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WO2016160407A1 - Détergents à base de tensioactifs ester gras alpha-sulfonés - Google Patents

Détergents à base de tensioactifs ester gras alpha-sulfonés Download PDF

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WO2016160407A1
WO2016160407A1 PCT/US2016/023525 US2016023525W WO2016160407A1 WO 2016160407 A1 WO2016160407 A1 WO 2016160407A1 US 2016023525 W US2016023525 W US 2016023525W WO 2016160407 A1 WO2016160407 A1 WO 2016160407A1
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Prior art keywords
weight
fatty
methyl
produce
detergent
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Brian Holland
Randal J. Bernhardt
Branko Sajic
Rick Tabor
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Stepan Co
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Stepan Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the invention relates to laundry detergents, and in particular to cold-water 5 detergents comprising ⁇ -sulfonated fatty ester surfactants based on fatty acids and C 8 - C 12 alcohols.
  • Surfactants are essential components of everyday products such as household 10 and industrial cleaners, agricultural products, personal care products, laundry detergents, oilfield chemicals, specialty foams, and many others.
  • laundry detergents have now been developed that are designed to perform well in hot, warm, or cold water.
  • One popular cold-water detergent utilizes a combination of a nonionic surfactant (a fatty alcohol ethoxylate) and two anionic surfactants (a linear alkylbenzene sulfonate and a fatty alcohol ethoxylate sulfate) among other conventional components.
  • Commercially available cold-water detergents 25 tend to perform well on many common kinds of stains, but they have difficulty removing greasy dirt, particularly bacon grease, beef tallow, cooked beef fat, and the like. These soils are often deposited as liquids but quickly solidify and adhere tenaciously to textile fibers.
  • the surfactant can be overmatched in the challenge to wet, liquefy, and remove these greasy, hardened soils.
  • Most surfactants used in laundry detergents have a polar head and a nonpolar tail.
  • the polar group (sulfate, sulfonate, amine oxide, etc.) is usually located at one end of the chain. Branching is thought to improve the solubility of the surfactant in cold water, especially for surfactants with higher chain lengths (C14 to C30) and therefore thought to improve cold-water cleaning performance. References suggesting that branching is helpful also teach to locate the polar group at the chain terminus (see, e.g., 5 U.S. Pat. Nos.6,020,303; 6,060,443; and 6,153,577).
  • Internal olefin sulfonates are well known. Although they are useful for enhanced oil recovery (see, e.g., U.S. Pat. Appl. No. 2010/0282467), they have also been suggested for use in detergent compositions, including laundry detergents (see U.S. Pat. No. 5,078,916). These are prepared by sulfonating mixtures of internal olefins. 10 Commercially available internal olefins, including the Neodene ® products of Shell, are mixtures that have a scattered location for the carbon-carbon double bond. Consequently, sulfonates made from these internal olefins (including the commercial Enordet ® products from Shell) do not have a well-defined location for the polar group.
  • ⁇ -Sulfonated fatty acid alkyl esters (hereinafter also called“ ⁇ -sulfonated fatty 15 esters”) are generally known as surface-active materials (see, e.g., T. Okano et al., J.
  • the ⁇ -sulfonated fatty acids are available from the reaction of fatty acids with a sulfonating agent, such as sulfur trioxide.
  • the ⁇ -sulfonated fatty esters 20 have been made from a variety of different fatty acids and using a variety of different aliphatic alcohols.
  • Okano for instance, describes ⁇ -sulfonated fatty esters made from C 10 -C18 fatty acids and C 8 -C18 alcohols. Okano does not formulate laundry detergents from the ⁇ -sulfonated fatty esters or provide cold-water cleaning results from testing laundry detergents.
  • 25 ⁇ -Sulfonated fatty acid methyl esters are well-known compositions useful for household and industrial cleaning products, including laundry detergents.
  • Commercially available products include Stepan’s ALPHA-STEP ® MC-48 and PC-48, which are C 12 -C18 mixtures of sodium methyl 2-sulfolaurate (MES) and disodium 2-sulfolaurate. This product derives from a mixture of C 12 -C18 fatty acids, 30 principally C 12 and C14 fatty acids with a minor proportion of C16 and C18 components.
  • the invention relates to a laundry detergent that is useful for cold- water cleaning.
  • the detergent comprises: (a) an ⁇ -sulfonated fatty ester surfactant comprising a compound having the formula:
  • M is hydrogen, an alkali metal, an alkaline earth metal, ammonium, and amine 20 salt, or a mixture thereof;
  • R 1 is an unsubstituted or hydroxy-substituted, saturated or unsaturated, linear or branched C6-C16 alkyl group; and
  • R 2 is a saturated or unsaturated linear or branched C 8 to C 12 alkyl group; and (b) an anionic surfactant, a nonionic surfactant, or a combination thereof.
  • the anionic surfactant is a linear alkylbenzene sulfonate, a fatty 25 alcohol ethoxylate sulfate, a fatty alcohol sulfate, or a mixture thereof.
  • the nonionic surfactant is a fatty alcohol ethoxylate.
  • the invention relates to a cold-water cleaning method. The method comprises laundering one or more textile articles in water having a temperature less than or equal to 30 o C, preferably within the range of 5 o C to 28 o C, in the presence of 30 a laundry detergent of the invention.
  • the invention includes processes for making the ⁇ -sulfonated fatty ester surfactants from fatty acids, lower fatty alkyl esters, and glycerides or natural oils.
  • ⁇ -sulfonated fatty ester surfactants having a long 5 enough alkyl chain for the alcohol portion, i.e., a C 8 to C 12 alkyl group, provide outstanding cold-water cleaning performance in removing greasy stains such as bacon grease, cooked beef fat, or beef tallow from soiled articles.
  • Detergents formulated with the surfactants outperform control cold-water detergents by a wide margin and also outperform similar detergents comprising ⁇ -sulfonated fatty esters made from lower 10 alcohols, such as methyl, butyl, or hexyl esters of ⁇ -sulfonated fatty acids.
  • the invention relates to detergents useful for cold-water cleaning.
  • the detergents comprise: (a) an ⁇ -sulfonated fatty ester surfactant; and (b) an anionic 15 surfactant, a nonionic surfactant, or a combination thereof.
  • the ⁇ -Sulfonated Fatty Ester Surfactant comprises: (a) an ⁇ -sulfonated fatty ester surfactant; and (b) an anionic 15 surfactant, a nonionic surfactant, or a combination thereof.
  • Suitable ⁇ -sulfonated fatty ester surfactants comprise a compound having the formula:
  • M is hydrogen, an alkali metal, an alkaline earth metal, ammonium, and amine salt, or a mixture thereof;
  • R 1 is an unsubstituted or hydroxy-substituted, saturated or unsaturated, linear or branched C6-C16 alkyl group; and
  • R 2 is a saturated or unsaturated linear or branched C 8 to C 12 alkyl group.
  • M is hydrogen or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), an alkaline earth metal cation (e.g., calcium or magnesium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium 30 cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium
  • an alkaline earth metal cation e.g., calcium or magnesium
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium c
  • M is hydrogen, sodium, potassium, or lithium, or some combination thereof. Preferably, M is sodium.
  • R 1 is a C6-C 8 alkyl group, a C6-C 12 group, a C6-C16 group, a C 8 - C 10 alkyl group, a C 10 -C 12 alkyl group, a C 10 -C14 alkyl group, a C 10 -C16 group, or a C 12 - C18 group.
  • R 2 is a C 8 , C9, C 10 , C11, or C 12 alkyl group.
  • R 1 has an average of 6 to 7 carbons. In other aspects, R 1 has 10 an average of 10 to 11 carbons. In still other aspects, R 1 has an average of 12 to 13 carbons.
  • the ⁇ -sulfonated fatty ester surfactants further comprise a proportion of“di-salt,” which may have the formula:
  • R 1 and M are as described above, and M 2 is independently selected from the choices enumerated above for M.
  • M and M 2 are both sodium.
  • the amount of di-salt present in the ⁇ -sulfonated fatty ester surfactant is less than 10 mole %, preferably less than 5 mole %, even more preferably 20 less than 1 mole %, based on the combined amounts of di-salt and ⁇ -sulfonated fatty ester compound.
  • the detergent may comprise 1 to 99 wt.% of combined actives from the ⁇ -sulfonated fatty ester surfactant, anionic surfactant, and nonionic surfactant; in other aspects, the detergent may comprise 5 to 90 wt.% of combined actives from the 25 ⁇ -sulfonated fatty ester surfactant, anionic surfactant, and nonionic surfactant. In still other aspects, the detergent may comprise 10 to 75 wt.% of combined actives from the ⁇ -sulfonated fatty ester surfactant, anionic surfactant, and nonionic surfactant.
  • the detergent may comprise 0.5 to 60 wt.% active, or 1 to 50 wt.% active, or 5 to 40 wt.% active, or 7 to 30 wt.% active, or 10 to 25 wt.% active of the 30 ⁇ -sulfonated fatty ester surfactant based on 100% actives.
  • the detergent may comprise 0.5 to 60 wt.% active (or 1 to 50 wt.% active, or 5 to 40 wt.% active) of the ⁇ -sulfonated fatty ester surfactant, 1 to 50% active (or 2 to 45 wt.% active) of the anionic surfactant, and 0.5 to 80 wt.% active (or 2 to 60 wt.% active) of the nonionic surfactant, all based on 100% actives.
  • Suitable ⁇ -sulfonated fatty esters having the formula shown above can be made from fatty acids, fatty alkyl esters, mono-, di- or triglycerides, natural oils, or other fatty acid derivatives (e.g., acid halides, anhydrides) using a variety of synthetic approaches, some of which may be more preferred than others. To illustrate just some of the possible synthetic methods:
  • a fatty acid, fatty acid mixture, monoglyceride, diglyceride, triglyceride, or natural oil is converted first to a fatty alkyl ester or ester mixture, particularly a C1-C6 alkyl ester mixture, and more typically a mixture of fatty methyl esters or fatty ethyl esters wherein the fatty chain has a distribution of carbon lengths.
  • the fatty ester mixture is preferably distilled or otherwise fractionated to obtain fatty esters having a desired carbon number range (e.g., C 8 -C 10 fatty methyl esters, C 12 -C14 fatty methyl esters or C16-C18 fatty methyl esters).
  • the desired fraction of fatty alkyl esters can be sulfonated at the carbon ⁇ - to the carbonyl using known sulfonating agents and methods. For instance, reaction of the fatty alkyl ester with sulfur trioxide 15 (e.g., 1.1 to 1.3 equivalents of SO 3 ) followed by digestion, optional bleaching, and neutralization provides an ⁇ -sulfonated fatty alkyl ester (see example below for preparation of ⁇ -sulfonated methyl esters).
  • sulfur trioxide 15 e.g., 1.1 to 1.3 equivalents of SO 3
  • Bleaching can be included 20 to reduce the color of the product and is conveniently accomplished using hydrogen peroxide or other oxidants.
  • Neutralization is typically performed using alkali metal hydroxides (e.g., sodium hydroxide) or alkali metal carbonates (e.g., sodium carbonate), which can be used as alternatives or in a stepwise neutralization process. Desirable conditions for digestion, bleaching, and neutralization are discussed in U.S. Pat. No. 25 5,587,500, the teachings of which are incorporated herein by reference.
  • the ⁇ -sulfonated fatty alkyl ester is then reacted with a C 8 - C 12 alcohol, optionally in the presence of a transesterification catalyst, to generate an ⁇ - sulfonated fatty ester useful for the inventive cold-water laundry detergents.
  • a transesterification catalyst for the inventive cold-water laundry detergents.
  • transesterify the ⁇ -sulfonated fatty 30 alkyl ester mixture with a C 8 -C 12 alcohol prior to any bleaching step and neutralization for more examples of ⁇ -sulfonation of fatty lower alkyl esters, especially the methyl esters, see U.S. Pat. Nos. 5,616,781; 5,637,758; 5,587,500; 4,671,900; 4,080,372; 3,350,428; and references cited therein, the teachings of which are incorporated herein by reference.
  • the inventive laundry detergents comprise, in addition to the 15 particular ⁇ -sulfonated fatty esters described above, at least one additional anionic surfactant.
  • Suitable anionic surfactants are well known in the art.
  • Anionic surfactants generally have a molecular weight below 10,000 and comprise one or more functional groups that exhibit a net anionic charge when in aqueous solution at the normal wash pH, which typically ranges from 6 to 11.
  • Suitable anionic surfactants include C4-C30 20 carboxylates, fatty alkyl sulfates (alcohol sulfates,“AS”), fatty alkyl ether sulfates (alcohol ether sulfates, “AES”), paraffin sulfonates, olefin sulfonates, alkyl aryl sulfonates (e.g., linear alkylbenzene sulfonates, “LAS”), fatty ester sulfonates, sulfosuccinate esters, organic phosphates, and the like.
  • AS fatty alkyl sulfates
  • AES fatty alkyl ether sulfates
  • paraffin sulfonates e.g., olefin sulfonates
  • alkyl aryl sulfonates e.g., linear alkylbenzene sulfonates, “LAS
  • Preferred anionic surfactants include alkylbenzene sulfonates having a linear C 8 -C18 alkyl group, more preferably a 25 linear C11-C14 alkyl group; primary fatty alkyl sulfates and fatty alkyl ether sulfates derived from C 8 -C18 alcohols; C 8 -C22 paraffin sulfonates; and C 8 -C22 olefin sulfonates.
  • the carboxylate, phosphate, sulfate, and sulfonate salts usually have a monovalent counterion, e.g., an alkali metal, ammonium, or quaternary nitrogen ion.
  • Linear alkylbenzene sulfonates (LAS) and alcohol ether sulfates (AES) are particularly 30 preferred. Additional examples of suitable anionic surfactants are described in U.S. Pat.
  • the amount of anionic surfactant can range from 1 to 70 wt.%, more preferably from 2 to 60 wt.%, and most preferably from 5 to 40 wt.% of the formulation.
  • the anionic surfactant is selected 5 from linear alkylbenzene sulfonates, fatty alcohol ethoxylate sulfates, fatty alcohol sulfates, and mixtures thereof. More details regarding suitable anionic surfactants appear in the following paragraphs.
  • anionic surfactants are defined here as amphiphilic molecules with an average molecular weight of less than about 10,000, comprising one or more 10 functional groups that exhibit a net anionic charge when present in aqueous solution at the normal wash pH, which can be a pH between 6 and 11.
  • the anionic surfactant can be any anionic surfactant that is substantially water soluble.
  • Water soluble surfactants are, unless otherwise noted, here defined to include surfactants which are soluble or dispersible to at least the extent of 0.01% by weight in distilled water at 25°C. At least 15 one of the anionic surfactants used may be an alkali or alkaline earth metal salt of a natural or synthetic fatty acid containing between about 4 and about 30 carbon atoms.
  • a mixture of carboxylic acid salts with one or more other anionic surfactants can also be used.
  • Another important class of anionic compounds is the water soluble salts, particularly the alkali metal salts, of organic sulfur reaction products having in their 20 molecular structure an alkyl radical containing from about 6 to about 24 carbon atoms and a radical selected from the group consisting of sulfonic and sulfuric acid ester radicals.
  • alkyl ether sulfates are preferred.
  • linear alkyl benzene 25 sulfonates are preferred.
  • Carboxylic acid salts are represented by the formula:
  • R 1 is a primary or secondary alkyl group of 4 to 30 carbon atoms and M is a solubilizing cation.
  • the alkyl group represented by R 1 may represent a mixture of 30 chain lengths and may be saturated or unsaturated, although it is preferred that at least two thirds of the R 1 groups have a chain length of between 8 and 18 carbon atoms.
  • suitable alkyl group sources include the fatty acids derived from coconut oil, tallow, tall oil and palm kernel oil. For the purposes of minimizing odor, however, it is often desirable to use primarily saturated carboxylic acids.
  • solubilizing cation M
  • the solubilizing cation, M may be any cation that confers water solubility to the product, although monovalent such moieties are generally preferred.
  • acceptable solubilizing cations for use with the present technology include alkali metals such as sodium and potassium, which are particularly preferred, and amines 10 such as triethanolammonium, ammonium and morpholinium.
  • R 2 is a primary alkyl group of 8 to 18 carbon atoms and can be branched or linear, saturated or unsaturated.
  • M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as 20 tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • alkali metal cation e.g., sodium, potassium, lithium
  • ammonium or substituted ammonium e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as 20
  • the alkyl group R 2 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 2 alkyl groups have a chain length of 8 to 18 carbon atoms. This will be the case if R 2 is coconut alkyl, for example.
  • the 25 solubilizing cation may be a range of cations which are in general monovalent and confer water solubility.
  • An alkali metal, notably sodium, is especially envisaged.
  • Other possibilities are ammonium and substituted ammonium ions, such as trialkanolammonium or trialkylammonium.
  • Alkyl ether sulfates are represented by the formula:
  • R 3 O(CH2CH2O)nSO 3 M
  • R 3 is a primary alkyl group of 8 to 18 carbon atoms, branched or linear, saturated or unsaturated, and n has an average value in the range from 1 to 6 and M is a solubilizing cation.
  • the alkyl group R 3 may have a mixture of chain lengths. It is preferred that at least two-thirds of the R 3 alkyl groups have a chain length of 8 to 18 5 carbon atoms. This will be the case if R 3 is coconut alkyl, for example.
  • n has an average value of 2 to 5.
  • Ether sulfates have been found to provide viscosity build in certain of the formulations of the present technology, and thus are considered a preferred ingredient.
  • alkyl ester sulfonate 10 surfactants including linear esters of C 8 - C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 (see, e.g., J. Am. Oil Chem. Soc.52 (1975) 323).
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, and the like.
  • alkyl ester sulfonate surfactants especially for laundry applications, 15 comprise alkyl ester sulfonate surfactants of the structural formula:
  • R 3 is a C6 -C20 hydrocarbyl, preferably an alkyl or combination thereof
  • R 4 is a C1 -C6 hydrocarbyl, preferably an alkyl, or combination thereof
  • M is a cation that forms a water soluble salt with the alkyl ester sulfonate.
  • Suitable salt-forming 20 cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine.
  • the group R 3 may have a mixture of chain lengths. Preferably at least two-thirds of these groups have 6 to 12 carbon atoms.
  • R 3 CH(-)CO2(-) is derived from a coconut source, for instance.
  • R 3 is 25 C 10 -C16 alkyl
  • R 4 is methyl, ethyl or isopropyl.
  • methyl ester sulfonates where R 3 is C 10 -C16 alkyl.
  • Alkyl benzene sulfonates are represented by the formula:
  • R 6 is an alkyl group of 8 to 18 carbon atoms
  • Ar is a benzene ring (-C6H4-) 30 and M is a solubilizing cation.
  • the group R 6 may be a mixture of chain lengths.
  • a mixture of isomers is typically used, and a number of different grades, such as "high 2- phenyl” and “low 2-phenyl” are commercially available for use depending on formulation needs. Many commercial suppliers exist for these materials, including Stepan, Akzo, Pilot, and Rhodia.
  • alkylbenzenes typically are produced by the sulfonation of alkylbenzenes, which can be produced by either the HF-catalyzed alkylation of benzene with olefins or 5 an AlCl3-catalyzed process that alkylates benzene with chloroparaffins, and are sold by, for example, Petresa (Chicago, IL) and Sasol (Austin, TX). Straight chains of 11 to 14 carbon atoms are usually preferred.
  • Paraffin sulfonates having about 8 to about 22 carbon atoms, preferably about 12 to about 16 carbon atoms, in the alkyl moiety, are contemplated for use here. They are 10 usually produced by the sulfoxidation of petrochemically derived normal paraffins.
  • surfactants are commercially available as, for example, Hostapur SAS from Clariant (Charlotte, NC).
  • Olefin sulfonates having 8 to 22 carbon atoms, preferably 12 to 16 carbon atoms, are also contemplated for use in the present compositions.
  • the olefin sulfonates are 15 further characterized as having from 0 to 1 ethylenic double bonds; from 1 to 2 sulfonate moieties, of which one is a terminal group and the other is not; and 0 to 1 secondary hydroxyl moieties.
  • U.S. Pat. No. 3,332,880 contains a description of suitable olefin sulfonates, and its teachings are incorporated herein by reference. Examples of specific surfactant species from that patent include the following:
  • x is an integer of from about 4 to about 18, preferably from about 4 to about 12, and M represents any cation that forms a water-soluble salt such as alkali metals, e.g., sodium and potassium, and ammonium and substituted ammonium compounds, e.g., trialkylammonium and trialkylolammonium compounds.
  • alkali metals e.g., sodium and potassium
  • ammonium and substituted ammonium compounds e.g., trialkylammonium and trialkylolammonium compounds.
  • substituted ammonium compounds are triethylammonium, trimethylammonium, and triethanolammonium.
  • Others will be apparent to those skilled in the art. Such materials are sold as, for example, Bio-Terge ® AS-40, a product of Stepan.
  • R 7 and R 8 are alkyl groups with chain lengths of between 2 and 16 carbons, and may be linear or branched, saturated or unsaturated. R 7 and R 8 can also be ethoxylated alkyl groups having an average of 1 to 100, preferably 1 to 50, more preferably 1 to 25 oxyethylene groups.
  • a preferred 15 sulfosuccinate is sodium bis(2-ethylhexyl)sulfosuccinate, which is commercially available under the trade name Aerosol OT from Cytec Industries (West Paterson, NJ).
  • Organic phosphate-based anionic surfactants include organic phosphate esters such as complex mono- or diester phosphates of hydroxyl-terminated alkoxide condensates, or salts thereof. Suitable organic phosphate esters include phosphate 20 esters of polyoxyalkylated alkylaryl phenols, phosphate esters of ethoxylated linear alcohols, and phosphate esters of ethoxylated phenols. Also included are nonionic alkoxylates having a sodium alkylenecarboxylate moiety linked to a terminal hydroxyl group of the nonionic through an ether bond. Counterions to the salts of all the foregoing may be those of alkali metal, alkaline earth metal, ammonium, 25 alkanolammonium and alkylammonium types.
  • anionic surfactants useful for detersive purposes can also be included in the detergent compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 8 -C22 primary of secondary alkanesulfonates, C 8 -C24 30 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Pat. No.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C 8 -C22 primary of secondary alkanesulfonates C 8 -C24 30 olefin sulfonates
  • sulfonated polycarboxylic acids prepared by sulfonation of the
  • alkyl poly glycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl 5 succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C 12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglu
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of 15 such surfactants are also generally disclosed in U.S. Pat. Nos. 3,929,678 and 6,949,498, the teachings of which are incorporated herein by reference.
  • anionic surfactants contemplated include isethionates, sulfated triglycerides, alcohol sulfates, ligninsulfonates, naphthelene sulfonates and alkyl naphthelene sulfonates, and the like.
  • anionic surfactants contemplated for use in the present compositions include alcohol ether sulfates (AES), linear alkylbenzene sulfonates (LAS), alcohol sulfates (AS), ⁇ -methyl ester sulfonates (MES), or combinations of two or more of these.
  • the amount of an anionic surfactant contemplated can be, for example, 1% to 70% of the composition more preferably between 1% and 60%, even more preferably between 25 1% and 40%.
  • surfactants see U.S. Pat. No.
  • the inventive laundry detergents comprise, in addition to the 30 particular ⁇ -sulfonated fatty esters described above, at least one nonionic surfactant.
  • the nonionic surfactant is a fatty alcohol ethoxylate.
  • Suitable nonionic surfactants are also well known.
  • Nonionic surfactants are neutral and comprise a hydrophobic group and a hydrophilic group.
  • the hydrophilic group comprises one or more recurring units derived from ethylene oxide, and the hydrophilic/lipophilic balance of the nonionic surfactant is adjusted to the 5 desired level by controlling the proportion of ethylene oxide used.
  • Suitable nonionic surfactants include fatty alcohols, fatty alcohol alkoxylates, alkylphenol alkoxylates, ether-capped fatty alcohol alkoxylates, alkoxylated fatty esters, alkoxylate block copolymers, alkylpolysaccharides, alkoxylated fatty amides, polyhydroxy fatty amides, fatty amine oxides, castor oil alkoxylates, polyol esters, glycerol esters, glycol fatty 10 esters, tallow amine ethoxylates, and the like.
  • C 12 -C18 alkyl ethoxylates especially C 12 -C15 primary alcohol ethoxylates having from 6 to 130 moles of ethylene oxide recurring units.
  • suitable nonionic surfactants are described in U.S. Pat. Nos. 3,630,929; 4,316,812; 5,929,022; 7,098,175; and U.S. Pat. Appl. Publ. No. 2010/0016198 (see especially pp. 14-15), the teachings of which 15 are incorporated herein by reference.
  • the amount of nonionic surfactant can range from 5 to 70 wt.%, more preferably from 10 to 50 wt.%, and most preferably from 15 to 40 wt.% of the formulation. More details regarding suitable nonionic surfactants appear in the paragraphs that follow below.
  • nonionic surfactants examples include alkyl polyglucosides (“APGs”), 20 alcohol ethoxylates, nonylphenol ethoxylates, methyl ester ethoxylates (“MEEs”), and others.
  • the nonionic surfactant may be used as from 1% to 90%, more preferably from 1 to 40% and most preferably between 1% and 32% of a detergent composition.
  • suitable nonionic surfactants are described in U.S. Pat. No.5,929,022, from which much of the following discussion comes.
  • Nonionic surfactants useful herein are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic- lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14.
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic and the length of the polyoxyethylene group which is condensed with any 30 particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • low HLB can be defined as having an HLB of 8 or less and preferably 6 or less.
  • a "low level" of co-surfactant can be defined as 6% or less of the HDL and preferably 4% or less of the HDL.
  • nonionic surfactants of this type are the C9 - C15 primary 5 alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C 12 - C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.
  • a surfactant is polyalkoxylated aliphatic base, sold for example as Makon ® NF-12 by Stepan Company.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds 10 of general formula:
  • Z is a moiety derived f is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x has an average value from 1.3 to 4.
  • the compounds include less than 10% unreacted fatty 15 alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070077, EP 0075996 and EP 0094118.
  • nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:
  • R 1 is H, or R 1 is C1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof
  • R 2 is C5-C31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • R 1 is methyl
  • R 2 is a straight C11-15 alkyl or 25 alkenyl chain such as coconut alkyl or mixtures thereof
  • Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Actives level and water content of the detergents
  • the detergent comprises water in addition to the ⁇ -sulfonated fatty ester surfactant and any anionic or nonionic surfactant.
  • the amount of water present may vary over a wide range and will normally depend on the intended application, the form in which the detergent is delivered, the desired actives level, and other factors. In actual use, the detergents will normally be diluted with a small, large, or very large proportion of water, depending on the equipment available for washing. Generally, the 5 amount of water used will be effective to give 0.001 to 5 wt.% of active surfactant in the wash.
  • the detergent will comprise 1 to 95 wt.% of combined actives from the ⁇ -sulfonated fatty ester surfactant, anionic surfactant, and nonionic surfactant.
  • the detergent will comprise 0.5 to 60 wt.% active of the ⁇ - 10 sulfonated fatty ester surfactant based on 100% actives.
  • the detergent will comprise 0.5 to 60 wt.% active of the ⁇ - sulfonated fatty ester surfactant, 1 to 50% active of the anionic surfactant, and 0.5 to 80 wt.% active of the nonionic surfactant, all based on 100% actives. 15 Laundry detergent formulations
  • the invention relates to particular laundry detergent formulations comprising the inventive detergents.
  • One such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention and has a pH within the range of 7 to 10.
  • This detergent further 20 comprises:
  • a sufficient amount of at least three enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, 25 lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases, and derivatives thereof.
  • enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, 25 lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulan
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention and has a pH within the range of 7 to 10.
  • This detergent 30 further comprises:
  • a sufficient amount of one or two enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, 5 lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases, and derivatives thereof.
  • one or two enzymes selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, 5 lipoxygenases, ligninases,
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention, has a pH within the range of 7 to 12, and is substantially free of enzymes.
  • This detergent further comprises:
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention and has a pH within the range of 7 to 10.
  • This detergent further comprises:
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention and has a pH greater than 10.
  • This detergent further comprises:
  • metasilicate 0.1% to about 5% by weight of metasilicate.
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention and has a pH greater than 10.
  • This detergent further 25 comprises:
  • Another such laundry detergent composition comprises 1 to 95 wt.% of a 30 detergent of the invention.
  • This detergent further comprises:
  • Yet another such laundry detergent composition comprises 1 to 95 wt.% of a 20 detergent of the invention. This detergent further comprises:
  • Another“green” laundry detergent composition comprises 1 to 95 wt.% of a detergent of the invention. This detergent further comprises:
  • sphingolipid 0% to 30% by weight of sphingolipid
  • glycolipid 15 0% to 30% by weight of glycolipid
  • the invention relates to methods for cold-water laundering.
  • cold water means water having a temperature less than or equal to 30 o C, preferably from 5 o C to 28 o C, more preferably 8 o C to 25 o C.
  • sourced water will have a temperature in this range without requiring added heat.
  • One such inventive method comprises laundering one or more textile articles in water having 25 a temperature less than or equal to 30 o C, preferably within the range of 5 o C to 28 o C, more preferably 8 o C to 25 o C, in the presence of a laundry detergent of the invention.
  • the inventive laundry detergent is used as a component of a laundry pre-spotter composition.
  • greasy or oily soils on the garments or textile fabrics are contacted directly with the pre-spotter in advance of laundering 30 either manually or by machine.
  • the fabric or garment is treated for 5-30 minutes.
  • the amount of active ⁇ -sulfonated fatty ester surfactant in the pre-spotter composition is preferably 0.5 to 50 wt.%, more preferably 1 to 30 wt.%, and most preferably 5 to 20 wt.%.
  • Treated fabric is machine laundered as usual, preferably at a temperature within the range of 5°C and 30°C, more preferably 10°C to 20°C, most preferably 12°C to 18°C.
  • the inventive laundry detergent is used in a pre-soaker composition for manual or machine washing.
  • the pre-soaker composition When used for manual washing, the pre-soaker composition is combined with cold water in a washing tub or other container.
  • the amount of active ⁇ -sulfonated fatty ester surfactant in the pre-soaker composition is preferably 1 to 80 wt.%, more10 preferably 3 to 50 wt.%.
  • Garments or textile fabrics are preferably saturated with pre- soaker in the tub, allowed to soak for 15-30 minutes, and laundered as usual. In manual washing, it is desirable to achieve high levels of foam to satisfy consumer perceptions.
  • the pre-soaker composition When used for machine washing, the pre-soaker composition is preferably added 15 to a machine containing water at a temperature within the range of 5°C and 30°C, more preferably 10°C to 20°C, most preferably 12°C to 18°C.
  • the amount of ⁇ -sulfonated fatty ester surfactant in the pre-soaker composition is preferably 1 to 80 wt.%, more preferably 3 to 50 wt.%.
  • Garments/textile fabrics are added to the machine, allowed to soak (usually with a pre-soak cycle selected on the machine) for 5-10 minutes, and then 20 laundered as usual.
  • the inventive laundry detergent is used as an additive for a laundry product or formulation.
  • the ⁇ -sulfonated fatty ester surfactant helps to improve or boost the grease removal or grease cutting performance of the laundry product or formulation.
  • the amount of ⁇ -sulfonated fatty ester 25 surfactant actives used will be within the range of 1 to 10 wt.%, more preferably 2 to 8 wt.%, and most preferably 3 to 5 wt.%.
  • the laundry product or formulation and the ⁇ - sulfonated fatty ester surfactant are preferably mixed until a homogeneous composition is obtained.
  • the detergent is in the form of a liquid, powder, paste, granule, 30 tablet, or molded solid, or a water-soluble sheet, sachet, pouch, capsule, or pod.
  • inventive compositions containing an ⁇ -sulfonated fatty ester surfactant it is desirable to achieve high levels of foam to satisfy consumer 5 cleaning perceptions.
  • inventive compositions based on ⁇ -sulfonated fatty ester surfactants it is desirable to have low or no foaming during the washing process. This aspect is especially valuable for proper functioning of the high-efficiency, side-loading washing machines under cold temperature conditions while achieving improved cleaning of 10 articles soiled with greasy soils.
  • Desirable surfactant attributes for laundry detergents include having the ability to be formulated as heavy duty liquid (HDL) detergents, powders, bar soaps, sachets, 15 pods, or other detergents forms.
  • HDL heavy duty liquid
  • HDLs this includes being in liquid form at room temperature, an ability to be formulated in cold-mix applications, and an ability to perform as well as or better than existing surfactants.
  • Desirable attributes for HDLs include, for example, the ability to emulsify, 20 suspend or penetrate greasy or oily soils and suspend or disperse particulates, in order to clean surfaces; and then prevent the soils, grease, or particulates from re-depositing on the newly cleaned surfaces.
  • ⁇ -sulfonated fatty ester surfactants of 30 the present disclosure will usually not be mere“drop-in” substitutions in an existing detergent formulation. Some amount of re-formulation is typically necessary to adjust the nature and amounts of other surfactants, hydrotropes, alkalinity control agents, and/or other components of the formulation in order to achieve a desirable outcome in terms of appearance, handling, solubility characteristics, and other physical properties and performance attributes. For example, a formulation might need to be adjusted by 5 using, in combination with the ⁇ -sulfonated fatty ester surfactant, a more highly ethoxylated nonionic surfactant instead of one that has fewer EO units. This kind of reformulating is considered to be within ordinary skill and is left to the skilled person’s discretion. 10 Additional Components
  • inventive laundry detergents can incorporate one or more of a variety of other components in addition to the ⁇ -sulfonated fatty ester surfactant, anionic surfactant, and nonionic surfactant described above. These components are detailed further below.
  • Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and where one of the aliphatic 20 substituents contains from about 8 to about 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. No. 3,664,961, the teachings of which are incorporated herein by reference).
  • Suitable ampholytic surfactants include fatty amine oxides and fatty amidopropylamine oxides.
  • cocoamidopropyl 25 betaine (CAPB) and coco betaine (CB).
  • Ampholytic surfactants can be used at a level from 1% to 50%, more preferably from 1% to 10%, even more preferably between 1% and 5% of the formulation, by weight.
  • compositions herein may comprise an amine oxide in accordance with the general formula :
  • R 1 (EO)x(PO)y(BO)z is preferably selected from hydrogen, methyl and -CH2OH.
  • R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary 5 alkyl moiety.
  • R 1 is a hydrocarbyl moiety having a chain length of from about 8 to about 18.
  • R 1 When x+y+z is different from 0, R 1 may be somewhat longer, having a chain length in the range C 12 -C24.
  • amine oxides where x+y+z is different from zero.
  • x+y+z is from about 1 to about 10
  • R 1 is a primary alkyl group containing about 8 to 15 about 24 carbons, preferably from about 12 to about 16 carbon atoms.
  • y+z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4;
  • EO represents ethyleneoxy;
  • PO represents propyleneoxy;
  • BO represents butyleneoxy.
  • Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with 20 dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
  • Preferred amine oxides are solids at ambient temperature. More preferably, they have melting points in the range of 30°C to 90°C.
  • Amine oxides suitable for use are made commercially by Stepan, Akzo Chemie, Ethyl Corp., Procter & Gamble, and others. See McCutcheon's compilation and a Kirk-Othmer review article for alternate 25 amine oxide manufacturers.
  • Preferred commercially available amine oxides are Ammonyx ® LO and Ammonyx ® MO surfactants (Stepan).
  • Preferred detergents include, e.g., hexadecyldimethylamine oxide dihydrate, octadecyldimethylamine oxide dihydrate, hexadecyltris(ethyleneoxy)dimethylamine oxide, and tetradecyldimethylamine oxide dihydrate.
  • R' is H
  • R' may be CH2OH, as in hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2- hydroxyethyl)amine oxide and oleylbis(2-hydroxyethyl)amine oxide.
  • Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and where one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent 10 contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono (see U.S. Pat. No. 3,664,961, the teachings of which are incorporated herein by reference).
  • Zwitterionic surfactants can be used as from 1% to 50%, more preferably from 1% to 10%, even more preferably from 1% to 5% by weight of the present formulations.
  • a laundry detergent composition in particular a 20 liquid composition (although the present disclosure is not limited to a liquid composition, or to a composition having any or all of these attributes) are that (1) a concentrated formulation is useful to save on shelf space of a retailer, (2) a“green” or environmentally friendly composition is useful, (3) a composition that works in modern high efficiency washing machines which use less energy and less water to wash clothes than previous 25 machines is useful, and (4) a composition that cleans well in cold water, i.e., less than 30 o C, preferably 5 o C to 30 o C.
  • a concentrated formulation is contemplated having two or even three, four, five, six, or even greater (e.g., 8x) times potency per unit volume or dose as conventional laundry detergents.
  • the use of less 30 water complicates the formulation of a detergent composition, as it needs to be more soluble and otherwise to work well when diluted in relatively little water.
  • the surfactants should be ultimately biodegradable and non-toxic.
  • a “green” formula may also advantageously be limited to the use of renewable hydrocarbons, such as vegetable or animal fats and oils, in the manufacture of 5 surfactants.
  • High efficiency (HE) washing machines present several challenges to the detergent formulation. As of January 2011, all washing machines sold in the U.S. must be HE, at least to some extent, and this requirement will only become more restrictive in the coming years. Front loading machines, all of which are HE machines, represent the 10 highest efficiency, and are increasingly being used.
  • Heavy duty liquid detergent formulas are impacted by HE machines because the significantly lower water usage requires that less foam be generated during the wash cycle. As the water usage levels continue to decrease in future generations of HE machines, detergents may be required to transition to no foam. In addition, HE HDLs 15 should also disperse quickly and cleanly at lower wash temperatures.
  • the detergent composition needs to work in relatively concentrated form in cold water, as these washing machines use relatively little water and cooler washing temperatures than prior machines.
  • the sudsing of such high-efficiency formulations must also be reduced, or even eliminated,20 in a low-water environment to provide effective cleaning performance.
  • the anti- redeposition properties of a high efficiency detergent formulation also must be robust in a low-water environment.
  • formulations that allow the used wash water to be more easily rinsed out of the clothes or spun out of the clothes in a washing machine are also contemplated, to promote efficiency.
  • Liquid fabric softener formulations and“softergent” (fabric softener/detergent dual functional) single-add formulations also may need to change as water usage continues to decline in HE machines.
  • a washer-added softener is dispensed during the rinse cycle in these machines.
  • the ⁇ -sulfonated fatty ester surfactants can be used in formulations that provide softening in addition to cleaning.
  • Laundry detergents and additives containing the presently described ⁇ - sulfonated fatty ester surfactants are contemplated to provide high concentration formulations, or“green” formulations, or formulations that work well in high efficiency washing machines.
  • Such detergents and additives are contemplated that have at least one of the advantages or desirable characteristics specified above, or combinations of two or more of these advantages, at least to some degree.
  • the ingredients 5 contemplated for use in such laundry detergents and additives are found in the following paragraphs.
  • a laundry detergent composition commonly contains other ingredients for various purposes. Some of those ingredients are also described below.
  • Any conventional builder system is suitable for use here, including 15 aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
  • phosphate builders could also be used here.
  • Suitable polycarboxylate builders for use here include citric acid, preferably in the form of a water-soluble salt, and derivatives of succinic acid of the formula:
  • R is C 10 -20 alkyl or alkenyl, preferably C 12 -C16, or where R can be substituted with hydroxyl, sulfo, sulfoxyl, or sulfone substituents.
  • Specific examples 25 include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenylsuccinate, or 2-tetradecenyl succinate.
  • Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium, and alkanolammonium salts.
  • suitable polycarboxylates are oxodisuccinates and mixtures of tartrate 30 monosuccinic and tartrate disuccinic acid, as described in U.S. Pat. No.4,663,071.
  • suitable fatty acid builders for use here are saturated or unsaturated C 10 -C-18 fatty acids, as well as the corresponding soaps.
  • Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
  • the preferred unsaturated fatty acid is oleic acid.
  • Another preferred builder system for 5 liquid compositions is based on dodecenyl succinic acid and citric acid.
  • alkaline agents include alkali metal (Na, K, or NH4) hydroxides, carbonates, citrates, and bicarbonates.
  • Na, K, or NH4 alkali metal hydroxides
  • carbonates carbonates
  • citrates citrates
  • bicarbonates Another commonly used builder is borax.
  • the builder or alkaline agent typically 10 comprises from 1% to 95% of the composition.
  • the builder or alkaline agent typically comprises from 1% to 60%, alternatively between 1% and 30%, alternatively between 2% and 15%.
  • the detergent compositions may further comprise one or more enzymes, which provide cleaning performance and/or fabric care benefits.
  • the enzymes include 20 cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ - glucanases, arabinosidases or mixtures thereof.
  • a preferred combination is a detergent composition having a cocktail of 25 conventional applicable enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with the lipolytic enzyme variant D96L at a level of from 50 LU to 8500 LU per liter of wash solution.
  • Suitable cellulases include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Pat. 30 No. 4,435,307, which discloses fungal cellulase produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275 and DE-OS- 2247832.
  • cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800. 5
  • suitable cellulases are cellulases originated from Humicola insolens having a molecular weight of about 50,000, an isoelectric point of 5.5 and containing 415 amino acid units.
  • suitable cellulases are the cellulases having color care benefits. Examples of such cellulases are cellulases described in EP Appl. No.91202879.2.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. 10 percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromoperoxidase.
  • Peroxidase- 15 containing detergent compositions are disclosed, for example, in PCT Int. Appl. WO 89/099813 and in EP Appl. No.91202882.6.
  • the cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
  • protease enzymes include those sold under the tradenames Alcalase ® , Savinase ® , Primase ® , Durazym ® , and Esperase ® by Novo Nordisk A/S (Denmark), those sold under the tradename Maxatase ® , Maxacal ® and Maxapem ® by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean ® and Optimase ® by Solvay Enzymes.
  • Other proteases 25 are described in U.S. Pat. No.5,679,630 can be included in the detergent compositions.
  • Protease enzyme may be incorporated into the detergent compositions at a level of from about 0.0001% to about 2% active enzyme by weight of the composition.
  • a preferred protease here referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a 30 precursor carbonyl hydrolase by substituting a different amino acid for the amino acid residue at a position in the carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus 5 amyloliquefaciens subtilisin, as described in U.S. Pat. No. 5,679,630, the teachings of which are incorporated herein by reference.
  • Lipases are enzymes that catalyze hydrolysis 10 of fats and oils to fatty acids and glycerol, monoglycerides, and/or diglycerides. Suitable lipases for use herein include those of animal, plant, fungal, and microbiological origin.
  • Suitable lipase enzymes can be found in cambium, bark, plant roots, and in the seeds of fruit, oil palm, lettuce, rice, bran, barley and malt, wheat, oats and oat flour, cotton tung kernels, corn, millet, coconuts, walnuts, fusarium, cannabis and cucurbit.
  • chemically modified or protein engineered mutants can be used.
  • Suitable lipases include lipases from microorganisms of the Humicola group (also called Thermomyces), e.g., from H. lanuginosa (T. lanuginosus) as described, e.g., in EP 258 068 and EP 305 216, or from H. insolens (see, e.g., PCT Internat. Appl. WO 20 96/13580); Pseudomonas lipases, e.g., from P. alcaligenes or P. pseudoalcaligenes (see, e.g., EP 218272), P. cepacia (see, e.g., EP 331376), P.
  • Lipase variants can be used, such as those described in U.S. Pat. Nos. 8,187,854; 7,396,657; and 6,156,552, the teachings of which are incorporated herein by reference. Additional lipase variants are described in PCT Internat. Appls. WO 92/05249, WO 94/01541, WO 95/35381, WO 96/00292, WO 95/30744, WO 94/25578, 30 WO 95/14783, WO 95/22615, WO 97/04079 and WO 97/07202, and in EP 0 407 225 and EP 0260105.
  • Suitable lipases include those sold under the tradenames Lipex TM , Lipolex TM , Lipoclean TM , Lipolase TM , Lipolase Ultra TM , Lipopan TM , Lipopan Xtra TM , Lypozyme TM , Palatase TM , Resinase TM , Novozym TM 435, and Lipoprime TM (all from Novozymes).
  • Other suitable lipases are available as Lipase P Amano TM (Amano Pharmaceutical). 5 Further suitable lipases are lipases such as M1 Lipase TM and Lipomax TM (DSM) and Lumafast TM (Danisco).
  • Preferred lipases include the D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa as described in U.S. Pat. No. 6,017,871.
  • the Humicola lanuginosa strain DSM 4106 is used.
  • the lipase can be used at any suitable level. Generally, the lipase is present in 10 the inventive detergents in an amount of 10 to 20000 LU/g of the detergent, or even 100 to 10000 LU/g.
  • the LU unit for lipase activity is defined in WO99/42566.
  • the lipase dosage in the wash solution is typically from 0.01 to 5 mg/L active lipase protein, more typically 0.1 to 2 mg/L.
  • the lipase can be used in the detergent at 0.00001 to 2 wt.%, usually 0.0001 to 1 wt.%, or even 0.001 to 0.5 wt.%.
  • the lipase may be incorporated into the detergent in any convenient form, e.g., non-dusting granules, stabilized liquids, or protected (e.g., coated) particles.
  • lipases useful herein, see U.S. Pat. Nos. 5,069,810; 5,093,256; 5,153,135; 5,614,484; 5,763,383; 6,177,012; 6,897,033; 7,790,666; 8,691,743; and 8,859,480, and U.S. Pat. Appl. Publ. No. 2011/0212877, the 20 teachings of which are incorporated herein by reference.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains. Suitable amylases are Termamyl ® (Novo Nordisk), Fungamyl ® and BAN ® amylases (Novo Nordisk).
  • compositions optionally contain a combination of enzymes or a single enzyme, with the amount of each enzyme commonly ranging from 0.0001% to 2%.
  • the detergent compositions optionally contain one or more soil suspending agents or resoiling inhibitors in an amount from about 0.01% to about 5% by weight, alternatively less than about 2% by weight.
  • Resoiling inhibitors include anti-redeposition 5 agents, soil release agents, or combinations thereof. Suitable agents are described in U.S. Pat. No. 5,929,022, and include water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Examples of such soil release and anti- redeposition agents include an ethoxylated tetraethylenepentamine. Further suitable ethoxylated amines are described in U.S. Pat. 4,597,898, the teachings of which are10 incorporated herein by reference.
  • clay soil removal/anti- redeposition agents are the cationic compounds disclosed in EP Appl. No. 111,965.
  • Other clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in EP Appl. No. 111,984; the zwitterionic polymers disclosed in EP Appl. No. 112,592; and the amine oxides disclosed in U.S. 15 Pat. No.4,548,744, the teachings of which are incorporated herein by reference.
  • CMC carboxymethylcellulose
  • Anti-redeposition polymers can be incorporated into HDL formulations described 20 herein. It may be preferred to keep the level of anti-redeposition polymer below about 2%. At levels above about 2%, the anti-redeposition polymer may cause formulation instability (e.g., phase separation) and or undue thickening.
  • Soil release agents are also contemplated as optional ingredients in the amount of about 0.1% to about 5% (see, e.g., U.S. Pat. No. 5,929,022).
  • Chelating agents in the amounts of about 0.1% to about 10%, more preferably about 0.5% to about 5%, and even more preferably from about 0.8% to about 3%, are also contemplated as an optional ingredient (see, e.g., U.S. Pat. No.5,929,022).
  • Polymeric dispersing agents in the amount of 0% to about 6% are also contemplated as an optional component of the presently described detergent 30 compositions (see, e.g., U.S. Pat. No. 5,929,022).
  • a suds suppressor is also contemplated as an optional component of the present detergent composition, in the amount of from about 0.1% to about 15%, more preferably between about 0.5% to about 10% and even more preferably between about 1% to about 7% (see, e.g., U.S. Pat. No. 5,929,022).
  • compositions that can be included are: carriers, hydrotropes, processing aids, dyes, pigments, solvents, bleaches, bleach activators, fluorescent optical brighteners, and enzyme stabilizing packaging systems.
  • compositions herein can also contain from about 0.25% to about 12%, preferably from about 0.5% to about 8%, more preferably from about 1% to about 4%, by weight of a cosurfactant selected from the 20 group of certain quaternary ammonium, diquaternary ammonium, amine, diamine, amine oxide and di(amine oxide) surfactants.
  • a cosurfactant selected from the 20 group of certain quaternary ammonium, diquaternary ammonium, amine, diamine, amine oxide and di(amine oxide) surfactants.
  • the quaternary ammonium surfactants are particularly preferred.
  • Quaternary ammonium surfactants can have the following formula:
  • R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R 3 is selected from the group consisting of
  • each R 4 is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R 4 groups,
  • R 6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0;
  • R 5 is the same as R 4 or is an alkyl chain wherein the total number of carbon atoms of R 2 plus R 5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and
  • X is any compatible anion.
  • alkyl quaternary ammonium surfactants 5 especially the mono-long chain alkyl surfactants described in the above formula when R 5 is selected from the same groups as R 4 .
  • the most preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate C 8 -C16 alkyl trimethylammonium salts, C 8 -C16 alkyl di(hydroxyethyl) methylammonium salts, C 8 -C16 alkyl hydroxyethyldimethylammonium salts, and C 8 -C16 alkyloxypropyl trimethylammonium 10 salts.
  • decyl trimethylammonium methylsulfate lauryl trimethylammonium chloride, myristyl trimethylammonium bromide and coconut trimethylammonium chloride and methylsulfate are particularly preferred.
  • U.S. Pat. No. 4,561,998 also provides that under cold water washing conditions, in this case less than about 65 o F (18.3 o C), the C 8 -C 10 alkyltrimethyl ammonium 15 surfactants are particularly preferred since they have a lower Kraft boundary and, therefore, a lower crystallization temperature than the longer alkyl chain quaternary ammonium surfactants herein.
  • Diquaternary ammonium surfactants can be of the formula:
  • R 2 , R 3 , R 4 , R 5 , y and X substituents are as defined above for the quaternary ammonium surfactants. These substituents are also preferably selected to provide diquaternary ammonium surfactants corresponding to the preferred quaternary ammonium surfactants. Particularly preferred are the C 8 -16 alkyl pentamethyl- ethylenediammonium chloride, bromide and methylsulfate salts.
  • Amine surfactants useful herein are of the formula:
  • R 2 , R 3 , R 4 , R 5 and y substituents are as defined above for the quaternary ammonium surfactants.
  • Particularly preferred are the C 12 -16 alkyl dimethyl amines.
  • R 2 , R 3 , R 4 , R 5 and y substituents are as defined above.
  • Preferred are the C 12 -C16 alkyl trimethylethylene diamines.
  • Amine oxide surfactants useful herein are of the formula:
  • R 2 , R 3 , R 4 , R 5 and y substituents are also as defined above for the quaternary ammonium surfactants.
  • Particularly preferred are the C 12 -16 alkyl dimethyl amine oxides.
  • Di(amine oxide) surfactants herein are of the formula:
  • R 2 , R 3 , R 4 , R 5 and y substituents are as defined above, preferably is C 12 -16 alkyl trimethylethylene di(amine oxide).
  • cleaning adjuncts are identified in U.S. Pat. No. 7,326,675 and PCT Int. Publ. WO 99/05242.
  • Such cleaning adjuncts are identified as including bleaches, bleach activators, suds boosters, dispersant polymers (e.g., from BASF Corp.15 or Dow Chemical) other than those described above, color speckles, silvercare, anti- tarnish and/or anti-corrosion agents, pigments, dyes, fillers, germicides, hydrotropes, anti-oxidants, enzyme stabilizing agents, pro-perfumes, carriers, processing aids, solvents, dye transfer inhibiting agents, brighteners, structure elasticizing agents, fabric softeners, anti-abrasion agents, and other fabric care agents, surface and skin care 20 agents.
  • dispersant polymers e.g., from BASF Corp.15 or Dow Chemical
  • color speckles e.g., from BASF Corp.15 or Dow Chemical
  • color speckles e.g., from BASF Corp.15
  • the detergent compositions may contain a fatty acid containing from about 10 to about 22 carbon atoms.
  • the fatty acid can also contain from about 1 to about 10 ethylene oxide units in the hydrocarbon chain.
  • Suitable fatty acids are saturated and/or unsaturated and can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oils, grease, and mixtures thereof) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
  • Examples of 5 suitable saturated fatty acids for use in the detergent compositions include capric, lauric, myristic, palmitic, stearic, arachidic and behenic acid.
  • Suitable unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid.
  • Examples of preferred fatty acids are saturated C 10 -C14 (coconut) fatty acids, from about 5:1 to about 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and mixtures 10 of the above lauric/myristic blends with oleic acid at a weight ratio of about 4:1 to about 1:4 mixed lauric/myristic:oleic.
  • fatty acid soaps are especially useful to control foam of the laundry compositions containing an ⁇ -sulfonated fatty ester surfactant of the present invention, especially when the laundering process is carried out in high- 15 efficiency, side-loading washing machines.
  • U.S. Pat. No. 4,507,219 identifies various sulfonate surfactants as suitable for use with the above-identified co-surfactants.
  • the disclosures of U.S. Pat. Nos. 4,561,998 and 4,507,219 with respect to co-surfactants are incorporated herein by reference.
  • Softergent technologies as described in, for example, U.S. Pat. Nos. 6,949,498, 5,466,394 and 5,622,925 can be used in the detergent compositions.
  • Softergent refers to a softening detergent that can be dosed at the beginning of a wash cycle for 25 the purpose of simultaneously cleaning and softening fabrics.
  • the ⁇ -sulfonated fatty ester surfactants can be used to make stable, aqueous heavy duty liquid laundry detergent compositions containing a fabric-softening agent that provide exceptional cleaning as well as fabric softening and anti-static benefits.
  • Some suitable softergent compositions contain about 0.5% to about 10%, 30 preferably from about 2% to about 7%, more preferably from about 3% to about 5% by weight of a quaternary ammonium fabric-softening agent having the formula: wherein R
  • R 1 and R2 are individually selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and --(C2H4O)x H where x has a value from 2 to 5;
  • X is an anion; and
  • R3 and R 4 are each a C 8 -C14 alkyl or (2) R3 is a C 8 -C22 alkyl and R4 5 is selected from the group consisting of C1-C 10 alkyl, C-C 10 hydroxy alkyl, benzyl, and --(C2 H4O)x H where x has a value from 2 to 5.
  • Preferred fabric-softening agents are the mono-long chain alkyl quaternary ammonium surfactants wherein in the above formula R1, R2, and R3 are each methyl and R4 is a C 8 -C18 alkyl.
  • the most preferred quaternary ammonium surfactants are the 10 chloride, bromide and methylsulfate C 8 -C16 alkyl trimethyl ammonium salts, and C 8 -C16 alkyl di(hydroxyethyl)-methyl ammonium salts.
  • lauryl trimethyl ammonium chloride, myristyl trimethyl ammonium chloride and coconut trimethylammonium chloride and methylsulfate are particularly preferred.
  • Another class of preferred quaternary ammonium surfactants are the di-C 8 -C14 15 alkyl dimethyl ammonium chloride or methylsulfates; particularly preferred is di- C 12 -C14 alkyl dimethyl ammonium chloride. This class of materials is particularly suited to providing antistatic benefits to fabrics.
  • a preferred softergent comprises the detergent composition wherein the weight ratio of anionic surfactant component to quaternary ammonium softening agent is from 20 about 3:1 to about 40: 1; a more preferred range is from about 5:1 to 20:1. Odor Control
  • Odor control technologies as described in, for example, U.S. Pat. No. 6,878,695 can be used in the detergent compositions.
  • a composition containing one or more of the ⁇ -sulfonated fatty ester surfactants can further comprise a low-degree of substitution cyclodextrin derivative and a perfume material.
  • the cyclodextrin is preferably functionally-available cyclodextrin.
  • the compositions can further comprise optional cyclodextrin-compatible and -incompatible materials, and other optional components.
  • Such a composition can be used for capturing unwanted molecules in a variety of contexts, preferably to control malodors including controlling malodorous molecules on inanimate surfaces, such as 5 fabrics, including carpets, and hard surfaces including countertops, dishes, floors, garbage cans, ceilings, walls, carpet padding, air filters, and the like, and animate surfaces, such as skin and hair.
  • the low-degree of substitution cyclodextrin derivatives useful herein are preferably selected from low-degree of substitution hydroxyalkyl cyclodextrin, low-10 degree of substitution alkylated cyclodextrin, and mixtures thereof.
  • Preferred low- degree of substitution hydroxyalkyl ⁇ -cyclodextrins have an average degree of substitution of less than about 5.0, more preferably less than about 4.5, and still more preferably less than about 4.0.
  • Preferred low-degree of substitution alkylated cyclodextrins have an average degree of substitution of less than about 6.0, more 15 preferably less than about 5.5, and still more preferably less than about 5.0.
  • the detergent compositions can comprise a mixture of cyclodextrins and derivatives thereof such that the mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivatives described hereinbefore.
  • Such cyclodextrin mixtures preferably comprise high-degree of 20 substitution cyclodextrin derivatives (having a higher average degree of substitution than the low-degree substitution cyclodextrin derivatives described herein) and non- derivatized cyclodextrin, such that the cyclodextrin mixture effectively has an average degree of substitution equivalent to the low-degree of substitution cyclodextrin derivative.
  • a composition comprising a cyclodextrin mixture containing 25 about 0.1% non-derivatized ⁇ -cyclodextrin and about 0.4% hydroxypropyl ⁇ -cyclodextrin having an average degree of substitution of about 5.5, exhibits an ability to capture unwanted molecules similar to that of a similar composition comprising low-degree of substitution hydroxypropyl ⁇ -cyclodextrin having an average degree of substitution of about 3.3.
  • Such cyclodextrin mixtures can typically absorb odors more broadly by 30 complexing with a wider range of unwanted molecules, especially malodorous molecules, having a wider range of molecular sizes preferably at least a portion of a cyclodextrin mixture is ⁇ -cyclodextrin and its derivatives thereof, ⁇ -cyclodextrin and its derivatives thereof, and/or ⁇ -cyclodextrin and its derivatives thereof; more preferably a mixture of ⁇ -cyclodextrin, or an ⁇ -cyclodextrin derivative, and derivatized ⁇ -cyclodextrin, even more preferably a mixture of derivatised ⁇ -cyclodextrin and derivatized ⁇ - 5 cyclodextrin; and most preferably a mixture of hydroxypropyl ⁇ -cyclodextrin and hydroxypropyl ⁇ -cyclodextrin, and/or a mixture of methylated ⁇ -cyclodextrin
  • the cavities within the functionally-available cyclodextrin in the detergent compositions should remain essentially unfilled (i.e., the cyclodextrin remains 10 uncomplexed and free) or filled with only weakly complexing materials when in solution, in order to allow the cyclodextrin to absorb (i.e., complex with) various unwanted molecules, such as malodor molecules, when the composition is applied to a surface containing the unwanted molecules.
  • Non-derivatized (normal) ⁇ -cyclodextrin can be present at a level up to its solubility limit of about 1.85% (about 1.85 g in 100 grams of 15 water) at room temperature.
  • ⁇ -Cyclodextrin is not preferred in compositions which call for a level of cyclodextrin higher than its water solubility limit.
  • Non-derivatized ⁇ - cyclodextrin is generally not preferred when the composition contains surfactant since it affects the surface activity of most of the preferred surfactants that are compatible with the derivatized cyclodextrins.
  • the level of low-degree of substitution cyclodextrin derivatives that are functionally-available in the odor control compositions is typically at least about 0.001%, preferably at least about 0.01%, and more preferably at least about 0.1%, by weight of the detergent composition.
  • the total level of cyclodextrin in the present composition will be at least equal to or greater than the level of functionally-available cyclodextrin.
  • the 25 level of functionally-available will typically be at least about 10%, preferably at least about 20%, and more preferably at least about 30%, by weight of the total level of cyclodextrin in the composition.
  • Concentrated compositions can also be used.
  • a concentrated product i.e., when the total level of cyclodextrin used is from about 3% to about 60%, 30 more preferably from about 5% to about 40%, by weight of the concentrated composition, it is preferable to dilute the concentrated composition before treating fabrics in order to avoid staining.
  • the concentrated cyclodextrin composition is diluted with about 50% to about 6000%, more preferably with about 75% to about 2000%, most preferably with about 100% to about 1000% by weight of the concentrated composition of water.
  • the resulting diluted compositions have usage concentrations of 5 total cyclodextrin and functionally-available cyclodextrin as discussed hereinbefore, e.g., of from about 0.1% to about 5%, by weight of the diluted composition of total cyclodextrin and usage concentrations of functionally-available cyclodextrin of at least about 0.001%, by weight of the diluted composition. 10 Forms
  • the detergent compositions can take any of a number of forms and any type of delivery system, such as ready-to-use, dilutable, wipes, or the like.
  • the detergent compositions can be a dilutable fabric detergent, which may be an isotropic liquid, a surfactant-structured liquid, a granular, spray-dried 15 or dry-blended powder, a tablet, a paste, a molded solid, a water soluble sheet, or any other laundry detergent form known to those skilled in the art.
  • a "dilutable” fabric detergent composition is defined, for the purposes of this disclosure, as a product intended to be used by being diluted with water or a non-aqueous solvent by a ratio of more than 100:1, to produce a liquor suitable for treating textiles.
  • Green concentrate 20 compositions like those on the market today can be formulated such that they could be a concentrate to be added to a bottle for final reconstitution.
  • the detergent compositions can also be formulated as a gel or a gel packet or pod like the dishwasher products on the market today.
  • Water-soluble sheets, sachets, or pods such as those described in U.S. Pat. Appl. No.2002/0187909, the teachings of 25 which are incorporated herein by reference, are also envisaged as a suitable form.
  • the detergent composition can also be deposited on a wiper or other substrate.
  • Polymeric suds enhancers are also be deposited on a wiper or other substrate.
  • polymeric suds enhancers such as those described in U.S. 30 Pat. No. 6,903,064 can be used in the detergent compositions.
  • the compositions may further comprise an effective amount of polymeric suds volume and suds duration enhancers. These polymeric materials provide enhanced suds volume and suds duration during cleaning.
  • each of R 1 , R 2 and R 3 are independently selected from the group consisting of hydrogen, C1 to C6 alkyl, and mixtures thereof;
  • L is O;
  • Z is CH2 ;
  • z is an integer selected from about 2 to about 12;
  • A is NR 4 R 5 , wherein each of R 4 and R 5 is independently selected from the group consisting of hydrogen, C1 to C 8 alkyl, and 10 mixtures thereof, or NR 4 R 5 form an heterocyclic ring containing from 4 to 7 carbon atoms, optionally containing additional hetero atoms, optionally fused to a benzene ring, and optionally substituted by C1 to C 8 hydrocarbyl;
  • the exemplary polymeric suds stabilizer described above has a molecular weight of from about 1,000 to about 2,000,000; more preferably the molecular weight is about 5,000 to about 1,000,000.
  • Methods for laundering fabrics with ⁇ -sulfonated fatty ester surfactant-based formulations are contemplated. Such methods involve placing fabric articles to be laundered in a high efficiency washing machine or a regular (non-high efficiency) 25 washing machine and placing an amount of the detergent composition sufficient to provide a concentration of the composition in water of from about 0.001% to about 5% by weight when the machine is operated in a wash cycle.
  • a high efficiency machine is defined by the Soap and Detergent Association as any machine that uses 20% to 66% of the water, and as little as 20% - 50% of the energy, of a traditional, regular agitator washer (SDA“Washers and Detergents” publication 2005; see www.cleaning101.com).
  • SDA“Washers and Detergents” publication 2005; see www.cleaning101.com The wash cycle is actuated or started to launder the fabric articles. Hand washing using 5 the inventive detergent compositions is also contemplated.
  • the invention is a method which comprises laundering one or more textile articles in water having a temperature less than or equal to 30 o C, preferably from 5 o C to 28 o C, the presence of an inventive detergent as described herein.
  • the surfactants should also be valuable in applications where greasy substances require removal or 15 cleaning.
  • Such applications include, for example, household cleaners, degreasers, sanitizers and disinfectants, light-duty liquid detergents, hard and soft surface cleaners for household, autodish detergents, rinse aids, laundry additives, carpet cleaners, spot treatments, softergents, liquid and sheet fabric softeners, industrial and institutional cleaners and degreasers, oven cleaners, car washes, transportation cleaners, drain 20 cleaners, industrial cleaners, foamers, defoamers, institutional cleaners, janitorial cleaners, glass cleaners, graffiti removers, adhesive removers, concrete cleaners, metal/machine parts cleaners, and food service cleaners, and other similar applications for which removal of greasy soils is advantageously accomplished, particularly at room temperature or below.
  • the detergents may also be beneficial for certain personal care 25 applications such as hand soaps and liquid cleansers, shampoos, and other hair/scalp cleansing products, especially for oily/greasy hair, scalp, and skin, which are also beneficial when effective with lukewarm or cold water.
  • personal care 25 applications such as hand soaps and liquid cleansers, shampoos, and other hair/scalp cleansing products, especially for oily/greasy hair, scalp, and skin, which are also beneficial when effective with lukewarm or cold water.
  • a small-scale batch reactor maintained at 20 o C under a flow of nitrogen is charged with“C12-14” methyl esters (81.3 g). Over 30 minutes, sulfur trioxide (33.7 g) is evaporated via a 140 o C flash-pot and bubbles through the batch reactor using a 2 L/m nitrogen stream. The temperature of the reaction mixture is maintained between 10 20 o C and 35 o C. After the addition, the reaction mixture is held for an additional 5 minutes. The contents are transferred to a jar and placed in an 85 o C oven for 1.5 h.
  • the product is filtered and washed with acetonitrile (250 mL), placed on a vacuum line, and dried. Ethanol (750 mL) is added and the acidic material is neutralized with 50% aq. NaOH solution (about 14 g). The sample is 25 concentrated and combined with 100% ethanol (about 500 mL). The ethanol solution is placed in a freezer. The resulting precipitate is subsequently filtered. The precipitate contains both the desired n-octyl ⁇ -sulfonated fatty ester and a proportion of ⁇ -sulfoacid di-salts.
  • Laundry detergent (to give 0.1% actives in washing solution) is charged to the washing machine, followed by soiled/stained fabric swatches that are attached to pillowcases. Wash temperature: 60 o F. Rinse temperature: 60 o F. The swatches are 5 detached from pillowcases, dried, and gently ironed. Swatches are scanned to measure the L* a* b* values, which are used to calculate a soil removal index (SRI) for each type of swatch. Finally, the ⁇ SRI is calculated, which equals the experimental sample SRI minus the SRI of a pre-determined standard laundry detergent formula (or control). When ⁇ SRI ⁇ 0.5 differences are perceivable to the naked eye.
  • the sample is superior. If ⁇ SRI is less than or equal to - 0.5, the sample is inferior. If ⁇ SRI is greater than -0.5 and less than 0.5, the sample is considered equal to the standard.
  • the following standard soiled/stained fabric swatches are used: bacon grease, cooked beef fat, and beef tallow on cotton fabric. At least three swatches of each kind 15 are used per wash. Swatches are stapled to pillowcases for laundering, and extra pillowcases are included to complete a six-pound fabric load.
  • a Hunter LabScan ® XE spectrophotometer is used to determine the L* a* b* values to calculate the SRI for every type of swatch, and the stain removal index (SRI) is calculated as follows:
  • Performance results for cold-water cleaning of cotton fabric treated with bacon grease, cooked beef fat, and beef tallow greasy soils are compared. All formulations are tested at 0.1% actives levels. Wash cycles are 30 min in front-loading high- efficiency washing machines.
  • the target performance (which corresponds to a ⁇ SRI 5 value of 0.0) is that of a commercial cold-water detergent or a control cold-water detergent used with a cold-water wash (60 o F) and cold-water rinse (60 o F).
  • Table 1 summarizes control, A, B, C, and D heavy-duty laundry formulations from ⁇ -sulfonated fatty esters made from“C 8 -10,” a mixture of about 57% C 8 methyl ester and about 43% C 10 methyl ester (average of 8.9 carbons in the fatty acid).
  • 10 Transesterification provides the ⁇ -sulfonated C 8 -C 10 fatty acid octyl, nonyl, decyl, and dodecyl esters listed in the table. These are used to replace a sodium C 12 -C14 alcohol ethoxylate (3 EO) sulfate [“NaAES (3EO)”], which is used in the control formulation.
  • 3 EO sodium C 12 -C14 alcohol ethoxylate
  • Table 2 summarizes control, E, F, and G formulations from ⁇ -sulfonated fatty esters made from“C12-14,” a mixture of about 71% C 12 methyl ester and about 29% 15 C14 methyl ester (average of 12.6 carbons in the fatty acid).
  • Transesterification provides the ⁇ -sulfonated C 12 -C14 fatty acid octyl, 2-ethylhexyl, or decyl esters listed in the table. These are used to replace Biosoft ® S-101, a linear alkylbenzene sulfonic acid (“HLAS”), which is used in the control formulation.
  • HLAS linear alkylbenzene sulfonic acid
  • Tables 3A and 3B summarize control, H, I, J, and K formulations, and control, L,20 M, N, and O formulations, respectively, from ⁇ -sulfonated fatty esters made from“C12- 18,” a mixture containing about 56% of C 12 methyl ester, about 23% of C14 methyl ester, about 9.5% C16 methyl ester, and about 18% of C18 methyl ester (average of 14.7 carbons in the fatty acid).
  • Transesterification provides the ⁇ -sulfonated C 12 -C18 fatty acid butyl, hexyl, octyl, nonyl, decyl, and dodecyl esters listed in the table.
  • Formulations 25 H, I, and J are comparative examples because the ⁇ -sulfonated fatty esters are based on alcohols having fewer than eight carbons.
  • the ⁇ - sulfonated C 12 -C18 fatty acid octyl, nonyl, decyl, or dodecyl ester replaces either [NaAES (3EO)] (Formulations K, M, N, and O) or HLAS (Formulation L).

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Abstract

L'invention concerne des détergents pour lessive utiles pour le nettoyage à l'eau froide et un procédé de nettoyage à l'eau froide. Les détergents comprennent : (a) un tensioactif de type ester gras α-sulfoné comprenant un composé de la formule : R1-CH(SO3M)-CO-OR2 dans laquelle M est un atome d'hydrogène, un métal alcalin, un métal alcalino-terreux, un ammonium et un sel d'amine, ou un mélange de ces derniers ; R1 est un groupe alkyle en C6-C16 linéaire ou ramifié, saturé ou insaturé, non substitué ou substitué par un hydroxy ; et R2 est un groupe alkyle en C8 à C12 linéaire ou ramifié, saturé ou insaturé ; et (b) un tensioactif anionique, un tensioactif non ionique ou une combinaison de ces derniers. De manière surprenante, les tensioactifs de type ester gras α-sulfoné dérivés d'un alcool en C8 à C12 fournissent d'excellentes performances dans l'élimination des taches grasses telles que la graisse de bacon, la graisse de bœuf cuite, ou le suif de bœuf d'articles salis, même à des températures de lavage à 30 °C ou moins. Les détergents formulés avec les tensioactifs surpassent les détergents à l'eau froide d'une large marge, y compris les détergents comprenant des esters gras α-sulfonés, fabriqués à partir d'alcools inférieurs, tels que les esters de méthyle, de butyle ou d'hexyle d'acides gras α-sulfonés.
PCT/US2016/023525 2015-03-31 2016-03-22 Détergents à base de tensioactifs ester gras alpha-sulfonés Ceased WO2016160407A1 (fr)

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WO2019017764A1 (fr) * 2017-07-19 2019-01-24 Kl-Kepong Oleomas Sdn Bhd Système tensioactif
CN111763310A (zh) * 2019-03-31 2020-10-13 江苏海云花新材料有限公司 一种脂肪酸甲酯乙氧基化物磺酸盐及其制备方法
WO2021035216A1 (fr) * 2019-08-22 2021-02-25 Henkel IP & Holding GmbH Compositions détergentes liquides comprenant un mélange de tensioactifs écologiquement responsables
WO2021190993A1 (fr) * 2020-03-24 2021-09-30 Evonik Operations Gmbh Compositions contenant des rhamnolipides, un polyglycoside d'alkyle et un acyllactylate
RU2764033C2 (ru) * 2017-09-06 2022-01-12 Као Корпорейшн Детергентная композиция для текстильных изделий
US20220154100A1 (en) * 2020-11-13 2022-05-19 Korex Canada Company Concentrated laundry cleaning compositions in unit dose packets or pouches
CN114685078A (zh) * 2020-12-30 2022-07-01 江苏苏博特新材料股份有限公司 一种高稳泡型混凝土引气剂、其制备方法及应用

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