Surfactants for cleaning products

Abstract

To provide a formulation including one or a plurality of surfactants, for use in cleaning and conditioning a fabric, a hard surface, and a plastic surface.SOLUTION: The formulation for use in cleaning a hard surface and a plastic surface, includes a surfactant including at least one of 6-(dodecyloxy)-N,N,N-trimethyl-6-(oxo-hexane)-1-aminium iodide, 6-(dimethylamino)hexanoate N-oxide, 6-(dodecyloxy)-N, N-dimethyl-6-(oxo-hexane)-1-aminium chloride, 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate, and 6-(dodecyloxy)-6-(oxo-hexane)-1-aminium chloride, and at least one detergent or at least one species of soap.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62 / 988,211, filed March 11, 2020, the entire contents of which are incorporated herein by reference.

[0002] The present disclosure relates to surfactants for use in cleaning products, including detergent products used to clean and condition fabrics, hard surfaces, and plastic surfaces. Such surfactants may include derivatives of amino acids that have surface-active properties. [Background technology]

[0003] Surfactants (molecules with surface-active properties) are widely used in commercial applications in a variety of formulations, from detergents to hair care products and cosmetics. Compounds with surface-active properties are used as soaps, detergents, lubricants, wetting agents, foaming agents, and spreading agents, among others. In personal care cleansing products (e.g., shampoos, body washes, facial cleansers, liquid hand soaps, etc.), surfactants are often the most important ingredient, as they provide many of the cleansing attributes of the composition.

[0004] Surfactants can be nonionic, zwitterionic, cationic, or anionic. In principle, any surfactant class (e.g., cationic, anionic, nonionic, amphoteric) is suitable for cleansing or cleaning applications, but in practice, many personal care cleansers and household cleaning products are formulated with a combination of two or more surfactants from two or more surfactant classes.

[0005] Surfactants are often amphiphilic molecules with a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can adsorb at interfaces, such as those between two liquids, between gas and liquid, or between solid and liquid. In systems containing a relatively polar component and a relatively non-polar component, the hydrophobic tail preferentially interacts with the relatively non-polar component, while the hydrophilic head preferentially interacts with the relatively polar component. In the case of an interface between water and oil, the hydrophilic head preferentially extends into the water, while the hydrophobic tail preferentially extends into the oil. When added to an air-water interface, the hydrophilic head preferentially extends into the water, while the hydrophobic tail preferentially extends into the air. The presence of a surfactant disrupts at least some of the intermolecular interactions between water molecules, replacing at least some of the interactions with the surfactant, which is generally weaker. This results in a reduction in surface tension and may also act to stabilize the interface.

[0006] At sufficiently high concentrations, surfactants can form aggregates that act to limit the exposure of their hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged in a spherical fashion, with the surfactant's hydrophobic tail preferentially located inside the sphere and the surfactant's hydrophilic head preferentially located on the outside of the micelle, where the head preferentially interacts with more polar solvents. The effect a given compound has on surface tension and the concentration at which it forms micelles can be useful characteristics for defining a surfactant. Summary of the Invention

[0007] The present disclosure provides compositions for cleaning and / or degreasing hard and plastic surfaces such as floors, walls, ceilings, roofs, countertops, furniture, plates, cups, glasses, cutlery, tableware, machines, machine parts, and equipment used in food preparation and / or packaging; laundry Fabric care formulations including detergents, stain removers, cleaning pre-treatments, fabric softeners, fabric dyes, and bleaches are provided, as well as compositions for use in cleaning upholstery and carpets. Some of the compositions of the present invention can be in the form of detergents, emulsifiers, dispersants, foaming agents, and combinations thereof. The products of the present invention can be formulated to include one or more surfactants from one or more surfactant classes.

[0008] The present disclosure provides derivatives of amino acids that have surface-active properties. The amino acids may be natural or synthetic amino acids, or may be obtained via ring-opening reactions of molecules such as lactams, e.g., caprolactam. The amino acids may be functionalized to form compounds with surface-active properties. Characteristically, these compounds may have a low critical micelle concentration (CMC) and / or the ability to reduce the surface tension of liquids.

[0009] The present disclosure provides formulations for aqueous cleaning products, which comprise at least one surfactant or co-surfactant of formula I:

[0010] [ka]

[0011] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with the compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; and one or more soaps that may themselves be characterized as surfactants, where the soap may include fatty acids, salts, and some soaps may include both water-soluble and oil-soluble portions.

[0012] The present disclosure provides formulations for laundry detergents, which comprise at least one surfactant or co-surfactant of formula I:

[0013] [ka]

[0014] In the formula, R 1 and R 2 may be the same or different, and are selected from hydrogen and C1-C6 alkyl. alkyl, wherein C1-C6 alkyl is optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with this compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; and at least one builder, which may include molecules that promote the effectiveness of the cleaning action in an aqueous environment; some useful builders include, but are not limited to, certain polymers, phosphates and aluminosilicates, calcium citrate, alkali metal salts, sodium salts, and some grades of zeolites.

[0015] The present disclosure provides formulations for bleach products, which comprise at least one surfactant or co-surfactant of formula I:

[0016] [ka]

[0017] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; a counterion associated with this compound, which may optionally be present and, if present, is selected from the group consisting of chloride, bromide, iodide, and hydroxide; and a bleaching agent, such as peroxide-based bleaches, including, but not limited to, inorganic persalts, organic peroxoacids, metal borates, percarbonates, perphosphates, persilicates, and persulfates.

[0018] The present disclosure provides formulations for use in dry cleaning, which comprise at least one surfactant or co-surfactant of formula I:

[0019] [ka]

[0020] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with the compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; a solvent and optional co-solvent, preferably a non-flammable oil immersion composition for use in either or both domestic or commercial dry cleaning processes.

[0021] One specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 1), which has the formula:

[0022] [ka]

[0023] A second specific compound provided by the present disclosure is dodecyl 6-(dimethylamino)hexanoate N-oxide (Surfactant 2), which has the following formula:

[0024] [ka]

[0025] In the above structures, the "N→O" notation is intended to mean a non-ionic bonding interaction between the nitrogen and oxygen.

[0026] A third specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride (Surfactant 3), which has the formula:

[0027] [ka]

[0028] A fourth specific compound provided by the present disclosure is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 4), which has the following formula:

[0029] [ka]

[0030] A fifth specific compound provided by the present disclosure is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride (Surfactant 5), which has the formula:

[0031] [ka]

[0032] The above and other features of the present disclosure, as well as the manner in which they are achieved, will become more apparent and will be better understood by referring to the following description of the embodiments taken in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0033] [Figure 1] FIG. 1 shows a plot of surface tension versus concentration measured for Surfactant 1 at pH=7, as described in Example 1b, where the Y-axis represents surface tension (γ) in milliNewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 2] FIG. 2 shows a plot of dynamic surface tension as a change in surface tension versus time for Surfactant 1, as described in Example 1c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 3]FIG. 3 shows a plot of surface tension versus concentration measured at pH=7 for surfactant 2, as described in Example 2b, where the Y-axis represents surface tension (γ) in millinewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 4] FIG. 4 shows a plot of dynamic surface tension as a change in surface tension versus time for Surfactant 2, as described in Example 2c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 5] FIG. 5 shows a plot of surface tension versus concentration measured for surfactant 3 at pH=7, as described in Example 3b, where the Y-axis represents surface tension (γ) in milliNewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 6] FIG. 6 shows a plot of dynamic surface tension as a change in surface tension versus time for Surfactant 3, as described in Example 3c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 7] FIG. 7 shows a plot of surface tension versus concentration measured for surfactant 4 at pH=7, as described in Example 4b, where the Y-axis represents surface tension (γ) in milliNewtons per meter (mN / m) and the X-axis represents concentration (c) in millimolar (mM). [Figure 8] FIG. 8 shows a plot of dynamic surface tension as a change in surface tension versus time for Surfactant 4, as described in Example 4c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). [Figure 9] FIG. 9 shows a plot of surface tension versus concentration measured for surfactant 5 at pH=7, as described in Example 5b, where the Y-axis represents surface tension (γ) in milliNewtons per meter (mN / m) and the X-axis represents concentration (c) in millimoles (mM). [Figure 10]FIG. 10 shows a plot of dynamic surface tension as a change in surface tension versus time for Surfactant 5, as described in Example 5c, where the Y-axis represents surface tension in milliNewtons per meter (mN / m) and the X-axis represents surface elapsed time in milliseconds (ms). DETAILED DESCRIPTION OF THE INVENTION

[0034] As used herein, the phrase "within any range defined between any two of the above values" literally means that any range from any two of the values ​​listed before the phrase may be selected, regardless of whether the values ​​are toward the lower end of the list or toward the upper end of the list. For example, a pair of values ​​may be selected from the two lower values, the two upper values, or a lower value and an upper value.

[0035] As used herein, the term "alkyl" means any saturated carbon chain, which may be straight or branched.

[0036] As used herein, the phrase "surface active" means that the associated compound is capable of lowering the surface tension of the medium in which it is at least partially dissolved and / or the interfacial tension with other phases, and thus may be at least partially adsorbed to air-liquid interfaces and / or other interfaces. The term "surfactant" may be applied to such compounds.

[0037] With respect to imprecision, the terms "about" and "approximately" may be used interchangeably and refer to a measurement that includes the stated measurement and any measurement that is reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount that is understood and readily ascertained by one of ordinary skill in the relevant art. Such deviations may be attributed, for example, to measurement error or small adjustments made to optimize performance. If it is determined that a value for such a reasonably small difference would not be readily ascertained by one of ordinary skill in the relevant art, the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

[0038] Unless expressly stated otherwise or implicitly used otherwise, the term "suds" as used herein refers to a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of liquid. Terms such as "bubble," "foam," and "lather" may be used interchangeably within the meaning of the present invention.

[0039] Unless expressly stated otherwise or implicitly used otherwise, the term "foam profile" as used herein means a property of a detergent composition that relates to the characteristics of foam during the wash-rinse cycle. The foam profile of a detergent composition may include, but is not limited to: These include, but are not limited to, the rate of foam generation upon dissolution in the wash liquor, foam volume and maintenance during the wash cycle, and foam volume and disappearance during the rinse cycle. Preferably, the foam profile includes a Wash Suds Index and a Rinse Suds Index, as specifically determined by the test methods disclosed hereinafter in the Examples. Additional foam-related parameters such as foam stability measured during the wash cycle may also be included.

[0040] Unless expressly stated otherwise or implicitly used otherwise, the term "fluid" as used herein includes liquid, gel, paste, and gas product forms.

[0041] Unless expressly stated otherwise or implicitly used otherwise, the term "liquid" as used herein means a liquid at 25°C and 20 seconds. -1 The term "fluid" refers to a liquid having a viscosity of about 1 to about 2000 mPa·s at a shear rate of 1000 mPa·s.

[0042] Unless expressly stated otherwise or implicitly used otherwise, the term "dry cleaning composition," as used herein, is intended to mean a composition used in a dry cleaning process, including a dry cleaning solvent, any surfactants, detergents, but excluding the laundry articles to be cleaned.

[0043] Unless expressly stated otherwise or implicitly used otherwise, the term "organic dry cleaning solvent," as used herein, is intended to mean any non-aqueous solvent that is preferably in the liquid phase at 20° C. and standard pressure. The term organic has its ordinary meaning, i.e., a compound having at least one carbon-hydrogen bond.

[0044] The present disclosure provides compositions for cleaning and / or degreasing hard and plastic surfaces such as floors, walls, ceilings, roofs, countertops, furniture, plates, cups, glasses, cutlery, eating utensils, machines, machine parts, and equipment used in food preparation and / or packaging; fabric care formulations including laundry detergents, stain removers, cleaning pre-treatments, fabric softeners, fabric dyes, and bleaches; and compositions used in cleaning upholstery and carpets.

[0045] I. Aqueous Cleansing Formulations Laundry detergents, degreasers, stain removers, and laundry pretreatment compositions may contain combinations of detergent surfactants, binders, enzymes, and conditioning agents. Laundry detergent formulations include solids, liquids, powders, bars, sticks, pods, aerosols, and / or gels.

[0046] The laundry detergent compositions of the present invention can be used in applications such as automatic washing machines, semi-automatic washing machines (i.e., machine washing requiring at least one or two manual steps), hand washing, etc. In some embodiments, the detergent compositions are designated for hand washing laundry detergent products.

[0047] Laundry detergent compositions may be in any form, i.e., liquid, emulsion, paste, gel, spray, or foam form; solids such as powders, granules, chunks, tablets, pouches, and bars; delivered in dual- or multi-compartment containers or pouches; wet or dry wipes that can be activated by the user with water (i.e., liquid detergent compositions combined with nonwoven materials or powder detergent compositions combined with nonwoven materials); and other homogeneous or multi-phase consumer cleaning products.

[0048] Part of the fabric care formulations of the present invention includes one or more surfactants, also referred to as a surfactant system. The surfactant system is included to impart cleaning performance to the composition. The formulation system includes at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, and, optionally, at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof. Such surfactants should be physically and chemically compatible with the essential ingredients described herein or should not otherwise unduly impair the stability, aesthetics, or performance of the product.

[0049] The compositions of the present invention may be in any suitable physical form, for example, particles (powder, granules, tablets), liquids, pastes, gels, or bars. Preferably, the detergent compositions are in the form of granules. The compositions may be formulated for hand washing or machine washing detergents.

[0050] A representative, but non-limiting, laundry detergent formulation may include a combination of soap, ionic surfactants, nonionic surfactants, optionally a builder system, and optionally other detergent ingredients. When a certain amount of soap is present in the form of a granule dry-mixed with other ingredients, the soap granule has a certain soap concentration.

[0051] Some preferred detergent compositions according to the present invention exhibit improved solubility characteristics in water of various hardnesses.

[0052] 1. Detergent and / or soap Detergents include anionic, cationic, nonionic, and zwitterionic detergents. Soaps can be prepared by the general formula: (RCO2 - ) n M n+ wherein R is an alkyl group and M is a metal; n+ is either +1 or +2, and in general the alkyl group may be part of a fatty acid, and M may be sodium, lithium, magnesium, calcium, etc.

[0053] The soap according to the invention may constitute about 5-85% by weight of the formulation, preferably 7-60% by weight, more preferably 10-35% by weight. The soap may in part comprise a surfactant system which constitutes about 20-50% by weight of the soap. Preferably, the surfactant system constitutes 30-40% by weight of the soap. In a preferred embodiment of the invention, 80-100% by weight, preferably 85-95% by weight of the soap is present in the form of granules.

[0054] The laundry detergent compositions of the present invention may comprise soap granules having a soap concentration of at least 75% by weight, based on the weight of the composition.

[0055] In some embodiments of the present invention, the soap granules have a soap concentration of 80-95% by weight, preferably 85-90% by weight. Preferably, the soap granules contain more than 90% by weight soap, less than 10% by weight water, and less than 1% by weight sodium hydroxide.

[0056] Useful soap compounds include, but are not limited to, alkali metal soaps such as sodium, potassium, ammonium, and substituted ammonium (e.g., monoethanolamine) salts of higher fatty acids containing about 8 to 24 carbon atoms, or any combination thereof.

[0057] In some embodiments of the present invention, the fatty acid soap is 10 ~C 22 , more preferably C 12 ~C 20 Suitable fatty acids can be obtained from natural sources, such as vegetable or animal esters, e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, rapeseed oil, sunflower oil, cottonseed oil, tallow, fish oil, grease lard, and mixtures thereof. Fatty acids can also be obtained by oxidation of petroleum or by the Fischer-Tropsch process using carbon monoxide. They can also be produced by synthetic means, such as hydrogenation of fatty acids. Resin acids, such as those in rosin and tall oil, are suitable. Naphthenic acids are also suitable. Sodium and potassium soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids produced in a separate manufacturing process. Sodium and potassium salts of fatty acids derived from coconut oil and tallow, and mixtures thereof, i.e., sodium tallow soap, sodium coconut soap, potassium tallow soap, and potassium coconut soap, are particularly useful.

[0058] In some embodiments of the present invention, the fatty acid soap is a lauric acid soap, such as Prifac 5908, a fatty acid soap from Uniqema, neutralized with caustic soda. This soap is an example of a fully hydrogenated or saturated lauric acid soap, which is typically based on coconut oil or palm kernel oil.

[0059] It is preferred, although not essential, that the soap not protrude from the rest of the ingredients, and therefore it should be whitish in colour and approximately round, i.e., with an aspect ratio of less than 2. This ensures that the laundry powder in its final format is free-flowing, and the inclusion of soap granules means that it blends in with the rest of the composition.

[0060] In one preferred embodiment, the soap has a particle size of 400 to 1400 um, preferably 500 to 1200 um.

[0061] In one preferred embodiment, the soap granules have a bulk density of 400 to 650 g / liter, and the bulk density of the fully formulated powder is 400 to 900 g / liter. Fabric washing powders containing a predominant amount of soap are preferred by some consumers for their good cleaning power and tendency to leave clothes feeling softer than those washed with powders based on synthetic detergent active compounds. Soap also has environmental advantages in that it is fully biodegradable and a natural material obtained from renewable sources. Saturated sodium soap has a high Kraft temperature and therefore poor solubility at the low temperatures applied by some consumers. Certain mixtures of saturated and unsaturated soaps are known to have significantly lower Kraft temperatures. However, unsaturated soaps tend to be less stable on storage and have a foul odor. Therefore, the soap mixture used in the granules requires a careful balance between solubility and stability characteristics. The stability of the soap is improved when concentrated in the granules compared to soap incorporated at low concentrations in the complex granules. The soap may be used in combination with a suitable antioxidant, such as ethylenediaminetetraacetic acid and / or ethane-1-hydroxy-1,1-diphosphonic acid. A preservative may also be present to prevent soap decomposition, which may lead to unpleasant odors or discoloration, such as sodium 1-hydroxyethylidene-1,1-diphosphonate.

[0062] 2. Surfactants Surfactants that can be used to practice this aspect of the present invention are compounds of formula I:

[0063] [ka]

[0064] In the formula, R 1 and R 2may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl is optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and an optional counterion associated with this compound, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0065] Anionic surfactants are known to those skilled in the art. Examples include alkyl benzene sulfonates, especially C8-C 15 Linear alkylbenzene sulfonates, primary and secondary alkyl sulfates, especially C8 to C 20 Examples include primary alkyl sulfates, alkyl ether sulfates, olefin sulfonates, alkylxylene sulfonates, dialkyl sulfosuccinates, and fatty acid ester sulfonates. Sodium salts are generally preferred. According to a preferred embodiment of the present invention, the granular laundry detergent composition comprises an anionic surfactant that is a sulfonate anionic surfactant. According to a particularly preferred embodiment, the sulfonate anionic surfactant comprises linear alkyl benzene sulfonate (LAS). In a preferred embodiment, the anionic surfactant is present in an amount of 15 to 50% by weight. In a preferred embodiment, the weight ratio of anionic surfactant to soap is 0.5:1 to 5:1, preferably 1:1 to 2:1. Some nonionic surfactants are also well suited for use in detergent formulations.

[0066] In some embodiments, the nonionic surfactant is present in an amount of 20 to 60% by weight. Nonionic surfactants that can be used include primary and secondary alcohol ethoxylates, particularly C8-C8 ethoxylated with an average of 1 to 20 moles of ethylene oxide per mole of alcohol. 20 Aliphatic alcohols, more particularly C ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol 10 ~C 15 Primary and secondary fatty alcohols. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamides).

[0067] Examples of suitable nonionic surfactants include C 12 ~C 15 Suitable examples include Neodol 255E manufactured by Shell, which is a poly(1-6) ethoxylate. Also suitable is Lutensol A7 manufactured by BASF, which is a C13-C15 ethoxylate with an average degree of ethoxylation of 7. The HLB value can be calculated according to the method set forth in Griffin, J. Soc. Cosmetic Chemists, 5 (1954) 249-256.

[0068] 3. Builder Builders may be added to detergent formulations to enhance the cleaning properties of detergents. Such compounds are used to remove Ca from water. 2+ and / or Mg 2+ They may function by at least one of the following: removing or scavenging divalent cations commonly present as surfactants; creating or contributing to the creation of an alkaline environment; improving surfactant performance; and stabilizing the dispersion of soils in the cleaning solution.

[0069] Commonly used builders include, but are not limited to, sodium tripolyphosphate Thorium, nitriloacetates, and zeolites.

[0070] The compositions of the present invention may contain a detergent builder. Preferably, the builder is present in an amount of 0 to 15% by weight, based on the weight of the total composition. Alternatively, the compositions may be essentially free of detergent builders.

[0071] The builder may be selected from strong builders such as phosphate builders, aluminosilicate builders, and mixtures thereof. Additionally or alternatively, one or more weak builders may be present, such as calcite / carbonate, citrate, or polymer builders.

[0072] The phosphate builder, if present, may be selected, for example, from alkali metal, preferably sodium, pyrophosphates, orthophosphates, and tripolyphosphates, and mixtures thereof.

[0073] The aluminosilicate, if present, may be selected from one or more crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1473201 (Henkel), amorphous aluminosilicates as disclosed in GB 1473202 (Henkel), and mixed crystalline / amorphous aluminosilicates as disclosed in GB 1470250 (Procter & Gamble), and layered silicates as disclosed in EP 164514(B) (Hoechst).

[0074] The alkali metal aluminosilicate may be either crystalline or amorphous or a mixture thereof and has the general formula: 0.8-1.5Na2O·Al2O3·0.8-6SiO2.

[0075] These materials may generally contain some bound water and are required to have a calcium ion-exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5 to 3.5 SiO2 units (in the formula above). Both amorphous and crystalline materials can be readily prepared by the reaction of sodium silicate with sodium aluminate, as extensively described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergent builders are described, for example, in British Patent No. 1429143 (Procter & Gamble). Preferred sodium aluminosilicates of this type are the well-known, commercially available zeolites A and X, and mixtures thereof.

[0076] The zeolite may be the commercially available Zeolite 4A, which is currently widely used in laundry detergent powders. However, according to a preferred embodiment of the present invention, the zeolite builder incorporated in the compositions of the present invention is Maximum Aluminum Zeolite P (Zeolite MAP) as described and claimed in EP 384070(A) (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the P-type zeolite having a silicon-to-aluminum ratio not exceeding 1.33, preferably in the range of 0.90 to 1.33, and more preferably in the range of 0.90 to 1.20.

[0077] Suitable inorganic salts include alkaline agents such as carbonates, sulfates, silicates, metasilicates of alkali metals, preferably sodium, as simple or complex salts. The inorganic salt may be selected from the group consisting of sodium carbonate, sodium sulfate, burkeite, and mixtures thereof.

[0078] 4.Surface active raw material components In addition to the surfactants and builders discussed above, the compositions may contain other active ingredients to enhance performance and properties, if desired.

[0079] The additional detergent-active compounds (surfactants) may be selected from soap and non-soap anionic, cationic, nonionic, amphoteric, and zwitterionic detergent-active compounds, and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents," Volumes I and II, by Schwartz, Perry, and Berch.

[0080] Cationic surfactants that can be used include those of the general formula RRRRNX, where the R groups are long or short chain hydrocarbyls, typically alkyl, hydroxyalkyl, or ethoxylated alkyl groups, and X is a solubilizing anion, a quaternary ammonium salt (e.g., where R is a C-C 22 Alkyl groups, preferably C8 to C 10 or C 12 ~C 14 R is an alkyl group, R is a methyl group, and R and R may be the same or different and are methyl or hydroxyethyl groups), and cationic esters (e.g., choline esters).

[0081] Amphoteric and / or zwitterionic surfactants may be present. Some amphoteric surfactants that may be used in the practice of the present invention include amine oxides.

[0082] Some zwitterionic surfactants that can be used in the practice of the present invention include betaines, such as amidobetaines.

[0083] 5. Bleach The detergent composition according to the present invention may suitably contain a bleaching agent system. The bleaching agent system is preferably based on a peroxide bleaching compound, such as an inorganic persalt or organic peroxoacid capable of yielding hydrogen peroxide in aqueous solution. Suitable peroxide bleaching compounds include organic peroxides such as urea peroxide, and inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates, and persulfates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. Sodium percarbonate having a protective coating against moisture destabilization is particularly preferred. Sodium percarbonate having a protective coating containing sodium metaborate and sodium silicate is disclosed in British Patent No. 2123044(B) (Kao).

[0084] The peroxide bleach compound is suitably present in an amount of from 5 to 35% by weight, preferably from 10 to 25% by weight.

[0085] The peroxide bleach compounds may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low wash temperatures. The bleach precursor is suitably present in an amount of 1 to 8% by weight, preferably 2 to 5% by weight.

[0086] Preferred bleach precursors are peroxycarboxylic acid precursors, more particularly peracetic acid precursors and peroxybenzoic acid precursors, and peroxycarbonic acid precursors. A particularly preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetraacetylethylenediamine (TAED). Also of interest are peroxybenzoic acid precursors, particularly N,N,N-trimethylammonium toluyloxybenzenesulfonate.

[0087] A bleach stabilizer (heavy metal scavenger) may also be present. Suitable bleach stabilizers include ethylenediaminetetraacetic acid (EDTA) and polyphosphonates such as Dequest, EDTMP, etc.

[0088] 6. Enzymes The detergent composition may also contain one or more enzymes. Suitable enzymes include, for example, proteases, amylases, cellulases, oxidases, mannanases, peroxidases, and lipases, which can be used for incorporation into the detergent composition. In particulate detergent compositions, detergent enzymes are generally used in the form of granules in an amount of about 0.1 to about 3.0% by weight. However, any suitable physical form of the enzyme may be used in any effective amount.

[0089] 7. Polymers Some detergents may contain cationic polymers, such as those described below, which, when used in laundry detergent compositions in an amount ranging from about 0.01% to about 15% by weight, are effective in improving the foam profile of such laundry detergent compositions compared to similar formulations but without such cationic polymers.

[0090] Cationic polymers useful in detergents, such as laundry detergents, can include terpolymers containing three different types of structural units, which are substantially free, and preferably essentially free, of any other structural components. The structural units or monomers can be incorporated into the cationic polymer in a random or block fashion.

[0091] The first structural unit of the cationic polymer is a nonionic structural unit derived from methacrylamide (AAm). The cationic polymer contains about 35 mol % to about 85 mol %, preferably about 55 mol % to about 85 mol %, and more preferably about 65 mol % to about 80 mol % of the AAm-derived structural unit.

[0092] The second structural unit of the cationic polymer may be, for example, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkyl methacrylamide, methacylamidoalkyl trialkylammonium salts, acrylamidoalkyl trialkylammonium salts, vinylamine, vinyl ... The cationic structural units are derived from any suitable water-soluble cationic ethylenically unsaturated monomers such as vinylimidazole, quaternized vinylimidazole, and diallyldialkylammonium salts.

[0093] For example, the second cationic structural unit can be derived from a monomer selected from the group consisting of diallyldimethylammonium salt (DADMAS), N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]trimethylammonium salt, N,N-dimethylaminopropyl acrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyltrimethylammonium salt (APTAS), methacrylamidopropyltrimethylammonium salt (MAPTAS), and quaternized vinylimidazole (PVi), and combinations thereof.

[0094] In some embodiments, the second cationic structural unit is derived from a diallyldimethylammonium salt (DADMAS), such as, for example, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium fluoride, diallyldimethylammonium bromide, diallyldimethylammonium iodine, diallyldimethylammonium bisulfate, diallyldimethylammonium alkyl sulfate, diallyldimethylammonium dihydrogen phosphate, diallyldimethylammonium alkyl phosphate, diallyldimethylammonium dialkyl phosphate, and combinations thereof. The second cationic structural unit can be derived from a [2-(methacryloylamino)ethyl]trimethylammonium salt, such as, for example, [2-(methacryloylamino)ethyl]trimethylammonium chloride, [2-(methacryloylamino)ethyl]trimethylammonium fluoride, [2-(methacryloylamino)ethyl]trimethylammonium bromide, [2-(methacryloylamino)ethyl]trimethylammonium iodine, [2-methacryloylamino)ethyl]trimethylammonium bisulfate, [2-(methacryloylamino)ethyl]trimethylammonium alkyl sulfate, [2-(methacryloylamino)ethyl]trimethylammonium dihydrogen phosphate, [2-(methacryloylamino)ethyl]trimethylammonium alkyl phosphate, [2-(methacryloylamino)ethyl]trimethylammonium dialkyl phosphate, and combinations thereof. Additionally, the second cationic structural unit can be derived from APTAS, including, for example, acrylamidopropyltrimethylammonium chloride (APTAC), acrylamidopropyltrimethylammonium fluoride, acrylamidopropyltrimethylammonium bromide, acrylamidopropyltrimethylammonium iodine, acrylamidopropyltrimethylammonium bisulfate, acrylamidopropyltrimethylammonium alkyl sulfate, acrylamidopropyltrimethylammonium dihydrogen phosphate, acrylamidopropyltrimethylammonium alkyl phosphate, acrylamidopropyltrimethylammonium dialkyl phosphate, and combinations thereof.Still further, the second cationic structural unit can be derived from MAPTAS, including, for example, methacrylamidopropyltrimethylammonium chloride (MAPTAC), methacrylamidopropyltrimethylammonium fluoride, methacrylamidopropyltrimethylammonium bromide, methacrylamidopropyltrimethylammonium iodine, methacrylamidopropyltrimethylammonium bisulfate, methacrylamidopropyltrimethylammonium alkyl sulfate, methacrylamidopropyltrimethylammonium dihydrogen phosphate, methacrylamidopropyltrimethylammonium alkyl phosphate, methacrylamidopropyltrimethylammonium dialkyl phosphate, and combinations thereof.

[0095] The second cationic structural unit is present in the cationic polymer in an amount within the range of about 10 mol % to about 65 mol %, preferably about 15 mol % to about 60 mol %, and more preferably about 15 mol % to about 30 mol %.

[0096] A relatively high amount of the first nonionic structural unit (e.g., 65 mol % to 80 mol %) and a moderate amount of the second cationic structural unit (e.g., 15 mol % to 30 mol %) ensures good foaming benefits and also good final product appearance. If the first nonionic structural unit is present at less than 65 mol % and the second cationic structural unit is present at more than 30 mol %, the foaming benefits or final product appearance begin to decrease; for example, the rinse foam volume may increase significantly, or the final product may no longer be transparent but have a cloudy appearance. Similarly, if the first nonionic structural unit is present at more than 85 mol % and the second cationic structural unit is present at less than 10 mol %, the rinse foam volume increases to an unacceptable level.

[0097] The third structural unit of the cationic polymer is an anionic structural unit derived from methacrylic acid (AA) or its anhydride. The cationic polymer may contain about 0.1 mol % to about 35 mol %, preferably about 0.2 mol % to about 20 mol %, more preferably about 0.5 mol % to about 10 mol %, and most preferably about 1 mol % to about 5 mol % of the third anionic structural unit.

[0098] The presence of a relatively small amount (e.g., 1 mol % to 5 mol %) of a third anionic structural unit helps increase the hydrophilicity of the resulting polymer, which in turn leads to better cleanability. , which can lead to better clay removal in particular. Too many third anionic structural units (e.g., greater than 30 mole %) can detract from the foaming benefits of the resulting polymer.

[0099] II. Dry cleaning According to some embodiments of the present invention, a formulation for a dry cleaning process is provided for domestic dry cleaning comprising a dry cleaning step of contacting laundry items contaminated with particulate soil with a dry cleaning composition, wherein the liquor-to-cloth ratio (wt / wt) (LCR) is at most 20, the composition comprising: a) a non-flammable, chlorine-free organic dry cleaning solvent; and b) a cleaning-effective amount of an acid surfactant.

[0100] In some embodiments, the dry cleaning process is a low-aqueous dry cleaning process and the composition is a low-aqueous dry cleaning composition comprising 0.01 to 10% by weight water.

[0101] According to yet another aspect of the present invention, a dry cleaning process further comprises a non-aqueous dry cleaning step of contacting a laundry article with a non-aqueous dry cleaning composition comprising 0.001 to 10 wt. % surfactant, 0 to 0.01 wt. % water, 0 to 50 wt. % co-solvent, and a non-flammable, chlorine-free organic dry cleaning solvent. According to another aspect of the present invention, the dry cleaning process further comprises a) contacting the article with a non-aqueous dry cleaning composition comprising 0.001 to 10 wt. % surfactant, 0 to 0.01 wt. % water, 0 to 50 wt. % co-solvent, and a non-flammable, chlorine-free organic dry cleaning solvent; and b) contacting the article with a low-aqueous dry cleaning composition comprising 0.001 to 10 wt. % acid surfactant, and optionally, at least one rinse step, wherein the rinse composition comprises 0 to 0.0001 wt. % of a surfactant; 0 to 10 wt. % of water; 0 to 50 wt. % of a co-solvent; and a non-flammable, chlorine-free organic dry cleaning solvent.

[0102] Depending on the cleaning desired, the low-aqueous and non-aqueous compositions may be used in any order. However, in some cases, it may be preferable to contact the article with the non-aqueous composition before the low-aqueous dry cleaning composition. Indeed, various other steps may be performed before or after the low-aqueous dry cleaning step, such as regeneration, garment care treatment, and / or rinsing steps, and indeed any other steps known to those skilled in the art.

[0103] Some aspects of the present invention may be particularly suitable for cleaning laundry items contaminated with household contaminants selected from the group consisting of kitchen grease, particulate soils, and mixtures thereof. Thus, according to one embodiment, the dry cleaning process preferably includes contacting laundry items with a dry cleaning composition, wherein the laundry items are contaminated with household contaminants selected from kitchen grease, particulate soils, and mixtures thereof. Typical particulate soil contamination includes any particulate matter capable of contaminating clothing, such as soil, mud, sand, charcoal, cosmetics, deodorants, toothpaste, etc., as well as corroded iron particles and mixtures thereof. Kitchen grease typically includes edible oils and fats of animal or plant origin, such as lard, sunflower oil, soybean oil, olive oil, palm oil, peanut oil, rapeseed oil, and mixtures thereof.

[0104] Generally, an article, such as clothing, is treated with a cleaning-effective amount of a dry cleaning composition according to one embodiment of the present invention for a time effective to clean or otherwise remove stains from the article. The laundry articles are cleaned by contacting the articles with the dry cleaning composition for a period of time. Preferably, the laundry articles are immersed in the dry cleaning composition. The amount of dry cleaning composition used and the length of time the composition is in contact with the articles can vary based on the equipment and the number of articles to be cleaned. Typically, the dry cleaning process includes at least one step of contacting the articles with the dry cleaning composition according to the first aspect of the present invention and at least one step of rinsing the articles with a fresh dose of dry cleaning solvent. The rinse composition typically comprises primarily solvent, although detergents may be added if desired.

[0105] In some embodiments of the present invention, the pretreatment composition may include an in situ formulation of a dry cleaning composition. Laundry items are pretreated with the pretreatment composition, and then the pretreated laundry items are contacted with the remaining ingredients of the dry cleaning composition, thereby formulating the dry cleaning composition in situ. The pretreatment step may be performed manually outside the drum of a washing machine, or mechanically inside the drum as part of the pretreatment step. The pretreatment step itself does not need to be performed by immersion; that is, it may be limited to treating only the soiled area, provided that the laundry item is immersed in the dry cleaning composition when it comes into contact with all ingredients that make up the final dry cleaning composition. For example, if the dry cleaning composition includes a dry cleaning solvent, water, and a surfactant, the soiled area of ​​the laundry item may be pretreated manually or by an automated process using a premix of water and surfactant. After an effective pretreatment time has elapsed, the laundry item may be contacted with the remaining ingredients in the drum. The remaining dry cleaning ingredients may include a dry cleaning solvent (and, optionally, additional water and / or detergent) to in situ produce at least one dry cleaning composition according to this aspect of the invention. Typically, the pretreatment time is at least 5 seconds, but may be less than 1 day, preferably less than 1 hour, and more preferably less than 30 minutes. The pretreatment composition may be formulated to treat specific soils. For example, to treat proteinaceous soils, a cleaning-effective amount of protease and other enzymes may be included. In another embodiment, the complete dry cleaning composition is premixed in a separate premix compartment. For example, if the dry cleaning composition includes a dry cleaning solvent, a surfactant, and water, these may be premixed in a separate compartment before contacting the dry cleaning composition with laundry items. In some embodiments, such a premix is ​​in the form of an emulsion or microemulsion. Formation of the premix, for example, a water-in-oil emulsion, may be effected by any number of suitable procedures.For example, the aqueous phase containing a detergent-effective amount of surfactant and the solvent phase can be metered into contact just before these components are introduced into a mixing device. Metering is preferably continued so that the desired solvent / water ratio remains relatively constant. Suitable mixing devices for this purpose include, for example, pump assemblies or in-line static mixers, centrifugal pumps or other types of pumps, colloid mills or other types of mills, rotary mixers, ultrasonic mixers, and other means for dispersing one liquid into another liquid. In some embodiments, immiscible liquids can be used to provide sufficient agitation to form an emulsion or pseudo-emulsion.

[0106] These static mixers comprise a device through which an emulsion is forced at high speed, where it undergoes abrupt changes in direction and / or diameter of the channels that make up the interior of the mixer, resulting in pressure losses that are a factor in obtaining the correct emulsion in terms of droplet size and stability.

[0107] In one variant of the method of the present invention, the mixing steps are, for example, sequential. The procedure consists of a first step in which the solvent and the emulsifier are mixed, and a second step in which this premix is ​​mixed with water and emulsified. In another variant of the method of the present invention, the steps are carried out in a continuous mode.

[0108] The premixing may be carried out at room temperature, which is also the temperature of the fluids and raw materials used.

[0109] Batch processes such as overhead mixers or continuous processes such as two-fluid coextrusion nozzles, in-line injectors, in-line mixers, or in-line screens may be used to prepare the emulsion. The size of the emulsion components in the final composition can be adjusted by changing the mixing speed, mixing time, mixing equipment, and the viscosity of the aqueous solution. Generally, emulsions with larger droplet sizes can be produced by reducing the mixing speed, shortening the mixing time, reducing the viscosity of the aqueous solution, or using a mixing equipment that generates less shear force during mixing. Ultrasonic mixers are particularly preferred. It is understood that although the above description relates to the addition of surfactants, it can also be applied to the addition of detergents.

[0110] 1. Solvent In general, dry cleaning solvents are typically nonflammable, chlorine-free, organic dry cleaning solvents. While the term "dry cleaning solvent" is used in the singular, it should be noted that mixtures of solvents may also be used. Therefore, the singular should be understood to encompass the plural, and vice versa. Due to typical environmental concerns associated with chlorine-containing solvents, it is preferable that the solvent not contain Cl atoms. Additionally, the solvent should not be flammable, such as most petroleum or mineral spirits, which typically have a flash point as low as 20°C or lower. The term "nonflammable" is intended to refer to dry cleaning solvents that have a flash point of at least 37.8°C, more preferably at least 45°C, and most preferably at least 50°C. The flash point limit of at least 37.8°C for nonflammable liquids is set forth in the 1996 edition of NFPA 30, the National Fire Protection Association's (USA) Standard for Flammable and Combustible Liquids. The preferred test method for determining a solvent's flash point is the standard test described in NFPA 30. One class of solvents is the fluorinated organic dry cleaning solvents, which include hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). However, even more preferred solvents are non-flammable, non-halogenated solvents such as siloxanes (see below). It should be noted that mixtures of different dry cleaning solvents may also be used.

[0111] Some solvents are non-ozone depleting, and a useful general definition for ozone depletion potential is provided by the U.S. Environmental Protection Agency, which is the ratio of a chemical's effect on the ozone compared to that of a similar mass of CFC-11. Thus, the ODP of CFC-11 is defined to be 1.0.

[0112] A hydrofluorocarbon may be used as the solvent. One suitable hydrofluorocarbon solvent is represented by the formula C,H,F(2x+2-y), where x is 3 to 8, y is 1 to 6, and the molar ratio of F / H in the hydrofluorocarbon solvent is greater than 1.6. Preferably, X is 4 to 6, and most preferably, X is 5 and y is 2. Hydrofluorocarbon solvents selected from the isomers of decafluoropentane and mixtures thereof are particularly suitable. In particular, 1,1,1,2,2,3,4,5,5,5-decafluoropentane is useful. EI Du Pont De Nemours and Company sells this compound under the trade name Vertrel XF™.

[0113] Hydrofluoroethers (HFEs) suitable for use in the present invention are generally low-polarity chemical compounds containing a minimum of carbon, fluorine, hydrogen, and catenary (i.e., chain-long) oxygen atoms. HFEs may optionally contain additional chain atoms such as nitrogen and sulfur. The HFE may contain a cyclic heteroatom. The HFE has a molecular structure that may be linear, branched, or cyclic, or a combination thereof (e.g., alkylalicyclic), preferably contains no ethylenic unsaturation, and has a total of about 4 to about 20 carbon atoms. Such HFEs are known and readily available as essentially pure compounds or as mixtures. Preferred hydrofluoroethers may have boiling points within the range of about 40°C to about 275°C, preferably about 50°C to about 200°C, and even more preferably about 50°C to about 121°C. It is highly desirable that the hydrofluoroether does not have a flash point. In general, if an HFE has a flash point, decreasing the F / H ratio or decreasing the number of carbon-carbon bonds each lowers the flash point of the HFE (see WO 00 26206).

[0114] Useful hydrofluoroethers include two types: segregated hydrofluoroethers and omega-hydrofluoroalkyl ethers. Structurally, segregated hydrofluoroethers contain at least one mono-, di-, or tri-alkoxy-substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound.

[0115] Several siloxane solvents may also be advantageously used in the present invention. The siloxane may be linear, branched, cyclic, or a combination thereof. One preferred branched siloxane is tris(trimethylsiloxyl)silane. Linear and cyclic oligodimethylsiloxanes are also preferred. One preferred class of siloxane solvents are alkylsiloxanes represented by the following formula: R 3 -Si(-O-SiR 2 ) w -R wherein each R is independently selected from alkyl groups having 1 to 10 carbon atoms, and w is an integer from 1 to 30. Preferably, R is methyl and w is 1 to 4, or even more preferably, w is 3 or 4.

[0116] Among the cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are particularly effective. Highly useful siloxanes are selected from the group consisting of decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

[0117] Suitable organic solvents for dry cleaning include at least one solvent selected from the group consisting of nonafluoromethoxybutane, nonafluoroethoxybutane, and isomers of decafluoropentane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Some preferred organic dry cleaning solvents include solvents selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

[0118] The dry cleaning compositions of the present invention generally contain greater than about 50 weight percent organic dry cleaning solvent, preferably greater than about 75 weight percent, more preferably greater than about 80 weight percent, more preferably greater than about 85 weight percent, and even more preferably greater than about 95 weight percent, but preferably less than 100 weight percent, based on the weight of the total dry cleaning composition. Such amounts can aid in improving drying times and maintaining a high or no flash point. In the rinsing or conditioning step, the dry cleaning composition further contains at least 99 weight percent organic dry cleaning solvent, and in some cases as much as 100 weight percent organic dry cleaning solvent, based on the weight of the total dry cleaning composition. The coating may include a coating solvent.

[0119] In some cases, water may be used in the dry cleaning process, and the amount of water is important. In such cases, the amount of water present at each step of the dry cleaning process is a level that allows for safe cleaning of laundry items. This includes laundry items that can only be dry cleaned. The amount of water present in low-aqueous dry cleaning compositions is preferably 0.01 to 50 wt. % water, more preferably 0.01 to 10 wt. %, even more preferably 0.01 to 0.9 wt. % water, or more preferably 0.05 to 0.8 wt. %, or most preferably 0.1 to 0.7 wt. % water, based on the weight of the dry cleaning composition. The amount of water present in non-aqueous dry cleaning compositions is preferably 0 to 0.1 wt. % water, or more preferably 0 to 0.01 wt. %, or even more preferably 0 to 0.001 wt. %, and most preferably 0 wt. % water, based on the weight of the dry cleaning composition.

[0120] If the dry cleaning composition contains water, preferably the water to fabric ratio (wt / wt) (WCR) is less than 0.45, more preferably less than 0.35, more preferably less than 0.25, more preferably less than 0.2, most preferably less than 0.15, but typically greater than 0.0001, preferably greater than 0.001, more preferably greater than 0.01.

[0121] When the dry cleaning process includes more than one step, especially when the dry cleaning composition includes water and a solvent, the WCR is preferably applied to all steps of the dry cleaning process. However, the WCR may or may not be different for each step. It is also preferred that the WCR be applied to each step of the dry cleaning process where the LCR is greater than 1.

[0122] 2. Co-solvent The composition of the present invention may contain one or more cosolvents. The purpose of the cosolvent in the dry cleaning composition of the present invention is often to increase the solvency of the dry cleaning composition against various soils. The cosolvent also allows for the formation of a homogeneous solution containing the cosolvent, the dry cleaning solvent, and the soil, or containing the cosolvent, the dry cleaning solvent, and, optionally, a cleaning agent. As used herein, a "homogeneous composition" refers to a single-phase composition or a composition that appears to have only a single phase, such as a macroemulsion, microemulsion, or azeotrope. However, when a cosolvent is used, it is preferable that the dry cleaning composition is not an azeotrope, because azeotropes may have poor robustness.

[0123] Useful cosolvents of the present invention are soluble in dry cleaning solvents or water, are compatible with typical cleaning agents, and are capable of improving the solubilization of hydrophilic complex soils and oils typically found in soils on clothing, such as vegetable oils, mineral oils, or animal oils. Any cosolvent or cosolvent mixture meeting the above criteria may be used.

[0124] Useful cosolvents include, for example, alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluoro-tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, fully or partially halogenated derivatives thereof, and mixtures thereof. Preferably, the cosolvent is selected from the group consisting of alcohols, alkanes, alkenes, cycloalkanes, ethers, esters, cyclic amides, aromatics, ketones, fully or partially halogenated derivatives thereof, and mixtures thereof. Representative examples of cosolvents that can be used in the dry cleaning compositions of the present invention include methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl alcohol ... -butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkylpyrrolidones (such as N-methylpyrrolidone and N-ethylpyrrolidone), methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane.

[0125] Preferably, the co-solvent is present in the compositions of the present invention in an amount by weight that is effective to form a homogeneous composition with other dry cleaning solvents, such as HFE. The effective amount of co-solvent will vary depending on which co-solvent or co-solvent blend is used and the other dry cleaning solvents used in the composition. However, the preferred maximum amount of any particular co-solvent present in the dry cleaning composition should be low enough to maintain the dry cleaning composition non-flammable, as defined above.

[0126] Generally, the co-solvent may be present in the compositions of the present invention in an amount of from about 1 to about 50 weight percent, preferably from about 5 to about 40 weight percent, and more preferably from about 10 to about 25 weight percent. In some cases, the co-solvent may be present in an amount from about 0.01 weight percent based on the total dry cleaning composition.

[0127] 3. Surfactants An embodiment of the present invention is at least one compound of formula I,

[0128] [ka]

[0129] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and optionally a counterion associated with this compound, when present, selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0130] The dry cleaning compositions of the present invention may employ a wide variety of cyclic, linear, or branched surfactants, both fluorinated and non-fluorinated, known in the art. Preferred solvent-compatible surfactants, as described below, have at least 4 carbon atoms, but preferably fewer than 200 carbon atoms, or more preferably fewer than 90 carbon atoms. Examples of suitable surfactants include nonionic, anionic, cationic, and zwitterionic surfactants. Solvent-compatible surfactants typically have a solvent-philic moiety that increases the surfactant's solubility in the dry cleaning solvent / composition. Effective surfactants may contain one or more polar hydrophilic groups and one or more dry cleaning solvent-philic moieties with at least four carbon atoms so that the surfactant is soluble in the dry cleaning solvent / composition. The surfactant is preferably soluble in the dry cleaning composition, i.e., soluble at 20°C up to the amount of surfactant used in the dry cleaning composition. The composition may contain one surfactant or a mixture of surfactants depending on the desired cleaning and fabric care. One preferred surfactant is an anionic surfactant. Another preferred surfactant is a cationic surfactant.

[0131] The polar hydrophilic group Z may be nonionic, ionic (i.e., anionic, cationic, or amphoteric), or a combination thereof. Typical nonionic moieties include polyoxyethylene and polyoxypropylene moieties. Typical anionic moieties include carboxylate, sulfonate, sulfate, or phosphate moieties. Typical cationic moieties include quaternary ammonium, protonated ammonium, imidazoline, amine, diamine, sulfonium, and phosphonium moieties. Typical amphoteric moieties include betaine, sulfobetaine, aminocarboxyl, amine oxide, and various other combinations of anionic and cationic moieties. Particularly suitable surfactants contain at least one polar hydrophilic group Z that is an anionic moiety, in which case the counterion may be as described below.

[0132] The polar hydrophilic group Z is preferably selected from the group including -SOM, -SOM, -POM, -POM, -COM, and mixtures thereof, and each M may independently be selected from the group including H, NR, Na, K, and Li, and each R is independently selected from H and C alkyl radicals, but is preferably H. Preferably, M is H, although in some cases a salt may be used.

[0133] The surfactant may be fluorinated, and more preferably is a fluorinated acid. Suitable fluorosurfactants are most often surfactants according to formula (1): (Xf)n(Y)m(Z)p It contains one, two, or three or more fluorinated radicals (Xf) and one or more polar hydrophilic groups (Z), which radicals and polar hydrophilic groups are usually (but not necessarily) connected together by one or more suitable linking groups (Y). Preferably, n and p are integers independently selected from 1 to 4, and m is selected from 0 to 4. When the surfactant contains two or more Xf, Y, or Z groups, each of Xf, Y, and Z can be the same or different. The polar hydrophilic group can be connected to Y by a covalent bond, or to Xf in the absence of Y.

[0134] The fluorinated radical Xf may generally be linear or cyclic, saturated or unsaturated, aromatic or non-aromatic, and preferably has at least three carbon atoms. The carbon chain may be linear or branched and may contain heteroatoms, such as oxygen or sulfur, but preferably not nitrogen. Xf is aliphatic and saturated. Perfluorinated Xf radicals are preferred, although hydrogen or chlorine may be present as substituents, provided that no more than two per two carbon atoms are present on any atom. Preferably, the radical contains at least a terminal perfluoromethyl group. Radicals containing about 20 or fewer carbon atoms are preferred, as larger radicals usually mean reduced fluorine utilization efficiency. Particularly suitable Xf groups may be based on perfluorocarbons: CF, where n is 1 to 40, preferably 2 to 26, and most preferably 2 to 18, or on oligomers of hexafluoropropylene oxide: ICF(CF)-CF.O. where n is 1 to 30. Suitable examples of the latter are commercially available from EI DuPont de Nemours and Co. under the name Krytox™ 157, particularly Krytox™ 157 FSL. Fluoroaliphatic radicals containing about 2 to 14 carbon atoms are more preferred.

[0135] The linking group Y is selected from groups such as alkyl, alkylene, alkylene oxide, arylene, carbonyl, ester, amide, ether oxygen, secondary or tertiary amine, sulfonamido alkylene, carboxamido alkylene, alkylenesulfonamido alkylene, alkyleneoxyalkylene, or alkylenethioalkylene, or mixtures thereof. In one preferred embodiment, Y is (CH) or (CH)O, and t is 1 to 10, preferably 1 to 6, and most preferably 2 to 4. Alternatively, Y may be absent, in which case X and Z are directly connected by a covalent bond.

[0136] Another suitable class of surfactants is non-fluorinated surfactants according to formula II: (Xh)n(Y)m(Z)p Formula II wherein Xh may be a linear, branched, or cyclic, saturated or unsaturated, aromatic or non-aromatic radical, preferably having at least 4 carbon atoms. Xh preferably comprises a hydrocarbon radical. When Xh is a hydrocarbon, the carbon chain may be linear, branched, or cyclic and may include heteroatoms such as oxygen, nitrogen, or sulfur, although nitrogen may not be preferred. In some embodiments, Xh is aliphatic and saturated. Radicals containing about 24 or fewer carbon atoms are preferred. Z is one or more polar hydrophilic groups, usually (but not necessarily) connected together by one or more suitable linking groups Y. Preferably, n and p are independently selected from 1, 2, 3, and 4, and m is selected from 0, 1, 2, 3, and 4.

[0137] One preferred surfactant is an acid surfactant.Some surfactants include anionic surfactants.Anionic surfactants are generally known in the art, such as alkylarylsulfonates (e.g., alkylbenzenesulfonates), alkylarylsulfonic acids (e.g., sodium salts and ammonium salts of toluene-, xylene-, and isopropylbenzene-sulfonic acids), sulfonated amines and sulfonated amides (e.g., amidosulfonates), carboxylated alcohols and carboxylated alkylphenol ethoxylates, diphenylsulfonates, fatty esters, isethionates, lignin-based surfactants, olefin sulfonates (e.g., R is C 10 ~C 16RCHCHSONa (e.g., RCHCHSONa), phosphorus-based surfactants, protein-based surfactants, sarcosine-based surfactants (e.g., N-acyl sarcosinate salts such as sodium N-lauroyl sarcosinate), sulfates and sulfonates of oils and / or fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of fatty esters, sulfates of aromatic or fluoro-containing compounds, sulfosuccinamates, sulfosuccinates (e.g., diamyl-, dioctyl-, and diisobutyl-sulfosuccinate), taurates, and sulfonic acids. Examples of suitable non-fluorinated anionic surfactants include Crodafos™ 810A (manufactured by Croda).

[0138] In addition to acid surfactants, other classes of surfactants may be used. Suitable surfactants include, but are not limited to, nonionic and cationic surfactants. Compounds suitable for use as nonionic surfactants in the present invention are compounds that do not have an individual charge when dissolved in an aqueous medium. Nonionic surfactants are generally known in the art and include, for example, alkanolamides (e.g., monoethanolamides, diethanolamides, and monoisopropyl ethers of coco, lauric, oleic, and stearic acids). ethoxylated alkylphenols (such as nonylphenyl ethoxylated amines and ethoxylated amides), ethoxylated fatty acids, ethoxylated fatty esters, and ethoxylated fatty oils (such as mono- and di-esters of acids such as lauric acid, isostearic acid, pelargonic acid, oleic acid, coco acid, stearic acid, and ricinoleic acid, and oils such as castor oil and tall oil), fatty esters, fluorocarbon-containing materials, glycerol esters (such as glycerol esters), and the like. Examples of surfactants include glycerol monostearate, glycerol monolaurate, glycerol dilaurate, glycerol monoricinoleate, and glycerol oleate, glycol esters (e.g., propylene glycol monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monolaurate, diethylene glycol monolaurate, diethylene glycol monooleate, and diethylene glycol stearate), lanolin-based surfactants, monoglycerides, phosphate esters, polysaccharide ethers, propoxylated fatty acids, propoxylated alcohols, and propoxylated alkylphenols, protein-based organic surfactants, sorbitan-based surfactants (e.g., sorbitan oleate, sorbitan monolaurate, and sorbitan palmitate), sucrose esters and glucose esters, and thio- and mercapto-based surfactants.

[0139] Other suitable nonionic surfactants include polyethylene oxide condensates of nonylphenol and myristyl alcohol, such as those described in U.S. Patent No. 4,685,930 to Kasprzak; and b) fatty alcohol ethoxylates, R—(OCH2CH2)OH, where a is 1 to 100, typically 1 to 30, and R is a hydrocarbon residue of 8 to 20 carbon atoms, typically a linear alkyl. Examples include, but are not limited to, polyoxyethylene lauryl ether having 4 or 10 oxyethylene groups; polyoxyethylene cetyl ether having 2, 6, or 10 oxyethylene groups; polyoxyethylene stearyl ether having 2, 5, 15, 20, 25, or 100 oxyethylene groups; and polyoxyethylene (2), (10) oleyl ether having 2 or 10 oxyethylene groups. Commercially available examples include, but are not limited to, BRIJ® and NEODOL. See also U.S. Patent No. 6,013,683 to Hill et al. Other suitable non-ionic surfactants include Tween™.

[0140] Suitable cationic surfactants include, but are not limited to, dialkyldimethylammonium salts having the formula R"R"N"(CH).X, where R' and R" are each independently selected from the group consisting of hydrocarbons containing moieties having 1 to 30 C atoms or derived from tallow, coconut oil, or soybean oil, and X is Cl, I, or Br. Examples include didodecyldimethylammonium bromide (DDAB), dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, didocosyldimethylammonium chloride, dicoconutdimethylammonium chloride, ditallowdimethylammonium bromide (DTAB). Commercially available examples include, but are not limited to, ADOGEN, ARQUAD, TOMAH, and VARIOUAT. See also U.S. Pat. No. 6,013,683 to Hill et al.

[0141] These and other compounds are suitable for use in combination with organic dry cleaning solvents as adjuvants. Other surfactants are known in the art and are described in Kirk Othmer's Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, incorporated herein by reference. "Surfactants and Detersive Systems." Additional suitable nonionic detergent surfactants are generally disclosed in U.S. Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13, line 14 to column 16, line 6, which is incorporated herein by reference. Other suitable detergent surfactants are generally disclosed in WO 0246517(A).

[0142] The surfactant or mixture of surfactants is present in a cleaning-effective amount. A cleaning-effective amount is the amount needed for the desired cleaning. This will vary depending, for example, on the number of items, the level of soiling, and the volume of dry cleaning composition used. Effective cleaning has been observed when the surfactant is present in an amount of at least 0.001% to 10% by weight of the dry cleaning composition. More preferably, the surfactant is present in an amount of 0.01 to 3% by weight, or even more preferably 0.05 to 0.9% by weight of the dry cleaning composition. More preferably, the surfactant is present in an amount of 0.1 to 0.8% by weight, or even more preferably 0.3 to 0.7% by weight of the dry cleaning composition.

[0143] The dry cleaning composition may contain one or more optional cleaning agents. Detergents include any agent suitable for improving the cleaning, appearance, condition, and / or care of clothing. Generally, the cleaning agent may be present in the composition of the present invention in an amount of about 0-20% by weight, preferably 0.001-10% by weight, and more preferably 0.01-2% by weight of the total dry cleaning composition.

[0144] Some suitable cleaning agents include, but are not limited to, the following compounds: builders, enzymes, bleach activators, bleach catalysts, bleach boosters, bleaches, alkalis, antimicrobials, colorants, fragrances, pro-perfumes, finishing aids, lime soap dispersants, composition malodor control agents, odor neutralizers, polymeric dye transfer inhibitors, crystal growth inhibitors, photobleaching agents, heavy metal ion scavengers, discoloration inhibitors, antimicrobial agents, antioxidants, anti-redeposition agents, soil release polymers, electrolytes, pH modifiers, thickeners, abrasives, divalent or trivalent ions, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines or polyamines and / or alkoxylates thereof, foam stabilizing polymers, processing aids, fabric softeners, optical brighteners, hydrotropes, foam or foam suppressors, foam or foam boosters, fabric softeners, antistatic agents, dye fixatives, dye wear inhibitors, anti-crocking agents, wrinkle reducing agents, anti-wrinkle agents, stain repellents, sunscreens, anti-fade agents, and mixtures thereof.

[0145] III. Surfactants The present disclosure provides surfactants for use in agricultural products that are in the form of derivatives of amino acids. The amino acids may be natural or synthetic, or may be obtained from the ring-opening reaction of lactams such as caprolactam. The compounds of the present disclosure have been shown to have surface-active properties and can be used, for example, as surfactants and wetting agents. In particular, the present disclosure provides compounds of formula I:

[0146] [ka]

[0147] In the formula, R 1 and R 2may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, wherein C1-C6 alkyl is optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; and an optional counterion associated with the compound, which, when present, is selected from the group consisting of chloride, bromide, iodide, and hydroxide.

[0148] One specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide (Surfactant 1), which has the formula:

[0149] [ka]

[0150] A second specific compound provided by the present disclosure is dodecyl 6-(dimethylamino)hexanoate N-oxide (Surfactant 2), which has the following formula:

[0151] [ka]

[0152] In the above structures, the "N→O" notation is intended to mean a non-ionic bonding interaction between the nitrogen and oxygen.

[0153] A third specific compound provided by the present disclosure is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride (Surfactant 3), which has the formula:

[0154] [ka]

[0155] A fourth specific compound provided by the present disclosure is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 4), which has the following formula:

[0156] [ka]

[0157] A fifth specific compound provided by the present disclosure is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride (Surfactant 5), which has the formula:

[0158] [ka]

[0159] These surfactants can be synthesized by various methods. One such method involves ring-opening a lactam to obtain an amino acid having an N-terminus and a C-terminus. The N-terminus can be reacted with one or more alkylating agents and / or acids to obtain a quaternary ammonium salt. Alternatively, the N-terminus can be reacted with an oxidizing agent to obtain an amine N-oxide. The C-terminus can be reacted with an alcohol in the presence of an acid to obtain an ester.

[0160] The amino acids may be natural or synthetic, or may be derived from the ring-opening reaction of a lactam such as caprolactam. The ring-opening reaction may be acid or alkali catalyzed, an example of an acid catalyzed reaction is shown in Scheme 1 below.

[0161] [ka]

[0162] The amino acid may have as few as one or as many as 12 carbons between the N-terminus and C-terminus. The alkyl chain may be branched or straight. The alkyl chain may be interrupted by nitrogen, oxygen, or sulfur. The alkyl chain may be further substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carboxyl, and carboxylate. The N-terminal nitrogen may be acylated or alkylated with one or more alkyl groups. For example, the amino acid may be 6-(dimethylamino)hexanoic acid.

[0163] Surfactant 1 can be synthesized as shown in Scheme 2 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then alkylated with methyl iodide in the presence of sodium carbonate.

[0164] [ka]

[0165] Surfactant 2 can be synthesized as shown in Scheme 3 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then oxidized with hydrogen peroxide to give the amine oxide.

[0166] [ka]

[0167] Surfactant 3 can be synthesized as shown in Scheme 4 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid under reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then alkylated with methyl iodide in the presence of sodium carbonate.

[0168] [ka]

[0169] Surfactant 4 can be synthesized as shown in Scheme 5 below. As shown, 6-aminohexanoic acid is treated with formaldehyde in formic acid at reflux to give 6-(dimethylamino)hexanoic acid. The free carboxylic acid is then treated with an alcohol such as dodecanol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-(dimethylamino)hexanoate. The N-terminus is then treated with 1,4-butanesultone in ethyl acetate at reflux to give the desired sulfonate.

[0170] [ka]

[0171] Surfactant 5 can be synthesized as shown below in Scheme 6. As shown, 6-aminohexanoic acid is treated with an alcohol in the presence of p-toluenesulfonic acid (PTSA) in toluene to give the corresponding ester, dodecyl 6-aminohexanoate. The N-terminus is protonated with hydrochloric acid to give the desired hydrochloride salt.

[0172] [ka]

[0173] The compounds of the present disclosure exhibit surface active properties. These properties can be measured and expressed by various methods. One way to express surfactants is by the critical micelle concentration (CMC) of the molecule. CMC can be defined as the concentration of surfactant that forms micelles, and at a higher concentration, all additional surfactants are incorporated into the micelles.

[0174] As surfactant concentration increases, surface tension decreases. When the surface is completely covered with surfactant molecules, micelles begin to form. This point represents the CMC, or minimum surface tension. Adding more surfactant does not further affect the surface tension. The CMC can therefore be measured by observing the change in surface tension as a function of surfactant concentration. One such method for measuring this value is the Wilhelmy plate method. A Wilhelmy plate is typically a thin iridium-platinum plate attached to a balance by wires and positioned perpendicular to the air-liquid interface. The balance is used to measure the force exerted on the plate by wetting. This value is then used to calculate the surface tension (γ) according to Equation 1: Equation 1: γ = F / l cosθ where l is equal to the wetted perimeter (2w+2d, where w and d are the thickness and width of the plate, respectively), and for cosθ, the contact angle between the liquid and the plate is assumed to be 0 in the absence of an existing literature value.

[0175] Another parameter used to evaluate the performance of surfactants is dynamic surface tension. Dynamic surface tension is the value of the surface tension of a particular surface or interface over time. For liquids to which surfactants have been added, this may differ from the equilibrium value. Immediately after the surface is created, the surface tension is equal to that of the pure liquid. As mentioned above, surfactants reduce surface tension, so the surface tension decreases until it reaches an equilibrium value. The time required to reach equilibrium depends on the diffusion and adsorption rates of the surfactant.

[0176] One method for measuring dynamic surface tension is with a maximum bubble pressure tensiometer. This device measures the maximum internal pressure of a bubble formed in a liquid by a capillary. The measured value corresponds to the surface tension at a specific surface elapsed time, which is the time from the start of bubble formation to the maximum pressure. The dependence of surface tension on surface elapsed time can be measured by varying the rate at which the bubbles are generated.

[0177] Surface-active compounds can also be evaluated by their wetting ability on solid substrates, measured by contact angle. When a liquid droplet contacts a solid surface in a third medium, such as air, a three-phase line is formed between the liquid, the gas, and the solid. The angle between the surface and the unit vector of surface tension, which plays a role in the three-phase line and is tangent to the droplet, is expressed as the contact angle. Contact angle (also known as wetting angle) The contact angle (also known as the CMC) is a measure of the wettability of a solid by a liquid. In complete wetting, the liquid spreads completely over the solid, and the contact angle is 0°. Wetting properties are typically measured at concentrations between 1 and 100 x CMC for a given compound, although measurements of wetting properties may be taken at higher or lower concentrations, as it is not a concentration-dependent property.

[0178] In one method, an optical contact angle goniometer can be used to measure contact angles. This instrument uses a digital camera and software to determine the contact angle by analyzing the contour shape of a sedentary drop of liquid on a surface.

[0179] Potential applications for the surface-active compounds of the present disclosure include formulations for use as shampoos, hair conditioners, detergents, spot-free rinse solutions, floor and carpet cleaners, cleaners for graffiti removal, wetting agents for crop protection, adjuvants for crop protection, and wetting agents for aerosol spray coatings.

[0180] Those skilled in the art will appreciate that small differences between compounds can lead to significantly different surfactant properties, and therefore different compounds may be used with different substrates in different applications.

[0181] The following non-limiting examples are provided to illustrate the different properties of different surfactants. Table 1 below associates surfactant abbreviations with their corresponding chemical structures.

[0182] [Table 1]

[0183] Each of the five compounds is effective as a surfactant and is useful as a wetting or foaming agent, dispersing agent, emulsifier, and detergent, among other uses.

[0184] Surfactant 1, Surfactant 3, and Surfactant 5 are cationic. These surfactants are useful in both the applications mentioned above and in some further specialty applications, such as surface treatments, personal hair care products, and can also be used to create water-repellent surfaces.

[0185] Surfactant 4 is non-ionic and can be used in shampoos, detergents, hard surface cleaners, and a variety of other surface cleaning formulations.

[0186] Surfactant 5 is zwitterionic. These surfactants are useful as co-surfactants in all of the applications mentioned above.

[0187] Example Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. The critical micelle concentration (CMC) was determined by the Wilhelmy plate method using a tensiometer (DCAT 11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate. The dynamic surface tension was determined at 23°C using a maximum bubble pressure tensiometer (Kruss BP100, Kruss GmbH). The contact angle was determined using an optical contact angle goniometer (OCA 15 Pro, DataPhysics GmbH) equipped with a digital camera.

[0188] Example 1a: Synthesis of 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide (surfactant 1) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0189] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in acetonitrile (10 mL). Sodium carbonate (0.388 g, 3.66 mmol) was then added, and the reaction was stirred at room temperature for 10 minutes. Methyl iodide (0.57 mL, 9.16 mmol) was added, and the reaction mixture was heated to 40° C. for 24 hours and then cooled to room temperature. The mixture was filtered and concentrated to give 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide as a yellow solid in 92% yield. 1 H NMR (DMSO)δ 4.00(t,J=6.7Hz,2H),3.30-3.22(m,2H),3.04(s,9H),2.34(t,J=7.4Hz,2H),1 .70-1.63(m,2H),1.62-1.46(m,4H),1.31-1.20(m,20H),0.86(t,J=6.9Hz,3H).

[0190] Example 1b: Identification of the critical micelle concentration (CMC) of surfactant 1 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 1 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 33 mN / m, i.e., 33 mN / m ± 3.3 mN / m. Figure 1 is a plot of these results, showing surface tension versus concentration. The plot shows that the surface tension is approximately 34 mN / m at the CMC and approximately 33.8 mN / m at concentrations above 1.0 mmol.

[0191] Example 1c: Determining the dynamic surface tension of surfactant 1 Dynamic surface tension was determined with a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 2 presents a plot of the results as surface tension versus time, showing that over the time interval from 1 ms to 75 ms, the surface tension rapidly decreases from approximately 55.5 mN / m to approximately 39.9 mN / m. Over the time interval from 75 ms to 50,410 ms, the surface tension decreases more slowly from approximately 39.9 mN / m to approximately 34 mN / m, asymptotically approaching the saturated value of surface tension at the CMC.

[0192] Example 1d: Identification of the wetting properties of surfactant 1 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit surface wetting with a contact angle of 32°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 67.1°, much lower than that of water (Table 2).

[0193] [Table 2]

[0194] Example 2a: Synthesis of dodecyl 6-(dimethylamino)hexanoate N-oxide (surfactant 2) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0195] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in distilled water (80 mL). Hydrogen peroxide (50% solution, 1.04 g, 30.5 mmol) was added. The reaction was heated to reflux for 12 hours, and then the solvent was removed in vacuo. The resulting solid was washed with acetone to give the desired N-oxide in 90% yield. 1 H NMR(500MHz,DMSO)δ 4.00(t,J=6.6Hz,2H),3.30-3.26(m,2H),3.18(s,6H),2.31(t,J=7.4Hz,2H),1 .76-1.73(m,2H),1.54-1.57(m,4H),1.30-1.24(m,22H),0.86(t,J=6.9Hz,3H).

[0196] Example 2b: Identification of the critical micelle concentration (CMC) of surfactant 2 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.08 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 28 mN / m, i.e., 28 mN / m ± 2.8 mN / m. Figure 3 is a plot of these results, showing surface tension versus concentration. The resulting plot indicates that the surface tension at the CMC is approximately 30 mN / m or less. The plot further indicates that at concentrations of 0.08 mmol or greater, the surface tension is 30 mN / m or less.

[0197] Example 2c: Determining the dynamic surface tension of surfactant 2 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 4 shows a plot of surface tension versus time, showing that the compound fully saturated the surface in approximately 7.6 seconds. As can be seen from the plot, the dynamic surface tension is below 40 mN / m for surface dwell times of over 4900 ms.

[0198] Example 2d: Identification of the wetting properties of surfactant 2 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit surface wetting with a contact angle of 39.3°, which is significantly lower than that of water. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was 57.4°, significantly lower than that of water (Table 3).

[0199] [Table 3]

[0200] Example 3a: Synthesis of 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride (surfactant 3) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0201] Dodecyl 6-(dimethylamino)hexanoate (100 mg, 0.305 mmol) was dissolved in water (10 mL). Concentrated hydrochloric acid (11.14 mg, 0.305 mmol) was added.

[0202] Example 3b: Identification of the critical micelle concentration (CMC) of surfactant 3 The critical micelle concentration (CMC) was investigated. From the change in surface tension with concentration in water, the CMC was determined to be approximately 1.4 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 30 mN / m, i.e., 30 mN / m ± 3 mN / m. Figure 5 is a plot of these results, showing surface tension versus concentration. The resulting plot indicates that the surface tension at the CMC is approximately 30 mN / m or less. The plot further indicates that the CMC is approximately 2.7 mmol. It also shows that at these concentrations, the surface tension is 33 mN / m or less.

[0203] Example 3c: Determining the dynamic surface tension of surfactant 3 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension over time at a newly created air-water interface. Figure 6 shows a plot of surface tension versus time, showing that over the time interval of 1 to 100 ms, the surface tension rapidly decreases from approximately 50 mN / m to approximately 40 mN / m. Over the time interval of 100 to 50,000 ms, the surface tension decreases more slowly from 40 mN / m to approximately 34 mN / m, asymptotically approaching the saturated value of surface tension at the CMC.

[0204] Example 3d: Identification of the wetting properties of surfactant 3 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit a surface wetting contact angle of 42.5°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 66.6°, much lower than that of water (Table 4).

[0205] [Table 4]

[0206] Example 4a: Synthesis of 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (surfactant 4) 6-(Dimethylamino)hexanoic acid (11.99 g, 75.36 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (12.68 g, 75.36 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (14.33 g, 75.36 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-(dimethylamino)hexanoate in 51% yield. 1H NMR(DMSO)δ 4.00(t,J=6.5Hz,2H),2.27(t,J=7.3Hz,2H),2.13-2.16(m,2H),2.01(s,6H),1.54-1.53(m,6H),1.27-1.18(m,20H),0.86(t,3H).

[0207] Dodecyl 6-(dimethylamino)hexanoate (1.0 g, 3.05 mmol) was dissolved in ethyl acetate (30 mL). 1,4-butanesultone (0.62 g, 4.57 mmol) was then added, and the mixture was heated to reflux for 12 hours. The reaction was cooled to room temperature, and the solvent was removed in vacuo. 1H NMR (DMSO) δ 4.00 (t, J = 6.7 Hz, 2H), 3.29-3.15 (m, 4H), 2.97 (s, 6H), 2.47 (t, J = 7.4 Hz, 2H), 2.33 (t, J = 7.4 Hz, 2H), 1.81-1.7 0(m,2H),1.66-1.55(m,6H),1.32-1.23(m,20H),0.86(t,J=6.9Hz,3H).

[0208] Example 4b: Identification of the critical micelle concentration (CMC) of surfactant 4 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.1 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 38 mN / m, i.e., 38 mN / m ± 3.8 mN / m. Figure 7 is a plot of these results, showing surface tension versus concentration. The resulting plot shows that the surface tension is approximately 38 mN / m at the CMC, and at concentrations of 1 mmol or greater, the surface tension is 37 mN / m or less.

[0209] Example 4c: Determining the dynamic surface tension of surfactant 4 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension of a newly created air-water interface over time. Figure 8 shows a plot of surface tension versus time, indicating that the compound fully saturated the surface in approximately 1 second. From the plot, the dynamic surface tension is below 40.5 mN / m for surface dwell times of 4000 ms or more.

[0210] Example 4d: Identification of the wetting properties of surfactant 4 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit a surface wetting contact angle of 46.5°. On oleophobic and hydrophobic substrates such as Teflon®, the measured contact angle was 62.7°, much lower than that of water (Table 5).

[0211] [Table 5]

[0212] Example 5a: Synthesis of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride (surfactant 5) 6-Aminohexanoic acid (5.0 g, 38.11 mmol) was dissolved in toluene (50 mL) in a round-bottom flask equipped with a Dean-Stark trap. Next, dodecanol (6.41 g, 38.11 mmol) and p-toluenesulfonic acid monohydrate (PTSA) (7.24 g, 38.11 mmol) were added. The reaction was heated to reflux for 24 hours until no water was observed in the Dean-Stark trap. The solvent was removed under vacuum, and the resulting solid was washed with hexane. The solid was dissolved in dichloromethane (200 mL) and washed with saturated sodium carbonate to give dodecyl 6-aminohexanoate in 40% yield.

[0213] Dodecyl 6-aminohexanoate (100 mg, 0.363 mmol) was dissolved in water (10 mL). Concentrated hydrochloric acid (13.23 mg, 0.363 mmol) was then added. .

[0214] Example 5b: Identification of the critical micelle concentration (CMC) of surfactant 5 The critical micelle concentration (CMC) was determined. From the change in surface tension with concentration in water, the CMC was determined to be approximately 0.75 mmol. The plateau value of the minimum surface tension achievable with this surfactant is approximately 23 mN / m, i.e., 23 mN / m ± 2.3 mN / m. Figure 9 is a plot of these results, showing surface tension versus concentration. The resulting plot shows that the surface tension is approximately 23 mN / m at the CMC, and at concentrations of 0.7 mmol or greater, the surface tension is 23.2 mN / m or less.

[0215] Example 5c: Determination of the dynamic surface tension of surfactant 5 Dynamic surface tension was determined using a maximum bubble pressure tensiometer, which measures the change in surface tension over time at a newly created air-water interface. Figure 10 shows a plot of surface tension versus time, indicating that the compound fully saturated the surface in approximately 1.5 seconds. From the plot, the dynamic surface tension is below 28.5 mN / m for a surface dwell time of 3185 ms or more.

[0216] Example 5d: Identification of the wetting properties of surfactant 5 In addition to surface tension and surface kinetics, the wetting properties of the compounds were tested on various surfaces. For example, hydrophobic substrates such as polyethylene-HD exhibit very low surface wetting with a contact angle of 16.6°. On oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was 39.3°, much lower than that of water (Table 6).

[0217] [Table 6]

[0218] Example 6: Soaps containing two or more surfactants of the present invention Detergent formulations containing soap, fully saturated lauric soap granules based on Prifac 5808 from Uniqema, a first surfactant of the present invention, and a nonionic surfactant of the present invention, which surfactant may be one or more of surfactants 1-5 described herein. All formulations contain 1.008 g / L of surfactant and 0.25-0.67 g / L of soap. The water was conditioned with a mixture of CaCl2·2H2O and MgCl2·H2O to achieve a calcium ion to magnesium ion ratio of 4:1.

[0219] Example 8: Dry cleaning agents Laundry articles are contacted with a low-aqueous dry cleaning composition containing a surfactant, which may be one or more of Surfactants 1-5 described herein. The articles are agitated for 15 minutes at 20°C using a liquor-to-cloth ratio of 13.

[0220] The dry cleaning composition is then removed, and the laundry items are rinsed with a rinse composition containing clean dry cleaning solvent. The experiment is repeated with the low-aqueous dry cleaning composition shown in Table 7 below, using a liquor-to-cloth ratio of 5. The non-aqueous solvent used may be HFE-7200™ (a mixture of ethyl nonafluoroisobutyl ether and ethyl nonafluorobutyl ether, available from 3M), dodecamethylpentasiloxane, decamethyltetrasiloxane, decamethylcyclopentasiloxane, or mixtures thereof.

[0221] [Table 7]

[0222] Aspects A first aspect of the present invention comprises a cleaning formulation, which comprises at least one surfactant of formula I,

[0223] [ka]

[0224] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with this compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; and at least one detergent and / or at least one soap.

[0225] A second aspect of the present invention includes the first aspect of the present invention, wherein the at least one detergent or soap is selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, and zwitterionic detergents.

[0226] In a third aspect of the present invention, the soap is a soap of the general formula (RCO2-)nMn+ This includes a first and second aspect of the invention, wherein R comprises an alkyl group, M is a metal, and n+ is either +1 or +2.

[0227] A fourth aspect of the present invention includes the first to third aspects of the present invention, further comprising at least one builder.

[0228] A fifth aspect of the present invention includes the first through fourth aspects of the present invention, wherein the at least one builder is at least one compound selected from the group consisting of tripolyphosphate, nitriloacetate, zeolite, calcite / carbonate, citrate or polymer, sodium pyrophosphate, orthophosphate, sodium aluminosilicate, inorganic salts of alkalinity agents, inorganic salts of alkali metals, sulfates, silicates, and metasilicates.

[0229] A sixth aspect of the present invention includes the first to fifth aspects of the present invention, further comprising at least one bleaching agent.

[0230] A seventh aspect of the present invention is a method for treating a skin ulcer comprising administering to a subject the at least one bleaching agent selected from the group consisting of metal borates, persalts, peroxyacids, percarbonates, perphophates, persilicates, persulfates, sodium hypochlorite, chlorine dioxide, hydrogen peroxide, sodium percarbonate, sodium perborate, peroxoacetic acid, benzol peroxide, potassium persulfate, potassium permanganate, A sixth aspect of the invention is at least one compound selected from the group consisting of sodium dithionite.

[0231] An eighth aspect of the present invention includes the first to seventh aspects of the present invention, further comprising at least one enzyme.

[0232] A ninth aspect of the invention includes the eighth aspect of the invention, wherein the at least one enzyme is selected from the group consisting of proteases, amylases, cellulases, oxidases, mannanases, peroxidases, and lipases.

[0233] A tenth aspect of the present invention includes the first to ninth aspects of the present invention, further comprising at least one polymer.

[0234] An eleventh aspect of the present invention includes the tenth aspect of the present invention, wherein the at least one polymer is at least one compound selected from the group consisting of polymers of methacrylamides; polymers of ethylenically unsaturated monomers: N,N-dialkylaminoalkyl methacrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-dialkylaminoalkyl methacrylamides, methacylamidoalkyltrialkylammonium salts, acrylamidoalkyltrialkylammonium salts, vinylamines, vinylimidazoles, quaternized vinylimidazoles, and diallyldialkylammonium salts; diallyldimethylammonium salts, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, [2-(methacryloylamino)ethyl]trimethylammonium salts, N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, acrylamidopropyltrimethylammonium salts, methacrylamidopropyltrimethylammonium salts, and quaternized vinylimidazoles.

[0235] In a twelfth aspect of the present invention, the surfactant is a compound represented by the following formula:

[0236] [ka]

[0237] The present invention includes first to eleventh aspects of the present invention, wherein the compound is 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0238] In a thirteenth aspect of the present invention, the surfactant is a compound represented by the following formula:

[0239] [ka]

[0240] This includes first to eleventh aspects of the present invention, wherein the compound is dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0241] In a fourteenth aspect of the present invention, the surfactant is represented by the following formula:

[0242] [ka]

[0243] The present invention includes first to eleventh aspects, in which the compound is 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0244] In a fifteenth aspect of the present invention, the surfactant is represented by the following formula:

[0245] [ka]

[0246] This includes first to eleventh aspects of the present invention, wherein the compound is 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0247] In a sixteenth aspect of the present invention, the surfactant is represented by the following formula:

[0248] [ka]

[0249] The present invention includes first to eleventh aspects, in which the compound is 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0250] A seventeenth aspect of the present invention comprises at least one dry cleaning formulation, which comprises at least one surfactant of formula I,

[0251] [ka]

[0252] In the formula, R 1 and R 2 may be the same or different and may be selected from the group consisting of hydrogen and C1-C6 alkyl, where C1-C6 alkyl may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 2 to 5, inclusive; m is an integer from 9 to 20, inclusive; and the terminal nitrogen is R 3 may be further substituted with, in which case R 3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C1-C6 alkyl, where C1-C6 alkyl may optionally be substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; an optional counterion associated with this compound, if present, selected from the group consisting of chloride, bromide, iodide, and hydroxide; and at least one solvent.

[0253] An eighteenth aspect of the present invention includes the seventeenth aspect of the present invention, wherein the at least one solvent is at least one compound selected from the group consisting of perchloroethylene, a hydrocarbon, trichloroethylene, decamethylcyclopentasiloxane, dibutoxymethane, and n-propyl bromide.

[0254] A nineteenth aspect of the present invention includes the seventeenth and eighteenth aspects of the present invention, further comprising at least one co-solvent.

[0255] A twentieth aspect of the present invention is directed to a process for preparing a fluoropolymerizable solvent, wherein the at least one co-solvent is selected from the group consisting of alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorotertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ...propyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene at least one selected from the group consisting of ethylene glycol methyl ether, ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkylpyrrolidone (N-methylpyrrolidone, N-ethylpyrrolidone, etc.), methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane; A nineteenth aspect of the invention is a compound.

[0256] In a twenty-first aspect of the present invention, the surfactant is represented by the following formula:

[0257] [ka]

[0258] The seventeenth to nineteenth aspects of the present invention include 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide having the formula:

[0259] In a twenty-second aspect of the present invention, the surfactant is a compound represented by the following formula:

[0260] [ka]

[0261] The seventeenth to nineteenth aspects of the present invention include dodecyl 6-(dimethylamino)hexanoate N-oxide having the formula:

[0262] A twenty-third aspect of the present invention is a surfactant having the formula:

[0263] [ka]

[0264] The seventeenth to nineteenth aspects of the present invention include 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the formula:

[0265] A twenty-fourth aspect of the present invention is a surfactant having the formula:

[0266] [ka]

[0267] The seventeenth to nineteenth aspects of the present invention include 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate having the formula:

[0268] A twenty-fifth aspect of the present invention is a surfactant having the following formula:

[0269] [ka]

[0270] The seventeenth to nineteenth aspects of the present invention include 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

[0271] A twenty-sixth aspect of the present invention is a surfactant having the following formula:

[0272] [ka]

[0273] 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the following formula:

[0274] [ka]

[0275] 6-(dimethylamino)hexanoate N-oxide, having the following formula:

[0276] [ka]

[0277] 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the following formula:

[0278] [ka]

[0279] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate, having the following formula:

[0280] [ka]

[0281] and at least one of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: and combinations thereof, including first to eleventh aspects of the present invention.

[0282] A twenty-seventh aspect of the present invention is a surfactant having the following formula:

[0283] [ka]

[0284] 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the following formula:

[0285] [ka]

[0286] 6-(dimethylamino)hexanoate N-oxide, having the following formula:

[0287] [ka]

[0288] 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the following formula:

[0289] [ka]

[0290] 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate, having the following formula:

[0291] [ka]

[0292] and at least one of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula:

Claims

1. A formulation for cleaning hard and plastic surfaces, comprising: The following formula: 【Chemical 1】 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the following formula: 【Chemistry 2】 6-(dimethylamino)hexanoate N-oxide, having the following formula: 【Chemistry 3】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the following formula: 【Chemistry 4】 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate, having the following formula: 【Chemistry 5】 and a surfactant comprising at least one of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: at least one detergent or at least one soap, 1. A formulation comprising:

2. 10. The formulation of claim 1, wherein the at least one detergent or soap is selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, and zwitterionic detergents.

3. The soap has the general formula: (RCO ２ － ) ｎ M ｎ＋ wherein R comprises an alkyl group and M is a metal; ｎ＋ 3. The formulation of claim 1 or claim 2, wherein is either +1 or +2.

4. A formulation according to any one of claims 1 to 3, further comprising at least one builder.

5. 5. The formulation of claim 4, wherein the at least one builder is at least one compound selected from the group consisting of tripolyphosphates, nitriloacetates, zeolites, calcites / carbonates, citrates or polymers, sodium pyrophosphates, orthophosphates, sodium aluminosilicates, inorganic salts of alkalinity agents, inorganic salts of alkali metals, sulfates, silicates, and metasilicates.

6. A formulation according to any one of claims 1 to 5, further comprising at least one bleaching agent.

7. 7. The formulation of claim 6, wherein the at least one bleaching agent is at least one compound selected from the group consisting of metal borates, persalts, peroxyacids, percarbonates, perphosphates, persilicates, persulfates, sodium hypochlorite, chlorine dioxide, hydrogen peroxide, sodium percarbonate, sodium perborate, peroxoacetic acid, benzoyl peroxide, potassium persulfate, potassium permanganate, and sodium dithionite.

8. The formulation of any one of claims 1 to 7, further comprising at least one enzyme.

9. 9. The formulation of claim 8, wherein the at least one enzyme is selected from the group consisting of proteases, amylases, cellulases, oxidases, mannanases, peroxidases, and lipases.

10. The formulation of any one of claims 1 to 9, further comprising at least one polymer.

11. 11. The formulation of claim 10, wherein the at least one polymer is at least one compound selected from the group consisting of polymers of methacrylamide; polymers of the ethylenically unsaturated monomers N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkyl methacrylamide, methacylamidoalkyltrialkylammonium salt, acrylamidoalkyltrialkylammonium salt, vinylamine, vinylimidazole, quaternized vinylimidazole, and diallyldialkylammonium salt, diallyldimethylammonium salt, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, [2-(methacryloylamino)ethyl]trimethylammonium salt, N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, acrylamidopropyltrimethylammonium salt, methacrylamidopropyltrimethylammonium salt, and quaternized vinylimidazole.

12. A formulation for dry cleaning, comprising: The following formula: 【Chemistry 6】 6-(dodecyloxy)-N,N,N-trimethyl-6-oxohexan-1-aminium iodide having the following formula: 【Chemistry 7】 6-(dimethylamino)hexanoate N-oxide, having the following formula: 【Chemistry 8】 6-(dodecyloxy)-N,N-dimethyl-6-oxohexane-1-aminium chloride having the following formula: 【Chemistry 9】 4-((6-(dodecyloxy)-6-oxohexyl)dimethylammonio)butane-1-sulfonate, having the following formula: 【Chemistry 10】 and a surfactant comprising at least one of 6-(dodecyloxy)-6-oxohexane-1-aminium chloride having the formula: at least one solvent, 1. A formulation comprising:

13. 13. The formulation of claim 12, wherein the at least one solvent is at least one compound selected from the group consisting of perchloroethylene, hydrocarbons, trichloroethylene, decamethylcyclopentasiloxane, dibutoxymethane, n-propyl bromide.

14. 14. The formulation of claim 12 or claim 13, further comprising at least one co-solvent.

15. The at least one co-solvent may be selected from the group consisting of alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorotertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol, propylene glycol methyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol methyl ether, propylene glycol n-butyl ether, propylene ... The formulation according to claim 14, wherein the at least one compound is selected from the group consisting of ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkylpyrrolidones (such as N-methylpyrrolidone and N-ethylpyrrolidone), methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane.

Images