-8 It may be replaced with esters, sulfated castor oil, etc. At least 95% by weight of the maleic anhydride polymer, copolymer, or terpolymer has a number average molecular weight in the range of about 700 to about 20,000, preferably about 1,000 to about 100,000.

[0102] For the purposes of the present invention, a variety of linear and branched alpha-olefins can be used. Particularly useful alpha-olefins include dienes containing 4 to 18 carbon atoms, such as butadiene, chloroprene, isoprene, and 2-methyl-1,5-hexadiene; and isobutylene, 1-butene, 1-hexene, 1-octene, and other alpha-olefins containing 4 to 8 carbon atoms, preferably C 4-10 It is a 1-alkene.

[0103] In one embodiment of the present invention, particularly preferred maleic anhydride / olefin copolymers have a molecular weight of about 1,000 to about 50,000, in one preferred embodiment about 5,000 to about 20,000, and in one most preferred embodiment about 7,500 to about 12,500. Examples of maleic anhydride / olefin copolymers that can be used in the present invention include, but are not limited to, Acusol 460N from The Dow Chemical Company (Wilmington, Delaware, USA). Maleic anhydride / olefin copolymer may be present in the cleaning composition in an amount of about 0.01% to about 30% by weight.

[0104] Disinfectant / Antibacterial agent Cleaning compositions may optionally contain disinfectants. Disinfectants, also known as antimicrobial agents, are chemical compositions that can be used in solid functional materials to prevent microbial contamination and degradation of material systems, surfaces, etc. Generally, these materials fall into specific classes, including phenols, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines, nitro derivatives, analides, organosulfurs and sulfur-nitrogen compounds, and other compounds.

[0105] It should be understood that reactive oxygen species compounds, such as those mentioned above in the section on bleaching agents, can also function as antibacterial agents and may even provide bactericidal activity. In fact, in some embodiments, the ability of reactive oxygen species compounds to function as antibacterial agents reduces the need for additional antibacterial agents in the composition. For example, percarbonate compositions have been shown to provide excellent antibacterial activity. Nevertheless, some embodiments still incorporate additional antibacterial agents.

[0106] A given antimicrobial agent, depending on its chemical composition and concentration, can simply limit the further growth of a number of microorganisms or destroy all or part of a microbial community. The terms "microbe" and "microorganism" typically refer mainly to bacteria, viruses, yeasts, spores, and fungal microorganisms. When used, antimicrobial agents are typically formed into solid functional materials, which can optionally be diluted, for example, using a stream of water, and dispensed to form aqueous disinfectant or bactericidal compositions that can come into contact with various surfaces, inhibiting or killing part of a microbial community. A 3-log reduction of the microbial community results in a bactericidal composition. Antimicrobial agents can be encapsulated, for example, to improve their stability.

[0107] Some common examples of antimicrobial agents include phenolic antimicrobial agents such as pentachlorophenol, orthophenylphenol, chloro-p-benzylphenol, and p-chloro-m-xylenol. Halogens containing antibacterial agents include bromine compounds such as sodium trichloroisocyanurate, sodium dichloroisocyanate (anhydrous or dihydrate), iodo-poly(vinylpyrrolidinone) complex, and 2-bromo-2-nitropropane-1,3-diol, as well as quaternary antimicrobial agents such as benzalkonium chloride, didecyldimethylammonium chloride, choline diiodochloride, and tetramethylphosphonium tribromide. Other antimicrobial compositions such as dithiocarbamates like hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine and sodium dimethyldithiocarbamate, and various other substances, are known in the art for their antimicrobial properties.

[0108] In embodiments of solid cleaning compositions that are phosphate-free and / or sulfate-free and also contain an antimicrobial agent, the antimicrobial agent is selected to satisfy these requirements. Embodiments of solid cleaning compositions containing only GRAS components may omit or not include the antimicrobial agents described in this section.

[0109] In some embodiments, the cleaning composition contains antimicrobial components in a range of up to about 10% by weight of the composition, up to about 5% by weight in some embodiments, or in a range of about 0.01 to about 3% by weight or 0.05 to 1% by weight of the composition.

[0110] Additional surfactants The solidified surfactant composition may contain optionally selected co-surfactants. Preferably, the co-surfactants are in solid form. Furthermore, the solidified surfactant composition of the present invention can be incorporated into cleaning compositions. Examples of such cleaning compositions, but not limited to, include detergent compositions, utensil cleaning compositions, laundry compositions, rinsing aids, and hard surface cleaning compositions. Surfactants that can be included as co-surfactants in the solidified surfactant composition and / or as surfactants in the cleaning composition include nonionic surfactants, semipolar nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures or combinations thereof.

[0111] When a co-surfactant carrier is included in the solidified surfactant composition of the present invention, the co-surfactant is preferably in a weight ratio of about 1:0 to about 0:1 with respect to the liquid surfactant. In further embodiments of the present invention, the co-surfactant carrier is present in an amount of about 20% to about 90% by weight, more preferably about 30% to about 90% by weight, and more preferably about 40% to about 80% by weight.

[0112] Nonionic surfactants Useful nonionic surfactants are generally characterized by the presence of organic hydrophobic and organic hydrophilic groups and are typically produced by the condensation of an organoaliphatic, alkyl aromatic, or polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety, which is generally ethylene oxide or its polyhydration product, polyethylene glycol. In practice, any hydrophobic compound having a hydroxyl, carboxyl, amino, or amide group with a reactive hydrogen atom can condense with ethylene oxide, its polyhydrate adduct, or a mixture thereof with an alkoxylene such as propylene oxide to form a nonionic surfactant. The length of the hydrophilic polyoxyalkylene moiety that condenses with any particular hydrophobic compound can be easily adjusted to produce a water-dispersible or water-soluble compound with a desired balance between hydrophilic and hydrophobic properties. Useful nonionic surfactants include:

[0113] The initiator-reactive hydrogen compounds include propylene glycol, ethylene glycol, glycerol, trimethylolpropane, and ethylenediamine-based block polyoxypropylene-polyoxyethylene polymer compounds. One class of compounds is a bifunctional (two-reactive hydrogen) compound formed by condensing ethylene oxide with a hydrophobic base formed by adding propylene oxide to the two hydroxyl groups of propylene glycol. This hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 4,000. The ethylene oxide is then added so as to sandwich this hydrophobic substance between hydrophilic groups, and its length is controlled to constitute about 10% to about 80% by weight of the final molecule. Another class of compounds is a trifunctional block copolymer obtained from the sequential addition of propylene oxide and ethylene oxide to ethylenediamine. The molecular weight of propylene oxide hydrotype ranges from approximately 500 to 7,000, and hydrophilic ethylene oxide is added to constitute approximately 10% to 80% by weight of the molecule.

[0114] Condensation products of 1 mole of alkylphenol containing about 8 to about 18 carbon atoms in a linear or branched alkyl chain, or a single or double alkyl component, with about 3 to about 50 moles of ethylene oxide. The alkyl group may be represented, for example, by diisobutylene, diamyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants may also be polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols. Examples of commercial compounds of this chemistry are commercially available under the trade names Igepal® from Rhone-Poulenc and Triton® from Union Carbide.

[0115] A condensation product of 1 mole of a saturated or unsaturated linear or branched alcohol having approximately 6 to 24 carbon atoms and approximately 3 to 50 moles of ethylene oxide. The alcohol portion may consist of a mixture of alcohols within the aforementioned carbon range, or of an alcohol having a specific number of carbon atoms within this range. Examples of equivalent commercially available surfactants are available under the trade names Neodol®, manufactured by Shell Chemical Co., and Alfonic®, manufactured by Vista Chemical Co.

[0116] A condensation product of 1 mole of a saturated or unsaturated linear or branched carboxylic acid having approximately 8 to 18 carbon atoms and approximately 6 to 50 moles of ethylene oxide. The acid portion may consist of a mixture of acids within the carbon atom range defined above, or of acids having a specific number of carbon atoms within this range. Examples of commercial compounds of this chemical are commercially available under the trade name Lipopeg® from Lipo Chemicals, Inc.

[0117] In addition to ethoxylated carboxylic acids, commonly known as polyethylene glycol esters, other alkanate esters formed by reactions with glycerides, glycerol, and polyhydric (saccharide or sorbitan / sorbitol) alcohols have applications as described herein, particularly in indirect food additive applications, in specialized embodiments. All of these ester moieties have one or more reactive hydrogen sites on their molecules that can be subjected to further acylation or ethylene oxide (alkoxide) addition to control the hydrophilicity of these substances.

[0118] Examples of nonionic low-foaming surfactants include the following: Compounds from (1) that are essentially inverted by adding ethylene oxide to ethylene glycol to provide a hydrophilic substance of a specified molecular weight; and then adding propylene oxide to obtain a hydrophobic block on the outside (ends) of the molecule. The hydrophobic portion of the molecule has a molecular weight of about 1,000 to about 3,100, and the central hydrophilic substance accounts for 10% to about 80% by weight of the final molecule. The hydrophobic portion of the molecule has a molecular weight of about 2,100 to about 6,700, and the central hydrophilic substance accounts for 10% to about 80% by weight of the final molecule.

[0119] Compounds from groups (1), (2), (3), and (4) modified by "capping" or "end blocking" the terminal hydroxyl group(s) (of the polyfunctional moiety) to reduce foaming in reaction with hydrophobic small molecules such as propylene oxide, butylene oxide, and benzyl chloride; and short-chain fatty acids, alcohols, or alkyl halides containing 1 to about 5 carbon atoms; and mixtures thereof. Also included are reactants such as thionyl chloride, which converts terminal hydroxyl groups to chloride groups. Such modifications to terminal hydroxyl groups can result in all-blocked, block-heteric, heteric-blocked, or all-heteric nonionic substances.

[0120] Examples of effective low-foaming nonionic substances to be added include: U.S. Patent No. 2,903,486, issued to Brown et al. on September 8, 1959, [ka] Alkylphenoxypolyethoxyalkanols are represented by the formula where R is an alkyl group with 8 to 9 carbon atoms, A is an alkylene chain with 3 to 4 carbon atoms, n is an integer from 7 to 16, and m is an integer from 1 to 10.

[0121] A polyalkylene glycol condensate of U.S. Patent No. 3,048,548, issued to Martin et al. on August 7, 1962, having alternating hydrophilic oxyethylene chains and hydrophobic oxypropylene chains, where the weight of the terminal hydrophobic chain, the weight of the intermediate hydrophobic unit, and the weight of the linking hydrophilic unit each account for approximately one-third of the weight of the condensate.

[0122] The general formula Z[(OR) ] is where Z is an alkoxylated material, R is a radical derived from an alkylene oxide which can be ethylene and propylene, n is an integer such as 10 to 2,000 or more, and z is an integer determined by the number of reactive oxyalkylated groups. n OH] z An antifoaming nonionic surfactant having the following properties, disclosed in U.S. Patent No. 3,382,178, issued to Lissant et al. on May 7, 1968.

[0123] Y is a residue of an organic compound having approximately 1 to 6 carbon atoms and 1 reactive hydrogen atom, n has an average value of at least about 6.4 determined by the hydroxyl value, and m has a value such that the oxyethylene moiety constitutes approximately 10% to 90% by weight of the molecule, given the formula Y(C3H6O). n (C2H4O) m A conjugated polyoxyalkylene compound corresponding to H, as described in U.S. Patent No. 2,677,700, issued to Jackson et al. on May 4, 1954.

[0124] Formula Y[(C3H6O n (C2H4O) m H] xA conjugated polyoxyalkylene compound as described in U.S. Patent No. 2,674,619, issued to Lundsted et al. on April 6, 1954, having (wherein Y is a residue of an organic compound having about 2 to 6 carbon atoms and x reactive hydrogen atoms (x having a value of at least about 2), n having a value such that the molecular weight of the polyoxypropylene hydrophobic base is at least about 900, and m having a value such that the oxyethylene content of the molecule is about 10% to about 90% by weight). Compounds that fall within the definition range for Y include, for example, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, and ethylenediamine. The oxypropylene chain optionally, but beneficially, contains a small amount of ethylene oxide, and the oxyethylene chain also optionally, but beneficially, contains a small amount of propylene oxide.

[0125] An additional conjugated polyoxyalkylene surfactant that can be advantageously used in the compositions of the present invention is of the formula: P[(C3H6O) n (C2H4O) m H] x Corresponding to the formula, where P is a residue of an organic compound having about 8 to 18 carbon atoms and x reactive hydrogen atoms, x has a value of or 2, n has a value such that the molecular weight of the polyoxyethylene portion is at least about 44, and m has a value such that the oxypropylene content of the molecule is about 10% to about 90% by weight. In any case, the oxypropylene chain may optionally, but advantageously, contain a small amount of ethylene oxide, and the oxyethylene chain may also optionally, but advantageously, contain a small amount of propylene oxide.

[0126] A polyhydroxy fatty acid amide surfactant suitable for use in this composition is, structural formula R2CON R1 Z(wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy group, or a mixture thereof; R2 may be a linear C5-C) 31The hydrocarbil is a polyhydroxyhydrocarbil having a hydrocarbil linear chain having at least three hydroxyls directly linked to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z can be obtained from reducing sugars in a reductive amination reaction, such as a glycityl moiety.

[0127] Alkyl ethoxylate condensation products of aliphatic alcohols with approximately 0 to 25 moles of ethylene oxide are suitable for use in this composition. The alkyl chain of the aliphatic alcohol can be either linear or branched, primary or secondary, and generally contains 6 to 22 carbon atoms.

[0128] Ethoxylation C6~C 18 Fatty alcohols and C6-C 18 Mixed ethoxylated and propoxylated fatty alcohols, especially those that are water-soluble, are suitable surfactants for use in this composition. Suitable ethoxylated fatty alcohols are C6-C6 alcohols with an ethoxylation degree of 3-50. 18 Contains ethoxylated fatty alcohols.

[0129] Nonionic alkyl polysaccharide surfactants particularly suitable for use in this composition include those disclosed in U.S. Patent No. 4,565,647, Llenado, issued on January 21, 1986. These surfactants contain a hydrophobic group containing about 6 to about 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, a hydrophilic group containing about 1.3 to about 10 saccharide units. Any reduced saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose, and the galactosyl portion can be substituted for the glucosyl portion. (Optionally, the hydrophobic group may be bonded at positions 2, 3, 4, etc., thus resulting in glucose or galactose as opposed to glucosides or galactosides.) Saccharid-saccharid bonds may be, for example, between one position of an additional saccharide unit and positions 2, 3, 4, and / or 6 on the preceding saccharide unit.

[0130] Fatty acid amide surfactants suitable for use in this composition include those having the formula: R6CON(R7)2, where R6 is an alkyl group containing 7 to 21 carbon atoms, and each R7 is independently hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, or --(C2H4O) X H is given by the equation, where x is in the range of 1 to 3.

[0131] A useful class of nonionic surfactants includes alkoxylated amines, or more specifically, the class defined as alcohol alkoxylated / amination / alkoxylated surfactants. These nonionic surfactants are at least in part, with the general formula: R 20 --(PO) S N--(EO) t H, R 20 --(PO) S N--(EO) t H(EO) t H and R 20 --N(EO) t It can be expressed by H, where R 20 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl group of 8 to 20 carbon atoms, preferably 12 to 14 carbon atoms, EO is oxyethylene, PO is oxypropylene, s is 1 to 20, preferably 2 to 5, t is 1 to 10, preferably 2 to 5, and u is 1 to 10, preferably 2 to 5. Other variations within the range of these compounds are shown in alternative formulas: R 20 --(PO) V --N[(EO) w H][(EO) z It can be expressed by H], where R 20The values ​​are as defined above, where 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 commercially represented by a product line marketed by Huntsman Chemicals as nonionic surfactants. Preferred chemicals in this class include Surfonic® PEA25 amine alkoxylates. Preferred nonionic surfactants for the compositions of the present invention include alcohol alkoxylates, EO / PO block copolymers, alkylphenol alkoxylates, and the like.

[0132] The paper, *Nonionic Surfactants*, edited by Schick, MJ, Vol. 1 of the Surfactant Science Series, Marcel Dekker, Inc., New York, 1983, is an excellent reference for a wide range of nonionic compounds commonly used in the practice of the present invention. A typical list of the nonionic class and species of these surfactants is described in U.S. Patent No. 3,929,678, issued December 30, 1975, to Laughlin and Heuring. Further examples are described in "Surface Active Agents and detergents" (Volumes I and II, Schwartz, Perry and Berch).

[0133] Semipolar nonionic surfactant Semipolar nonionic surfactants are another class of nonionic surfactants useful in the compositions of the present invention. Generally, semipolar nonionic substances are foaming agents and foam stabilizers, which may limit their application in CIP systems. However, in the compositional embodiments of the present invention designed for high-foaming cleaning methods, semipolar nonionic substances have immediate practical applications. Semipolar nonionic surfactants include amine oxides, phosphine oxides, sulfoxides, and their alkoxylated derivatives.

[0134] Amine oxides are tertiary amine oxides corresponding to the general formula, [ka] In the formula, the arrow is the conventional representation of a semipolar bond, R 1 , R 2 , and R 3 These can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. Generally, in detergent-related amine oxides, R 1 However, it is an alkyl radical with approximately 8 to 24 carbon atoms, R 2 and R 3 However, it is an alkyl or hydroxyalkyl group with 1 to 3 carbon atoms, or a mixture thereof, R 2 and R 3 However, they can bond to each other via, for example, oxygen or nitrogen atoms, forming a ring structure, R 4 However, it is an alkali or a hydroxyalkylene group containing 2-3 carbon atoms, and n is in the range of 0 to about 20.

[0135] Useful water-soluble amine oxide surfactants are selected from coconut or taro alkyl di-(lower alkyl)amine oxides, and specific examples thereof are dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, 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 oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0136] Useful semipolar nonionic surfactants also include water-soluble phosphine oxides having the following structure: [ka] In the formula, the arrow is the conventional representation of a semipolar bond, R 1 R is an alkyl, alkenyl, or hydroxyalkyl moiety with a chain length range of 10 to approximately 24 carbon atoms. 2 and R 3 Each of these is an alkyl moiety separately selected from alkyl or hydroxyalkyl groups containing 1 to 3 carbon atoms.

[0137] Examples of useful phosphine oxides include dimethyldecylphosphine oxide, dimethyltetradecylphosphine oxide, methylethyltetradecylphosphon oxide, dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosphine oxide, bis(2-hydroxyethyl)dodecylphosphine oxide, and bis(hydroxymethyl)tetradecylphosphine oxide.

[0138] Semipolar nonionic surfactants useful in this specification also include water-soluble sulfoxide compounds having a structure. [ka] In the formula, the arrow is the conventional representation of a semipolar bond, R 1 R consists of approximately 8 to 28 carbon atoms, 0 to 5 ether bonds, and 0 to 2 alkyl or hydroxyalkyl moieties of hydroxyl substituents. 2 This is an alkyl moiety consisting of alkyl and hydroxyalkyl groups having 1 to 3 carbon atoms.

[0139] Useful examples of these sulfoxides include dodecyl methyl sulfoxide; 3-hydroxytridecyl methyl sulfoxide; 3-methoxytridecyl methyl sulfoxide; and 3-hydroxy-4-dodecoxybutyl methyl sulfoxide.

[0140] Semipolar nonionic surfactants for the compositions of the present invention include dimethylamine oxides, such as lauryldimethylamine oxide, myristyldimethylamine oxide, cetyldimethylamine oxide, and combinations thereof. Useful water-soluble amine oxide surfactants are selected from octyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyldi-(lower alkyl)amine oxides, specific examples of which include octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, isododecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylamine oxide, heptadecyldimethylamine oxide, and These are tadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldipropylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

[0141] Suitable nonionic surfactants for use with the composition of the present invention include alkoxylated surfactants. Suitable alkoxylated surfactants include EO / PO copolymers, capped EO / PO copolymers, alcohol alkoxylates, capped alcohol alkoxylates, and mixtures thereof. Suitable alkoxylated surfactants for use as solvents include EO / PO block copolymers such as Pluronic and reverse Pluronic surfactants; alcohol alkoxylates such as Dehypon LS-54 (R-(EO)5(PO)4) and Dehypon LS-36 (R-(EO)3(PO)6); capped alcohol alkoxylates such as Plurafac LF221 and Tegoten EC11; and mixtures thereof.

[0142] Anionic surfactants Surfactants classified as anionic substances because the hydrophobic portion of the substance has a negative charge, or surfactants whose hydrophobic portion of the molecule has no charge unless the pH rises above neutral (e.g., carboxylic acids), are also useful in the present invention. Carboxylates, sulfonates, sulfates, and phosphates are polar (hydrophilic) solubilizing groups found in anionic surfactants. Of the cations (counterions) associated with these polar groups, sodium, lithium, and potassium confer water solubility, ammonium and substituted ammonium ions provide both water and oil solubility, and calcium, barium, and magnesium promote oil solubility. As those skilled in the art will understand, anionic substances are excellent cleaning surfactants and are therefore preferred additives to heavy detergent compositions.

[0143] Suitable anionic sulfate surfactants for use in this composition include alkyl ether sulfates, alkyl sulfates, linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleylglycerol sulfates, alkylphenol ethylene oxide ether sulfates, and C5-C 17Examples include acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates, as well as alkyl polysaccharide sulfates such as alkyl polyglucoside sulfates. Also included are alkyl sulfates, alkyl poly(ethyleneoxy) ether sulfates, and aromatic poly(ethyleneoxy) sulfates, such as ethylene oxide and nonylphenol sulfates or concentrated products (typically containing 1 to 6 oxyethylene groups per molecule).

[0144] Suitable anionic sulfonate surfactants for use in this composition include alkyl sulfonates, linear and branched primary and secondary alkyl sulfonates, and aromatic sulfonates with or without substituents.

[0145] Suitable anionic carboxylate surfactants for use in the present composition include carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester carboxylic acids (e.g., alkyl succinates), ether carboxylic acids, sulfonated fatty acids, such as sulfonated oleic acid, and the like. Such carboxylates include alkyl ethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants, and soaps (e.g., alkyl carboxyls). Secondary carboxylates useful in the present composition include those containing a carboxyl unit connected to a secondary carbon. The secondary carbon may be in a ring structure, such as in p - octylbenzoic acid or in an alkyl - substituted cyclohexyl carboxylate. Secondary carboxylate surfactants typically do not contain ether bonds, ester bonds, and hydroxyl groups. Further, they typically lack a nitrogen atom within the head group (amphiphilic moiety). Suitable secondary soap surfactants typically contain from 11 to 13 total carbon atoms, although more carbon atoms (e.g., up to 16) may be present. Suitable carboxylates also include acyl amino acids (and salts) such as acyl glutamate, acyl peptide, sarcosinate (e.g., N - acyl sarcosinate), and taurate (e.g., fatty acid amides of N - acyl taurate and methyl tauride).

[0146] Suitable anionic surfactants include alkyl or alkyl aryl ethoxy carboxylates of the following formula: R - O - (CH2CH2O) n (CH2) m -CO2X (3) wherein R is a C8 - C 22 alkyl group or

Chemical formula

[0147] In other embodiments, R is

Chemical formula

[0148] Such alkyl and alkylaryl ethoxycarboxylates are commercially available. These ethoxycarboxylates are typically available in acid form and can be easily converted into anionic or salt forms. Commercially available carboxylates include Neodox 23 - 4, C 12~13 alkyl polyethoxy(4) carboxylic acid (Shell Chemical), and Emcol CNP - 110, C9 alkylaryl polyethoxy(10) carboxylic acid (Witco Chemical). Carboxylates such as the product Sandopan® DTC, C 13 alkyl polyethoxy(7) carboxylic acid are also available from Clariant.

[0149] Cationic surfactant Surface active substances are classified as cationic if the charge on the hydrotrope portion of the molecule is positive. Surfactants that are cationic (e.g., alkylamines) after the hydrotrope is not charged unless the pH is near or below neutral also belong to this group. Theoretically, cationic surfactants can be synthesized from any combination of elements containing the "onium" structure RnX+Y-- and can include compounds other than nitrogen (ammonium), such as phosphorus (phosphonium) and sulfur (sulfonium). In practice, the field of cationic surfactants is dominated by nitrogen-containing compounds, perhaps because the synthetic pathway from nitrogen to cationic surfactants is simple and easy, producing high-yield products, and thus making nitrogen cationic surfactants cheaper.

[0150] Cationic surfactants preferably comprise, and more preferably, compounds containing at least one long-carbon hydrophobic group and at least one positively charged nitrogen atom. The long-carbon group may be directly bonded to the nitrogen atom by simple substitution, or more preferably, indirectly bonded by a crosslinking functional group(s) in so-called interrupted alkylamines and amidoamines. Such functional groups can make the molecule more hydrophilic and / or more water-dispersible, allowing it to dissolve more readily in water with co-surfactant mixtures and / or making it water-soluble. To increase water solubility, additional primary, secondary, or tertiary amino groups may be introduced, or the amino nitrogen may be quaternized using a low molecular weight alkyl group. Furthermore, the nitrogen may be part of a branched or linear portion with varying degrees of unsaturation, or part of a saturated or unsaturated heterocyclic ring. In addition, cationic surfactants may contain complex bonds having two or more cationic nitrogen atoms.

[0151] Surfactant compounds classified as amine oxides, amphoteric substances, and zwitterionic compounds are generally cationic in solutions with near-neutral to acidic pH, overlapping with the classification of surfactants. Polyoxyethylated cationic surfactants generally behave like nonionic surfactants in alkaline solutions and like cationic surfactants in acidic solutions.

[0152] The simplest cationic amines, namely amine salts and quaternary ammonium compounds, are as follows: [ka] In the formula, R represents an alkyl chain, R', R'', and R'''' may be either an alkyl chain or an aryl group, or a hydrogen atom, and X represents an anion. Amine salts and quaternary ammonium compounds are preferred for practical use in the present invention due to their high water solubility.

[0153] The majority of commercially available cationic surfactants can be subdivided into four main classes and additional subgroups known to those skilled in the art, as described in “Surfactant Encyclopedia”, Cosmetics & Toiletries, Vol. 104(2) 86-96 (1989). The first class includes alkylamines and their salts. The second class includes alkylimidazolines. The third class includes ethoxylated amines. The fourth class includes quaternary products such as alkylbenzyldimethylammonium salts, alkylbenzene salts, heterocyclic ammonium salts, and tetraalkylammonium salts. Cationic surfactants are known to possess a variety of properties that can be beneficial in this composition. These desirable properties may include cleaning power in compositions with neutral or sub-neutral pH, antimicrobial efficacy, and thickening or gelling in conjunction with other agents.

[0154] A cationic surfactant useful in the composition of the present invention is formula R 1 m R 2 x YL Examples include those having Z, where each R 1 It contains a linear or branched alkyl or alkenyl group, optionally substituted with up to three phenyl or hydroxyl groups, and has up to four of the following structures: [ka] Alternatively, it is an organic group optionally interrupted by isomers or mixtures of these structures, containing approximately 8 to 22 carbon atoms. 1 The group may contain up to 12 additional ethoxy groups. m is a number from 1 to 3. Preferably, there is one or fewer R groups in the molecule. 1 The group has 16 or more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3. Each R 2 This is an alkyl or hydroxyalkyl group containing 1 to 4 carbon atoms or a benzyl group, and has 1 or fewer R groups in the molecule. 2 is benzyl, and x is a number from 0 to 11, preferably from 0 to 6. The remaining carbon atoms at any position on the Y group are filled with hydrogen. Y is not limited, [ka] Or it may be a mixture thereof. Preferably, L is 1 or 2, and when L is 2, the Y group has 1 to about 22 carbon atoms and 2 free carbon single bonds. 1 and R 2 The components are separated by a portion selected from analogs (preferably alkylene or alkenylene). Z is a water-soluble anion such as a halide anion, sulfate anion, methyl sulfate anion, hydroxide anion, or nitrate anion, with chloride anions, bromide anions, iodide anions, sulfate anions, or methyl sulfate anions being particularly preferred in terms of the number of components that impart electrical neutrality to the cationic components.

[0155] Amphoteric surfactants Amphoteric or ampholytic surfactants contain both basic and acidic hydrophilic groups, as well as organic hydrophobic groups. These ionic entities may be either anionic or cationic groups as described herein for other types of surfactants. Basic nitrogen and acidic carboxylate groups are typical functional groups used as basic and acidic hydrophilic groups. In some surfactants, sulfonates, sulfates, phosphonates, or phosphates provide a negative charge.

[0156] Amphoteric surfactants can be broadly described as derivatives of aliphatic secondary and tertiary amines, where the aliphatic radical may be linear or branched, and one of the aliphatic substituents comprises about 8 to 18 carbon atoms, and one comprises an anionic water-soluble group, e.g., carboxy, sulfo, sulfato, phosphat, or phosphono. Amphoteric surfactants are known to those skilled in the art and are subdivided into two main classes, as described in the "Surfactant Encyclopedia" Cosmetics & Toiletries, Vol. 104(2) 69-71 (1989), which is incorporated herein by reference in its entirety. The first class includes acyl / dialkylethylenediamine derivatives (e.g., 2-alkylhydroxyethylimidazoline derivatives) and their salts. The second class includes N-alkyl amino acids and their salts. Some amphoteric surfactants may be assumed to fit into both classes.

[0157] Amphoteric surfactants can be synthesized by methods known to those skilled in the art. For example, 2-alkylhydroxyethylimidazoline is synthesized by condensation and ring closure of a long-chain carboxylic acid (or derivative) with a dialkylethylenediamine. Commercially available amphoteric surfactants are derivatized using, for example, chloroacetic acid or ethyl acetate by subsequent hydrolysis and ring opening of the imidazoline ring by alkylation. During alkylation, one or two carboxyalkyl groups react to form a tertiary amine and an ether linkage, and different alkylating agents yield different tertiary amines.

[0158] The long-chain imidazole derivatives that have applications in the present invention generally have the following general formula: [ka] [ka] In the formula, R is an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M is a cation, generally sodium, for neutralizing the charge of the anion. Commercially well-known amphoteric compounds derived from imidazolines that can be used in this composition include, for example, cocoamphopropionate, cocoamphocarboxy-propionate, cocoamphoglycinate, cocoamphocarboxy-glycinate, cocoamphopropyl-sulfonate, and cocoamphocarboxy-propionic acid. Amphocarboxylic acids can be produced from aliphatic imidazolines, where the dicarboxylic acid functional group of the amphodicarboxylic acid is diacetic acid and / or dipropionic acid.

[0159] In this specification, the carboxymethylated compounds (glycinates) described above are often referred to as betaines. Betaines are a special class of amphoteric compounds described below in the following section entitled Zwitterionic surfactants.

[0160] Long-chain N-alkyl amino acids are readily prepared by the reaction RNH2, where R = C8-C 18These are aliphatic amines having linear or branched alkyl and halogenated carboxylic acids. Alkylation of the primary amino group of an amino acid yields secondary and tertiary amines. The alkyl substituent may have additional amino groups that provide multiple reactive nitrogen centers. The most commercially available N-alkylamine acids are alkyl derivatives of β-alanine or β-N(2-carboxyethyl)alanine. Examples of commercially available N-alkylamino acid amphoteric electrolytes applicable to the present invention include alkyl β-aminodipropionates, RN(C2H4COOM)2 and RNHC2H4COOM. In one embodiment, R may be an acyclic hydrophobic group containing about 8 to about 18 carbon atoms, and M may be a cation for neutralizing the charge of the anion.

[0161] Suitable amphoteric surfactants include those derived from coconut products such as coconut oil or coconut fatty acids. Additional suitable coconut-derived surfactants include, as part of their structure, an ethylenediamine moiety, an alkanolamide moiety, an amino acid moiety, e.g., glycine, or a combination thereof, and an aliphatic substituent with about 8 to 18 (e.g., 12) carbon atoms. Such surfactants may also be considered alkylamphodicarboxylic acids. These amphoteric surfactants are C 12 -alkyl-C(O)-NH-CH2-CH2-N + (CH2-CH2-CO2Na)2-CH2-CH2-OH or C 12 -alkyl-C(O)-N(H)-CH2-CH2-N + It may include a chemical structure represented as (CH2-CO2Na)2-CH2-CH2-OH. Disodium cocoamphodipropionate is one preferred amphoteric surfactant, commercially available from Rhodia Inc., Cranbury, NJ under the trade name Miranol® FBS. Another preferred coconut-derived amphoteric surfactant having the chemical name disodium cocoamphodiacetate is also sold by Rhodia Inc., Cranbury, NJ under the trade name Mirataine® JCHA.

[0162] A typical list of amphoteric classes and species of these surfactants is described in U.S. Patent No. 3,929,678, published December 30, 1975, to Laughlin and Heuring. Further examples are described in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry, and Berch). Each of these references is incorporated herein by reference in its entirety.

[0163] Zwitterionic surfactants Zwitterionic surfactants can be considered a subset of amphoteric surfactants and may contain anionic charges. Zwitterionic surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Typically, zwitterionic surfactants contain a positively charged quaternary ammonium, or optionally a sulfonium or phosphonium ion, a charged carboxyl group, and an alkyl group. Zwitterionic compounds generally contain cationic and anionic groups that ionize to approximately the same degree in the isoelectric region of the molecule, potentially leading to a strong "internal salt" attraction between positive and negative charge centers. Examples of such zwitterionic synthetic surfactants include derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium compounds, in which the aliphatic group may be linear or branched, and one of the aliphatic substituents contains 8 to 18 carbon atoms and one contains an anionic water-soluble group, such as a carboxyl, sulfonate, sulfate, phosphate, or phosphonate.

[0164] Betaine and sultaine surfactants are examples of zwitterionic surfactants for use herein. The general formulas of these compounds are as follows: [ka] In the formula, R 1Y comprises an alkyl, alkenyl, or hydroxyalkyl radical with 8 to 18 carbon atoms having 0 to 10 ethylene oxide moieties and 0 to 1 glyceryl moiety, Y is selected from the group consisting of nitrogen atoms, phosphorus atoms, and sulfur atoms, and R 2 x is an alkyl group or monohydroxyalkyl group containing 1 to 3 carbon atoms, where x is 1 when Y is a sulfur atom, and 2 when Y is a nitrogen atom or a phosphorus atom, and R 3 Z is an alkylene or hydroxyalkylene or hydroxyalkylene with 1 to 4 carbon atoms, and Z is a radical selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfate group, a phosphonic acid group, and a phosphate group.

[0165] Examples of zwitterionic surfactants having the above structure include 4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate, 5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sulfate, 3-[P,P-diethyl-P-3,6,9-trioxatetracosanphosphonio]-2-hydroxypropane-1-phosphate, 3-[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate, 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate. Examples include xadecylammonio)-2-hydroxy-propane-1-sulfonate, 4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate, 3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate, 3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate, and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxypentane-1-sulfate. The alkyl group contained in the detergent surfactant may be linear or branched, and may be saturated or unsaturated.

[0166] Suitable zwitterionic surfactants for use in this composition include betaine with a general structure. [ka] These surfactant betaines typically do not exhibit strong cationic or anionic characteristics at extreme pH levels, nor do they show a reduction in water solubility within these isoelectric ranges. Unlike "external" quaternary ammonium salts, betaines can coexist with anions. Examples of suitable betaines include coconut acylamidopropyl dimethyl betaine, hexadecyldimethyl betaine, C12-14 acylamidopropyl betaine, and C12-14 acylamidopropyl betaine. 8-14 Acylamidehexyldiethylbetaine, 4-C 14-16 Acylmethylamide diethylammonio-1-carboxybutane, C 16-18 Acylamide dimethyl betaine, C 12-16 Acylamidopentanediethylbetaine, and C 12-16 Acylmethylamide dimethylbetaine is one example.

[0167] The sultaine useful in this invention is of formula (R(R 1 )2N + R 2 SO 3- The compound comprises a compound having a C6-C6 compound, where R is C6-C6 18 It is a hydrocarbyl group, and each R 1 Typically, independently, R is a C1-C3 alkyl group, such as methyl. 2 These are C1-C6 hydrocarbyl groups, such as C1-C3 alkylene or hydroxyalkylene groups.

[0168] A typical list of zwitterionic classes and species of these surfactants is provided in U.S. Patent No. 3,929,678, issued December 30, 1975, by Laughlin and Heuring. Further examples are provided in “Surface Active Agents and Detergents” (Vol. I and II by Schwartz, Perry, and Berch). Each of these references is incorporated herein in its entirety.

[0169] Method for manufacturing a detergent composition The solidified surfactant composition of the present invention can be included in various cleaning compositions. Preferably, the cleaning composition is a solid composition. Suitable solid cleaning compositions include, but are not limited to, granular and pelletized solid compositions, powders, solid block compositions, cast solid block compositions, extruded solid block compositions, and pressed solid compositions. Preferably, the cleaning composition is a pressed solid.

[0170] Solid particulate cleaning compositions can be prepared by simply blending dry solid components formed according to the present invention in appropriate ratios, or by agglomerating the materials in an appropriate agglomeration system. Pelleted materials can be prepared by compressing solid granular or agglomerated materials in an appropriate pelletizing apparatus to obtain appropriately sized pelletized materials. Solid blocks and cast solid block materials can be prepared by introducing either a pre-cured block of material or a castable liquid that hardens into a solid block in the container into a container. Preferred containers include disposable plastic containers or water-soluble film containers. Other suitable packaging for the compositions includes flexible bags, parcels, shrink wrap, and water-soluble films such as polyvinyl alcohol.

[0171] Solid cleaning compositions can be formed using batch or continuous mixing systems. In exemplary embodiments, a single-screw or twin-screw extruder is used to combine and mix one or more components at high shear to form a homogeneous mixture. In some embodiments, the processing temperature is below the melting temperature of the components. Once the processed mixture has hardened into a solid form, it can be dispensed from the mixer by forming, molding, or other suitable means. The structure of the matrix can be characterized according to its hardness, melting point, material distribution, crystalline structure, and other similar properties according to methods known in the art. Generally, solid cleaning compositions processed according to the methods of the present invention are substantially homogeneous and dimensionally stable throughout their entire mass with respect to the distribution of components.

[0172] In the extrusion process, liquid and solid components are introduced into a final mixing system and continuously mixed until a substantially homogeneous semi-solid mixture is formed in which the components are distributed throughout their entire mass. The mixture is then discharged from the mixing system into or through a die or other molding means. The product is then packaged. In exemplary embodiments, the formed composition begins to harden into a solid state in approximately 1 minute to approximately 3 hours. More specifically, the formed composition begins to harden into a solid state in approximately 1 minute to approximately 2 hours. More specifically, the formed composition begins to harden into a solid state in approximately 1 minute to approximately 20 minutes.

[0173] In the casting process, liquid and solid components are introduced into a final mixing system and continuously mixed until a substantially homogeneous liquid mixture is formed in which the components are distributed throughout their entire mass. In an exemplary embodiment, the components are mixed in the mixing system for at least approximately 60 seconds. Once mixing is complete, the product is transferred to a packaging container where solidification occurs. In an exemplary embodiment, the casting composition begins to harden into a solid state in approximately 1 minute to approximately 3 hours. More specifically, the casting composition begins to harden into a solid state in approximately 1 minute to approximately 2 hours. More specifically, the casting composition begins to harden into a solid state in approximately 1 minute to approximately 20 minutes.

[0174] In a press solid process, fluid solids, such as granular solids or other particulate solids, are combined under pressure. In a compression solid process, the fluid solids of the composition are placed within a mold (e.g., a mold or container). The method may include gently pressing the fluid solids within the mold to produce a solid cleaning composition. Pressure may be applied by a block machine or rotary plate press, etc. Pressure may be applied at about 1 to about 3000 psi, about 5 to about 2500 psi, or about 10 to about 2000 psi. As used herein, the terms “psi” or “pounds per square inch” refer to the actual pressure applied to the fluid solid being pressed, and not to a gauge or water pressure measured at a point within the pressing apparatus. The method may include a curing step to produce a solid cleaning composition. As referred herein, an uncured composition containing fluid solids is compressed to provide sufficient surface contact between the particles constituting the fluid solids, which will solidify the uncured composition into a stable solid composition. A sufficient amount of particles in contact with one another (e.g., granules) provides effective particle-to-particle bonding to produce a stable solid composition. The inclusion of an optional curing step may include allowing the pressed solid to solidify for a period of time such as several hours or about a day (or longer). In additional embodiments, the method may include vibrating a fluid solid in a mold or formwork, such as the method disclosed in U.S. Patent No. 8,889,048, which is incorporated herein by reference in whole.

[0175] The use of pressed solids offers numerous advantages over conventional solid block or tablet compositions produced by extrusion, which requires casting that necessitates high pressure or significant energy consumption of the composition within a tablet press, and / or requires expensive equipment and advanced technical expertise. Pressed solids overcome the various limitations of other solid formulations required for the production of solid cleaning compositions. Furthermore, pressed solid compositions retain their shape under conditions in which the composition may be stored or handled.

[0176] The term “solid” means that the cured composition will not flow under moderate stress or pressure or mere gravity and will substantially retain its shape. A solid can be in various forms, such as powder, flakes, granules, pellets, tablets, lozenges, packs, briquettes, bricks, solid blocks, unit doses, or other solid forms known to those skilled in the art. The hardness of solid cast compositions and / or pressed solid compositions can range from the hardness of relatively dense and hard fused solid products, such as concrete, to the hardness characteristic of a cured paste. In addition, the term “solid” refers to the state of the cleaning composition under the expected storage and use conditions of a solid cleaning composition. Generally, cleaning compositions are expected to remain in a solid form when exposed to temperatures up to approximately 100°F, specifically up to approximately 120°F.

[0177] The resulting solid cleaning composition may take the form of, but is not limited to, a cast solid product; extruded, molded, or formed solid pellets, blocks, tablets, powders, granules, or flakes; or a pressed solid or formed solid may be subsequently ground or formed into powder, granules, or flakes. In exemplary embodiments, the extruded pellet material formed by the solidification matrix has a weight of approximately 50 to approximately 250 grams, the extruded solid formed by the composition has a weight of approximately 100 grams or more, and the solid block detergent formed by the composition has a mass of approximately 1 to approximately 10 kilograms. The solid composition provides a stabilized source of functional material. In some embodiments, the solid composition may be dissolved in, for example, an aqueous medium or other medium to produce a concentrated solution and / or a solution for use. This solution may be directed to a reservoir for subsequent use and / or dilution, or it may be applied directly to the point of use.

[0178] The following patents disclose various combinations of coagulants, binders, and / or curing agents that may be used in the solid cleaning compositions of the present invention. The following U.S. Patents: U.S. Patents No. 7,153,820, No. 7,094,746, No. 7,087,569, No. 7,037,886, No. 6,831,054, No. 6,730,653, No. 6,660,707, No. 6,653,266, No. 6,583,094, No. 6,410,495, No. 6,258,765, No. 6, Patents No. 177,392, No. 6,156,715, No. 5,858,299, No. 5,316,688, No. 5,234,615, No. 5,198,198, No. 5,078,301, No. 4,595,520, No. 4,680,134, RE32,763, and RE32818 are incorporated herein by reference.

[0179] Liquid compositions can typically be prepared by forming components in aqueous liquids or aqueous solvent systems. Such systems are typically prepared by dissolving or suspending the active ingredient in water or a compatible solvent, and then diluting the product to an appropriate concentration to form either a concentrate or a working solution. Gelatinous compositions can similarly be prepared by dissolving or suspending the active ingredient in a compatible aqueous, aqueous liquid, or mixed aqueous organic system containing a gelling agent at an appropriate concentration. All publications and patent applications herein represent the level of those skilled in the art to which the present invention pertains. All publications and patent applications are incorporated herein by reference to the same extent as each individual publication or patent application is incorporated by reference specifically and individually. [Examples]

[0180] Embodiments of the present invention are further defined in the following non-limiting examples. These examples illustrate specific embodiments of the present invention, but should be understood to be given for illustrative purposes only. From the above considerations and these examples, those skilled in the art can identify the essential features of the present invention and make various changes and modifications to the embodiments of the present invention without departing from the spirit and scope of the invention to suit various uses and conditions. Therefore, to those skilled in the art, various modifications to the embodiments of the present invention will be apparent from the foregoing description in addition to those shown and described herein. Such modifications are also intended to fall within the scope of the appended claims.

[0181] The materials used in the following embodiments are provided herein. Ammonyx LO (30%), a lauramine oxide available from Stepan Co. Cocamidopropyl betaine, available from Amphosol CG, Stepan Co. Barlox 12, a cocoamine oxide available from Lonza. Mackam CB35, Coco-Betaine, available from Solvay. Lauramidopropyl hydroxysultaine, available from Macham LSB50 and Rhodia. Macham 50SB, cocamidopropyl hydroxysultaine, available from Rhodia.

[0182] Additional ingredients, available from multiple commercial suppliers, were incorporated, including sodium alpha-olefin sulfate, sodium chloride, sodium sulfate, sodium acetate, and magnesium sulfate.

[0183] Example 1 Liquid surfactant solidified with a carrier Exemplary liquid amine oxides, betaines, and sultaine surfactants were solidified on various exemplary solid carriers according to the methods described herein. These formulations are shown in Table 4. [Table 4]

[0184] Table 4 demonstrates that the liquid surfactant can be solidified with the carrier.

[0185] The foregoing description, or the following claims, presented in a particular form, or from the perspective of means for carrying out the disclosed functions, or methods or processes for achieving the disclosed results, may, as appropriate, be utilized separately or in any combination of such features, to realize the present invention in its various forms.

[0186] From the fact that the present invention is thus described, it will be apparent that the present invention can be modified in many ways. Such modifications should not be regarded as departing from the spirit and scope of the present invention, and all such corrections are intended to be included within the scope of the following claims. The above specification provides an explanation 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 present invention, the present invention falls within the scope of the claims. Examples of embodiments of the present disclosure are listed in the following sections [1] to

[44] . [1] A liquid surfactant comprising one or more of amine oxide, betaine, and sultaine, A carrier comprising an anionic surfactant, an organic salt, an inorganic salt, or a combination thereof, <X A solidified liquid surfactant composition comprising, The carrier and the liquid surfactant are in a ratio of approximately 5:1 to approximately 1:30 based on the active substance. A solidified liquid surfactant composition wherein the composition is a solid, the liquid surfactant is solidified in the composition, and the solidified surfactant composition contains less than 5% by weight of water. [2] The solidified surfactant composition according to item 1, wherein the carrier and the liquid surfactant have an active substance ratio of about 2:1 to about 1:25. [3] The solidifying surfactant composition according to item 1 or 2, wherein the liquid surfactant is one or more of dodecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, 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 oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide. [4] [[ID=3{X The liquid surfactant is coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C 12-14 Acylamidopropyl betaine, C 8-14 Acylamide hexyl diethyl betaine, C 16-18 Acylamide dimethyl betaine, C 12-16 Acylamidopentanediethylbetaine, C 12-16 A solidifying surfactant composition according to any one of items 1 to 3, which is one or more acylmethylamide dimethyl betaines, or a combination thereof. [5] The aforementioned liquid surfactant is of formula (R(R 1 ) 2 N + R 2 SO 3- It is a compound having, where R is C 6 -C 18 It is a hydrocarbyl group, R 1 However, C 1 -C 3 It is alkyl, R 2 However, C 1 -C 6 A solidifying surfactant composition according to any one of items 1 to 4, wherein the group is a hydrocarbyl group. [6] The solidifying surfactant composition according to any one of items 1 to 5, wherein the carrier comprises an anionic surfactant, and the anionic surfactant is a sulfonate, a sulfate, or a combination thereof. [7] The solidifying surfactant composition according to any one of items 1 to 6, wherein the carrier is an alpha-olefin sulfonate, a linear alkyl sulfonate, sodium lauryl sulfate, sodium alkyl sulfate, or a combination thereof. [8] The solidifying surfactant composition according to any one of items 1 to 7, wherein the carrier is an alkali metal carbonate, an alkali metal carbonate, an alkali metal acetate, an alkali metal acetate, an alkali metal sulfate, an alkali metal sulfate, sodium chloride, or a combination thereof. [9] The solidifying surfactant composition according to any one of items 1 to 8, wherein the carrier is sodium carbonate, magnesium carbonate, sodium acetate, magnesium acetate, sodium sulfate, magnesium acetate, or a combination thereof.

[10] The solidifying surfactant composition according to any one of items 1 to 9, wherein the carrier is a solid.

[11] The solidifying surfactant composition according to any one of items 1 to 10, wherein the carrier is a powder.

[12] The solidifying surfactant composition according to any one of items 1 to 9, wherein the carrier is a liquid.

[13] The solidifying surfactant composition according to any one of items 1 to 12, wherein the carrier has a water solubility of about 0.2 g / L or more at 20°C.

[14] The solidifying surfactant composition according to any one of items 1 to 13, wherein the solidifying surfactant composition contains less than about 5% by weight of water.

[15] The solidifying surfactant composition according to any one of items 1 to 14, wherein the solidifying surfactant composition contains at least about 10% by weight of an active surfactant.

[16] The solidifying surfactant composition according to any one of items 1 to 15, wherein the solidifying surfactant composition contains at least about 25% by weight of an active surfactant.

[17] The solidifying surfactant composition according to any one of items 1 to 16, wherein the solidifying surfactant composition contains at least about 50% by weight of an active surfactant.

[18] A method for preparing a solidifying surfactant composition according to any one of items 1 to 17, wherein the method is: Adding the liquid surfactant and the carrier to the drying device, The process includes drying the liquid surfactant and the carrier to form a solidified surfactant composition, A method wherein the liquid surfactant solidifies in the solidified surfactant composition, and the solidified surfactant composition contains less than about 5% by weight of water.

[19] The solidification surfactant method according to item 18, wherein the drying device is a continuous tunnel dryer, rotary dryer, vacuum dryer, tower shrinker, vibrating conveyor shrinker, drum dryer, screw conveyor dryer, fluidized bed, jet bed, pneumatic conveyor, spray dryer, or a combination thereof.

[20] The method according to item 18 or 19, wherein there are at least two drying devices arranged in series or in parallel.

[21] The method according to any one of items 18 to 20, wherein the drying process is carried out in a batch system.

[22] The method according to any one of items 18 to 21, wherein the drying process is carried out in a continuous system.

[23] The method according to any one of items 18 to 22, wherein the drying device includes a fluidized bed.

[24] The method according to item 23, wherein the fluidized bed has a liquid flow rate of bed material of about 0.001 to about 0.15 lbs / min.

[25] The method according to item 23 or 24, wherein the fluidized bed has an atomizing air pressure of about 0 psig to about 100 psig per nozzle.

[26] The method according to any one of items 23 to 25, wherein the fluidized bed has an airflow velocity of about 1 to about 100 feet / second.

[27] The method according to any one of items 23 to 26, wherein the method employs an aggregation process and the carrier is a solid.

[28] The method according to any one of items 23 to 27, wherein the method employs a granulation process and the carrier is a liquid.

[29] A solidifying surfactant composition described in any one of items 1 to 17, A solid cleaning composition comprising a solidifying agent.

[30] The cleaning composition according to item 29, wherein the cleaning composition is a manual utensil cleaning composition, a laundry composition, or a hard surface composition.

[31] The cleaning composition according to item 29 or 30, further comprising an alkali source selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, metal silicates, metal borates, alkanolamines, and combinations thereof.

[32] The cleaning composition according to item 31, wherein the alkali source is present in an amount of about 0.01% to about 99% by weight of the cleaning composition.

[33] The cleaning composition according to item 31 or 32, wherein the alkali source is in an amount sufficient to provide a pH of about 7 to about 14 in the solution used.

[34] The cleaning composition according to any one of items 31 to 33, wherein the cleaning composition provides a pH of about 1 to about 7 in the solution used.

[35] A cleaning composition according to any one of items 31 to 34, further comprising additional surfactants selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, semipolar nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

[36] The cleaning composition according to any one of items 31 to 35, wherein the cleaning composition is a granular solid, a pelletized solid, a cast solid, an extruded solid block, or a pressed solid.

[37] The cleaning composition according to item 36, wherein the cleaning composition is a pressed solid.

[38] A cleaning composition according to any one of items 29 to 37, further comprising: at least one of the following additional ingredients: an acid source, an activator, an anti-redeposition agent, a bleaching agent, a chelating agent, a dye, an odorant, a filler, a functional polydimethylsiloxane, a curing agent, a hydrateable salt, a polymer, or a disinfectant.

[39] A method for cleaning a surface, Dissolve the cleaning composition described in any one of items 29 to 38 and perform liquid cleaning. Forming a composition, A method comprising bringing the surface into contact with the liquid cleaning composition.

[40] The method according to item 39, wherein the liquid cleaning composition is diluted.

[41] The method according to item 40, wherein the dilution of the liquid cleaning composition is performed after the dissolution of the solid cleaning composition and before the surface is brought into contact with the liquid cleaning composition.

[42] The method according to any one of items 39 to 41, wherein the surface includes a hard surface, an object, or laundry.

[43] The method according to any one of items 39 to 42, further comprising rinsing the surface with water.

[44] The method according to any one of items 39 to 43, wherein the cleaning composition provides substantially the same foaming properties as a cleaning composition having the same components, except that the solidifying surfactant composition is a liquid surfactant.

Claims

1. A liquid surfactant comprising one or more of amine oxide, betaine, and sultaine, A solid support containing an inorganic salt, A solidifying surfactant composition comprising, The ratio of the solid carrier and the liquid surfactant is 1:5 to 1:25 (solid carrier:liquid surfactant) based on the active substance. The composition is a free-flowing solid, the liquid surfactant is solidified in the composition, and the solidified surfactant composition contains less than 5% by weight of water. The amine oxide 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, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamine oxide, and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide. The betaine is coconut acylamidopropyl dimethyl betaine, hexadecyl dimethyl betaine, C １２－１４ Acylamidopropyl betaine, C ８－１４ Acylamidehexyldiethylbetaine, C １６－１８ Acylamide dimethyl betaine, C １２－１６ Acylamidopentanediethylbetaine, and C １２－１６ One or more of the following: acylmethylamide dimethyl betaine The sultaine is a compound having the formula R(R １ ), ２ N ＋ R ２ SO ３－ where R is a C ６ -C １８ hydrocarbyl group, R １ is a C １ -C ３ alkyl, and R ２ is a C １ -C ６ hydrocarbyl group, a solid surfactant composition.

2. The solidifying surfactant composition according to claim 1, wherein the liquid surfactant comprises the amine oxide.

3. The solidifying surfactant composition according to claim 1 or 2, wherein the liquid surfactant comprises the betaine.

4. The solidifying surfactant composition according to any one of claims 1 to 3, wherein the liquid surfactant comprises the sultaine.

5. The solidifying surfactant composition according to any one of claims 1 to 4, wherein the solid carrier comprises magnesium sulfate.

6. The solidifying surfactant composition according to any one of claims 1 to 5, wherein the solid carrier is a powder.

7. The solidifying surfactant composition according to any one of claims 1 to 6, wherein the solid carrier has a water solubility of 0.2 g / L or more at 20°C.

8. The solidifying surfactant composition according to any one of claims 1 to 7, wherein the solidifying surfactant composition contains at least 10% by weight of a surfactant.

9. The solidifying surfactant composition according to any one of claims 1 to 8, wherein the solidifying surfactant composition contains at least 25% by weight of a surfactant.

10. The solidifying surfactant composition according to any one of claims 1 to 9, wherein the solidifying surfactant composition contains at least 50% by weight of a surfactant.

11. A method for preparing a solidifying surfactant composition according to any one of claims 1 to 10, wherein the method is: Adding the liquid surfactant and the solid support to the drying device, The process includes drying the liquid surfactant and the solid carrier to form a solidified surfactant composition, A method wherein the liquid surfactant solidifies in the solidified surfactant composition, and the solidified surfactant composition contains less than 5% by weight of water.

12. The method according to claim 11, wherein the drying device is a continuous tunnel dryer, a rotary dryer, a vacuum dryer, a tower shrinker, a vibrating conveyor shrinker, a drum dryer, a screw conveyor dryer, a fluidized bed, a jet bed, a pneumatic conveyor, a spray dryer, or a combination thereof.

13. The method according to claim 11 or 12, wherein there are at least two drying devices arranged in series or in parallel.

14. The method according to any one of claims 11 to 13, wherein the drying is carried out in a batch system.

15. The method according to any one of claims 11 to 14, wherein the drying is carried out in a continuous system.

16. The method according to any one of claims 11 to 15, wherein the drying device includes a fluidized bed.

17. The method according to claim 16, wherein the fluidized bed has a liquid flow rate of 0.001 to 0.15 lb / min of bed material.

18. The method according to claim 16 or 17, wherein the fluidized bed has an atomizing air pressure of 0 psig to 100 psig per nozzle.

19. The method according to any one of claims 16 to 18, wherein the fluidized bed has an airflow velocity of 1 to 100 feet / second.

20. The method according to any one of claims 16 to 19, wherein the method employs an aggregation process.

21. A solidifying surfactant composition according to any one of claims 1 to 10, A solid cleaning composition comprising a solidifying agent.

22. The cleaning composition according to claim 21, wherein the cleaning composition is a manual utensil cleaning composition, a laundry composition, or a hard surface composition.

23. The cleaning composition according to claim 21 or 22, further comprising an alkali source selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, metal silicates, metal borates, alkanolamines, and combinations thereof.

24. The cleaning composition according to claim 23, wherein the alkali source is in an amount of 0.01% to 99% by weight of the cleaning composition.

25. The cleaning composition according to claim 23 or 24, wherein the alkali source is in an amount sufficient to provide a pH of 7 to 14 in the solution used.

26. The cleaning composition according to any one of claims 21 to 24, wherein the cleaning composition provides a pH of 1 to 7 in the solution used.

27. The cleaning composition according to any one of claims 23 to 26, further comprising an additional surfactant selected from the group consisting of nonionic surfactants, cationic surfactants, anionic surfactants, semipolar nonionic surfactants, amphoteric surfactants, zwitterionic surfactants, and combinations thereof.

28. The cleaning composition according to any one of claims 23 to 27, wherein the cleaning composition is a granular solid, a pelletized solid, a cast solid, an extruded solid block, or a pressed solid.

29. The cleaning composition according to claim 28, wherein the cleaning composition is a pressed solid.

30. The cleaning composition according to any one of claims 22 to 29, further comprising at least one of the following additional ingredients: an acid source, an activator, an anti-redeposition agent, a bleaching agent, a chelating agent, a dye, an odorant, a filler, a functional polydimethylsiloxane, a curing agent, a hydrateable salt, a polymer, or a disinfectant.

31. A method for cleaning a surface, Dissolving the cleaning composition according to any one of claims 21 to 30 to form a liquid cleaning composition, A method comprising bringing the surface into contact with the liquid cleaning composition.

32. The method according to claim 31, wherein the liquid cleaning composition is diluted.

33. The method according to claim 32, wherein the dilution of the liquid cleaning composition is performed after the dissolution of the solid cleaning composition and before the surface is brought into contact with the liquid cleaning composition.

34. The method according to any one of claims 31 to 33, wherein the surface includes a hard surface, an object, or laundry.

35. The method according to any one of claims 31 to 34, further comprising rinsing the surface with water.

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