Classifications

• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
  • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
• • 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
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with cationic compounds
  • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol 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
  • C11D1/66—Non-ionic compounds
  • C11D1/662—Carbohydrates or derivatives
• • 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
  • C11D1/835—Mixtures of non-ionic with cationic 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
• • 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
• • 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
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
• • 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
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
  • C11D1/28—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
  • C11D1/12—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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• This invention relates to detergent compositions containing detersive surfactant and polymeric dispersing agent.
• this invention relates to detergent compositions containing deter ⁇ sive surfactant systems including a polyhydroxy fatty acid amide surfactant.
• Detergent compositions useful for cleaning purposes such as laundering of fabrics, have commonly utilized a variety of surfactants, adjunct cleaning ingredients specifically tailored to the type of cleaning that is needed, as well as other ingredients added for processing and/or aesthetic purposes.
• adjunct cleaning ingredients that is commonly added to detergent compositions to be used for laundry and other textile-cleaning application is polymeric dispersing agent such as polycarboxylate dispersing agents and polyethylene glycol dispersing agents, to assist in removal of particulate soil from fabrics, textiles, etc. These polymeric dispersing agents are used in combination with detersive surfactants and other optional detergent adjuncts known in the art.
• surfactants in recent years have been derived from petroleum-based feedstocks. These include, most prominently, surfactants such as the linear alkyl benzene sulphonates, which can provide excellent overall cleaning performance over a wide variety of conditions.
• the linear alkyl benzene sulfonates provide excellent grease and oil cleaning without necessitating either high wash temperatures or high concentration, unlike the conventional nonionic surfactants which can alternately be utilized for grease and oil cleaning but which require high wash temperature and/or high wash concentration.
• these surfactants have provided admirable results, it would be desirable to reduce the level of surfactant material in the compositions based upon petroleum feedstocks while retaining comparable overall cleaning performance.
• detergent for ulators are traditionally forced with the problem of providing detergent composition which provides both good grease and oil cleaning ability with good particulate soil removal, since conventional techniques for improving grease and oil cleaning can adversely affect particulate soil removal, and vice versa.
• Other surfactants which can interfere with particulate soil removal performance include alkyl ethoxy!ates and alkyl phenol ethoxylates.
• polyhydroxy fatty acid amide surfactants can provide excellent overall cleaning performance, including excellent grease and oil cleaning performance over a wide range of wash conditions, especially when combined with other anionic and/or nonionic surfactants.
• detergent composition containing these polyhydroxy fatty acid amides in combination with one or more polymeric dispersing agents can additionally provide excellent particulate clay soil removal.
• detergent compositions which contain certain polyhydroxy fatty acid amides, optional anionic or other nonionic surfactants, and a polymeric polycarboxylate dispersing agent.
• N-acyl, N-methyl glucamides for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles," Liquid Crystals, 1988, Volume 3, No. 11, pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R. Hilgenfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem.
• N-alkyl polyhydroxyamide surfactants have been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the journal article "N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K. Hildreth.
• N-alkyl glucamides in detergent compositions has also been discussed.
• U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and G.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent.
• These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms.
• These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and carbonates. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.
• U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz relates to aqueous detergent compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid.
• the product of this reaction is said to be useable in aqueous detergent compositions without further purification.
• PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth relates to a phiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing of liposomes.
• R'C0N(R)CH2R" and R"C0N(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.
• N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R ⁇ C(0)N(X)R2 wherein Ri is a C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a Ci-Ci ⁇ (preferably Ci-C ⁇ ) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four too seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide.
• the thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfac- tant systems can contain other anionic surfactants, such as alkyl- aryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc.
• anionic surfactants such as alkyl- aryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates
• nonionic surfactants such as fatty alcohol polyglycol ether, alkyl
• Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified.
• the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attributes.
• U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al. relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylglucamide nonionic surfactant which is selected from N-methyl,N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.
• glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al., which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxyalkyl-amine of the formula R ⁇ C(0)N(R2)CH2(CHOH) n - CH OH, wherein Ri is a C1-C3 alkyl, R2 is a C10-C22 alkyl, and n is 3 or 4.
• the N-acylpolyhydroxyalkyl-amine is added as a soil sus ⁇ pending agent.
• U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al. relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxylalkyl compound of the formula R ⁇ N(Z)C(0)R2 wherein Ri is a C10-C22 alkyl, R2 is a C7-C21 alkyl, Ri and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CH0H) m CH20H where m is 3 or 4.
• Patent 4,021,539 issued May 3, 1977, to H. M ⁇ ller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxylalkyl-amines which include compounds of the formula RlN(R)CH(CH0H) m R2 wherein Ri is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as Rl but both cannot be H, and R2 is CH2OH or COOH.
• French Patent 1,360,018, April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of amides of the formula RC(0)N(R ⁇ )G wherein R is a carboxylic acid functionality having at least seven carbon atoms, Ri is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.
• German Patent 1,261,861, February 29, 1968, A. Heins relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(R ⁇ )(R2) wherein R is a sugar residue of glucamine, Rl is a C10-C20 alkyl radical, and R2 is a C1-C5 acyl radical.
• G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc.
• the compounds are expressed by the formula N(R)(R ⁇ )C(0)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, Ri is a onovalent hydrocarbon radical, and -C(0)R2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.
• U.S. Patent 3,312,627 discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenedia ine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(0)NRl(R 2 ) wherein RC(0) contains from about 10 to about 14 carbon atoms, and Rl and R2 each are H or Ci-Cs alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxy! groups of from 2 to about 6.
• RC(0)NRl(R 2 ) wherein RC(0) contains from about 10 to about 14 carbon atoms, and Rl and R2 each are H or Ci-Cs alkyl groups
• R 1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, R2 is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls, or an alkoxylated derivative thereof;
• the polymeric dispersing agents hereof include polycarboxylate and polyethylene glycol polymers.
• This invention further provides a method for improving the performance of detergents containing polymeric dispersing agent and detersive surfactant by additionally incorporating into such composition at least about 1%, by weight, of the polyhydroxy fatty acid amide surfactant described above.
• This invention further provides a method for cleaning substrates, such as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate, with a detergent composition comprising one or more anionic, nonionic, or cationic surfactants, at least about 0.5%, by weight, polymeric dispersing agent, and at least 1% of the polyhydroxy fatty acid amide.
• a detergent composition comprising one or more anionic, nonionic, or cationic surfactants, at least about 0.5%, by weight, polymeric dispersing agent, and at least 1% of the polyhydroxy fatty acid amide.
• compositions hereof will comprise at least about 1%, typically from about 3% to about 50%, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide surfactant described below.
• the polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula: 0 Rl
• R2 - C - N - Z wherein: R is H, C1-C hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R 2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.
• Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
• Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose.
• high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials.
• Z preferably will be selected from the group consisting of -CH 2 -(CH0H) n -CH 2 0H, -CHfCHjOHMCHOHJn- ! - CH 2 0H, -CH 2 -(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosacchar- ide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
• R 1 can be, for example, N-methyl, N-ethyl , N-propyl, N-isopropyl, N-butyl , N-2-hydroxy ethyl, or N-2-hydroxy propyl .
• R 2 -C0-N ⁇ can be, for example, cocamide, steara ide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
• Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl , 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl , 1-deoxymalto- triotityl, etc.
• Methods for making polyhydroxy fatty acid amides are known in the art.
• compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,060, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 2,965,575, issued December 20, 1960 to E. R. Wilson, and U.S.
• the amount of catalyst is preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis.
• the reaction is preferably carried out at from about 138'C to about 170'C for typically from about 20 to about 90 minutes.
• the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, and mixtures thereof.
• this process is carried out as follows:
• polyhydroxy "fatty acid” amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, non-petro ⁇ chemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.
• the processes used to produce them will also typically produce quantities of nonvolatile by-product such as esteramides and cyclic polyhydroxy fatty acid amide.
• the level of these by-products will vary depending upon the particular reactants and process conditions.
• the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid amide- containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide.
• the preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product. Additional Detersive Surfactants
• the composi ⁇ tions can contain other detersive surfactants.
• the compositions will comprise from 1% to about 45% of such other surfactants, preferably from about 5% to about 40%, more typically from about 5% to about 25% of such other surfactants.
• These addi ⁇ tional surfactants can include any surfactants useful for detersive purposes. They include anionic and nonionic surfactants, as well as other surfactants such as cationic, zwitterionic, and ampholytic surfactants.
• the present invention is particularly beneficial when the detergent compositions include anionic surfactants which are relatively sensitive to wash water hardness, such as alkyl benzene sulfonates, alkyl sulfates, alkyl ester sulfonates, and alkyl alkoxylated sulfonates.
• anionic surfactants which are relatively sensitive to wash water hardness
• Other surfactants especially commonly used ones such as alkyl ethoxylates, alkyl polyglycosides, and paraffin sulfonates can also be included.
• the utilization of the polyhydroxy fatty acid amide can assist in .the formulation of detergent compositions containing such surfactants.
• Alkyl ester sulfonate anionic surfactants hereof include linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.
• alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
• R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof
• R 4 is a Ci-C ⁇ hydrocarbyl, preferably an alkyl, or combination thereof
• M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
• Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g.
• R 3 is C10-C16 alkyl
• R 4 is methyl, ethyl or isopropyl.
• methyl ester sulfonates wherein R 3 is C14-C16 alkyl.
• Alkyl Sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like.
• alkyl chains of C12-C16 are preferred
• Alkyl Alkoxylated Sulfate surfactants hereof are water soluble salts or acids of the formula R0(A) m S03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C1Q-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-arnmonium cation.
• R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C1Q-C24 alkyl component, preferably a C
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines, e.g. onoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
• Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate, wherein M is conveniently selected from sodium and potassium.
• Other Anionic Surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate, wherein M is conveniently selected from sodium and potassium.
• Other Anionic Surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-C
• anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 olefinsulphonates, sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
• salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
• C9-C20 linear alkylbenzenesulphonates C8-C22 primary or secondary alkanesulphonates
• C8-C24 olefinsulphonates C8-C24
• alkyl glycerol sulfonates alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N * -acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolygluco
• 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 such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al . at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
• Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.
• the polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide.
• the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol.
• nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM ⁇ _45, ⁇ -n4, ⁇ _ ⁇ oo, and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates) .
• the condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol.
• nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation product of C11-C15 linear secondary alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the condensation product of C1 -C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), NeodolTM 45.4 (the condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and KyroTM EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company.
• the hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility.
• the addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
• Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
• the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine consist of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
• This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000.
• this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
• Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
• Semi-polar nonionic detergent surfactants include the amine oxide surfactants having the formula
• R 3 (0R ) X ?N(R5) 2 wherein R 3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms;
• R 4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each ⁇ ⁇ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups.
• the R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
• amine oxide surfactants in particular include Cio-Cis alkyl dimethyl amine oxides and C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
• Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties.
• the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.
• the intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
• a polyalkylene- oxide chain joining the hydrophobic moiety and the polysaccharide moiety.
• the preferred alkyleneoxide is ethylene oxide.
• Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms.
• the alkyl group is a straight chain saturated alkyl group.
• the alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties.
• Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl , pentadecyl , hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses.
• Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.
• the preferred alkylpolyglycosides have the formula
• R2 ⁇ (C n H2nO)t(glycosyl) x
• R2 is selected from the group consisting of alkyl, alkyl- phenyl, hydroxyalkyl, hydroxyalkylphenyl , and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about- 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
• the glycosyl is preferably derived from glucose.
• the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position).
• the additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.
• R 6 is an alkyl group containing from about 7 to about 21
• each ⁇ 7 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4 ⁇ ) ⁇ H where x varies from about 1 to about 3.
• Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
• Cationic detersive surfactants can also be included in detergent compositions of the present invention.
• Cationic surfactants include the ammonium surfactants such as alkyldimethyl- ammonium halogenides, and those surfactants having the 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 -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2 ⁇ H)-, -CH2CH2CH2-, and mixtures thereof
• 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, -CH2CHOH-CHOHCOR6CHOHCH2OH wherein 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
• cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Ca bre, issued October 14, 1980, incorporated herein by reference..
• Other Surfactants Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched.
• One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.
• Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfoniu compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.
• Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.
• Polymeric Dispersing Agents are generally used in combination with one or more anionic and/or nonionic surfactants.
• Polymeric dispersing agents can advantageously be utilized in the compositions hereof. These materials can aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that the polymeric dispersing agents enhance overall detergent cleaning performance by crystal growth inhibition, aiding in particulate soil peptization, and anti-redeposition.
• the compositions hereof will contain at least about 0.5%, preferably from about 1% to about 10%, more preferably from about 2% to about 5%, of the polymeric dispersing agent.
• Polycarboxylate materials which can be employed as the polymeric dispersing agent component herein are these polymers or copolymers which contain at least about 60% by weight of monomer units with the general formula
• X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M a salt-forming cation and n is from about 30 to about 400.
• X is hydrogen or hydroxy
• Y is hydrogen or carboxy
• Z is hydrogen
• M is hydrogen, alkali metal, ammonia or substituted ammonium.
• Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copoly erizing suitable unsaturated carboxylate monomers, preferably in their acid form.
• suitable monomer starting materials include acrylates, maleates, fumarates, itaconates, aconitates, mesaconates, citraconates, and methylene- malonates.
• Corresponding unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
• polymeric polycarboxyl ⁇ ates herein of monomeric segments, containing non-carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
• Particularly suitable polymeric polycarboxylates are the polymeric poly-acrylates which, preferably, are derived from acrylic acid.
• acrylic acid-based polymers which are useful herein include the water-soluble salts of polymerized acrylic acid.
• the average molecular weight of such polyacrylate polymers will preferably be at least about 1,000, and will preferably range from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000, said molecular weights being based upon the acid form.
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967. This patent is incorporated herein by reference.
• Acrylic/maleic-based copolymers may also be used as a preferred component of the polymeric dispersing agent.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
• the average molecular weight of such copolymers in the acid form ranges from about 2,000 to 100,000, more preferably from about 5,000 to about 75,000, most preferably from about 7,000 to 65,000.
• the ratio of acrylate to aleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, which publication is incorporated herein by reference.
• PEG polyethyl ⁇ ene glycol
• PEG can exhibit dispersing agent performance as well as act as a clay soil removal/anti-redeposition agent.
• Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
• Builders Detergent compositions of the present invention can comprise inorganic or organic detergent builders to assist in mineral hard ⁇ ness control .
• the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
• Liquid formula- tions typically comprise at least about 1%, more typically from about 5% to about 50%, preferably about 5% to about 30%, by weight of detergent builder.
• Granular formulations typically comprise at least about 1%, more typically from about 10% to about 80%, prefer ⁇ ably from about 15% to about 50% by weight of the detergent builder.
• Lower or higher levels of builder are not meant to be excluded.
• Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
• Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions hereinafter collectively “borate builders"
• non-borate builders are used in compositions of the invention intended for use at wash conditions less than about 50'C, especially less than about 40'C.
• silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
• layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
• other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
• carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference.
• Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
• Preferred aluminosilicates are zeolite builders which have the formula:
• aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
• the crystalline aluminosilicate ion exchange material has the formula: Nai2[(A10 2 )i2(Si ⁇ 2)i2]-xH 2 0 wherein x is from about 20 to about 30, especially about 27.
• This material is known as Zeolite A.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.
• phosphonate builder salts are the water-soluble salts of ethane 1-hydroxy-l, 1-diphosphonate particularly the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzyl ethylidene and halo methylidene phosphonates.
• Phosphonate builder salts of the aforementioned types are di-sclosed in U.S. Patent Nos.
• Polycarboxylate builder can generally be added to the composition in acid form, but can also.be added in the form of a neutralized salt.
• alkali metals such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium (e.g., alkanolammonium) salts are preferred.
• Included among the polycarboxylate builders are a variety of categories of useful materials.
• One important category of polycarboxylate builders encompasses the ether polycarboxylates.
• a number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S.
• a specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula:
• TDS tartrate disuccinic acid
• Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which are incorporated herein by reference.
• Other useful detergency builders include the ether hydroxypoly- carboxylates represented by the structure:
• n H0-[C(R)(C00M)-C(R)(C00M)-0] n -H wherein M is hydrogen or a cation wherein the resultant salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R is the same or different and selected from hydrogen, C1-4 alkyl or C1-4 substituted alkyl (preferably R is hydrogen).
• Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-tri ydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.
• Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids.
• polyacetic acid builder salts are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid and nitrilotriacetic acid.
• polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.
• Citric builders e.g., citric acid and soluble salts thereof, is a polycarboxylate builder of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions.
• Suitable salts include the metal salts such as sodium, lithium, and potassium salts, as well as ammonium and substituted ammonium salts.
• carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.
• Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference.
• Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof.
• a particularly preferred compound of this type is dodecenylsuccinic acid.
• Alkyl succinic acids typically are of the general formula R-CH(C00H)CH2(C00H) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxy! , sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
• R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxy! , sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents.
• the succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium, ammonium and alkanolammonium salts.
• succinate builders include: laurylsuccin- ate, yristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
• Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
• useful builders also include sodium and potassium carboxy ethyloxymalonate, carboxy ethyloxysuccinate, cis-cyclohex- anehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about 2,000 can also be effectively utilized as dispersants), and the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
• polyacetal carboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al . , issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together, under polymeriza ⁇ tion conditions, an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.
• Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of ho o- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citra- conic acid and methylenema!onic acid.
• Detersive enzymes can be included in the detergent formulations for a variety of reasons including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer.
• the enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
• proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name Esperase ® . The preparation of this enzyme and analogous enzymes is described in British patent specification No. 1,243,784 of Novo.
• protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands).
• Protease A and Protease B are enzymes referred to herein as Protease A and Protease B.
• Protease A and methods for its prepara- tion are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference.
• Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence.
• Protease B is described in European Patent Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference. Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985, incorporated herein by reference.
• Amylases include, for example, a-amylases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Novo), previously incorporated herein by reference.
• Amylolytic proteins include, for example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries.
• the cellulases usable in the present invention 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.
• cellulases examples include cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aero onas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).
• Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No.
• Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application No. 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
• Lipase P Lipase P
• Amano-P Lipase P
• Such lipases of the present invention should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunodiffusion procedure accord ⁇ ing to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
• These lipases, and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent 4,707,291, Thorn et al., issued November 17, 1987, incorporated herein by reference.
• Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), lipase ex Psuedomonas nitroreducens var. l ipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum e.g. Chromobacter viscosum var. l ipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli .
• Amano-P lipase the lipase ex Pseudomonas fragi FERM P 1339 (available under the trade
• Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. 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 haloperoxidase such as chloro- and bro o-peroxidase.
• Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by 0.
• the enzymes are preferably coated or prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplish ⁇ ing this are well known in the art.
• an enzyme stabilization system is preferably utilized. Enzyme stabili ⁇ zation techniques for aqueous detergent compositions are well known in the art.
• one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, perferably formates. See, for example, U.S.
• Patent 3,600,319 issued August 17, 1971 to Gedge, et al., both incorporated herein by reference, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas.
• Non-boric acid and borate stabilizers are preferred.
• Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
• the detergent compositions hereof may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators.
• bleaching compounds When present bleaching compounds will typically be present at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition.
• bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.
• the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become, known. These include oxygen bleaches as well as other bleaching agents.
• the compositions hereof not contain borate or material which can form borate in situ (i.e. borate-forming material) under detergent storage or wash conditions.
• borate-forming material i.e. borate-forming material
• detergents to be used at these temperatures are substant ally free of borate and borate-forming material.
• substantially free of borate and borate-forming material shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 0%.
• One category of bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hart an, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al., filed June 3, 1985, European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S.
• Highly preferred bleaching agents also include 6-nonylamino-6- oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns, et al., incorporated herein by reference.
• hypohalite bleach-ing agents include trichloro isocyanuric acid and the sodium and potassium diehloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.
• Peroxygen bleaching agents can also be used. Suitable peroxy- gen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
• Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e- > during the washing process) of the peroxy acid corresponding to the bleach activator.
• Preferred bleach activators incorporated into compositions of the present invention have the general formula:
• R is an alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms and L is a leaving group, the conjugate acid of which has a pK a in the range of from about 4 to about 13.
• bleach activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao, et al., incorporated herein by reference, and U.S. Patent 4,412,934, which was previously incorporated herein by reference.
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• Non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the sub ⁇ strate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
• photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These materials can be deposited upon the sub ⁇ strate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached.
• Preferred zinc phthalocya ⁇ nine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe
• Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
• polymeric soil release agents in any of the detergent compositions hereof, especially those compositions utilized for laundry or other applications wherein removal of grease and oil from hydrophobic surfaces is needed
• the presence of polyhydroxy fatty acid amide in detergent compositions also containing anionic surfactants can enhance performance of many of the more commonly utilized types of polymeric soil release agents.
• Anionic surfactants interfere with the ability of certain soil release agents to deposit upon and adhere to hydrophobic surfaces.
• These polymeric soil release agents have nonionic hydrophile segments or hydrophobe segments which are anionic surfactant-interactive.
• compositions hereof for which improved polymeric soil release agent performance can be obtained through the use of polyhydroxy fatty acid amide are those which contain an anionic surfactant system, an anionic surfactant-interactive soil release agent and a soil release agent-enhancing amount of the polyhydroxy fatty acid amide (PFA), wherein: (I) anionic surfactant- interaction between the soil release agent and the anionic surfactant system of the detergent composition can be shown by a comparison of the level of soil release agent (SRA) deposition on hydrophobic fibers (e.g., polyester) in aqueous solution between (A) a "Control" run wherein deposition of the SRA of the detergent composition in aqueous solution, in the absence of the other detergent ingredients, is measured, and (B) an "SRA/Anionic surfactant" test run wherein the same type and amount of the anionic surfactant system utilized in detergent composition is combined in aqueous solution with the SRA, at the same weight ratio of SRA to the anionic surfactant system of the detergent
• an "SRA/Anionic surfactarit/PFA test run" wherein the same type and level of polyhydroxy fatty acid amide of the detergent composition is combined with the soil release agent and anionic surfactant system corresponding to said SRA/Anionic surfactant test run, whereby improved deposition of the soil release agent in test run (C) relative to test run (B) indicates that a soil release agent-enhancing amount of polyhydroxy fatty acid amide is present.
• the tests hereof should be conducted at anionic surfactant concentrations in the aqueous solution that are above the critical micelle concentration (CMC) of the anionic surfactant and preferably above about 100 ppm.
• the polymeric soil release agent concentration should be at least 15 ppm.
• a swatch of polyester fabric should be used for the hydrophobic fiber source. Identical swatches are immersed and agitated in 35'C aqueous solu ⁇ tions for the respective test runs for a period of 12 minutes, then removed, and analyzed. Polymeric soil release agent deposition level can be determined by radiotagging the soil release agent prior to treatment and subsequently conducting radioche ical analysis, according to techniques known in the art.
• soil release agent deposition can alternately be determined in the above test runs (i.e., test runs A, B, and C) by determination of ultraviolet light (UV) absorbance of the test solutions, according to techniques well known in the art. Decreased UV absorbance in the test solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition.
• UV analysis should not be utilized for test solutions containing types and levels of materials which cause excessive UV absorbance interference, such as high levels of surfactants with aromatic groups (e.g., alkyl benzene sulfonates, etc.).
• soil release agent-enhancing amount of polyhydroxy fatty acid amide is meant an amount of such surfactant that will enhance deposition of the soil release agent upon hydrophobic fibers, as described above, or an amount for which enhanced grease/oil cleaning performance can be obtained for fabrics washed in the detergent composition hereof in the next subsequent cleaning operation.
• compositions will comprise from about 0.01% to about 10%, by weight, of the polymeric soil release agent, typically from about 0.1% to about 5%, and from about 4% to about 50%, more typically from about 5% to about 30% of anionic surfactant.
• Such compositions should generally contain at least about 1%, preferably at least about 3%, by weight, of the polyhydroxy fatty acid amide, though it is not intended to necessarily be limited thereto.
• the polymeric soil release agents for which performance is enhanced by polyhydroxy fatty acid amide in the presence of anionic surfactant include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydro ⁇ philicity great enough to increase the hydrophilicity of conven ⁇ tional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for
• the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
• Suitable oxy C4-C6 alkylene hydrophobe seg ⁇ ments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2)nOCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, incorporated herein by reference.
• Polymeric soil release agents useful in the present invention include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like.
• Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as MethocelR (Dow).
• Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
• C1-C4 alkyl and C4 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
• a variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al., incorporated herein by reference.
• Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
• poly(vinyl ester) e.g., Ci-C ⁇ vinyl esters
• poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
• Suitable commercially available soil release agents of this kind include the SokalanTM type of material, e.g., SokalanTM
• One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about
• Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and 6:1.
• this polymer include the commercially available material Zelcon R 5126 (from Dupont) and Milease R T (from ICI). These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, which is incorporated herein by reference.
• Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone, said soil release agent being derived from allyl alcohol ethoxy!ate, dimethyl terephthalate, and 1,2 propylene diol, wherein after sulfonation, the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups.
• These soil release agents are described fully in U.S. Patent 4,968,451 issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink, U.S. Serial No. 07/474,709, filed January 29, 1990, incorporated herein by reference.
• Suitable polymeric soil release agents include the ethyl- or methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al . , the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG), the block polyester oligomeric compounds of U.S.
• PEG polyethylene glycol
• Patent 4,702,857 issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(0CH2CH2)n- wherein n is from 12 to about 43 and X is a C1-C4 alkyl, or preferably methyl, all of these patents being incorporated herein by reference.
• Additional polymeric soil release agents include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters, said patent being incorporated herein by reference.
• the terephthalate esters contain unsym etrically substituted oxy-1,2-alkyleneoxy units.
• Included among the soil release polymers of U.S. Patent 4,877,896 are materials with polyoxyethylene hydrophile components or C3 oxyalkylene terephthalate (propylene terephthalate) repeat units within the scope of the hydrophobe components of (b)(i) above. It is the polymeric soil release agents characterized by either, or both, of these criteria that particularly benefit from the inclusion of the polyhydroxy fatty acid amides hereof, in the presence of anionic surfactants.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• the detergent compositions herein may also optionally contain one or more iron and manganese chelating agents as a builder adjunct material.
• chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in " part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two, units of the substructure
• M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1.
• these amino carboxylat e s do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethyl- ethylenediaminetriacetates, nitri1otriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetri- aminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.
• Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions.
• M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates), nitrilotris (methylenephosphonates) and diethylenetriaminepentakis ( ethylene- phosphonates).
• these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Alkylene groups can be shared by substructures.
• Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula OH
• R is -SO3H or -COOH or soluble salts thereof and mixtures thereof.
• Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono- or triethanol-amine) salts.
• these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
• compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
• Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions, typically about 0.01% to about 5% These compounds are selected preferably from the group consisting of:
• R is C2-C12 alkylene, hydroxyal kyl ene , alkenyl ene, arylene or alkarylene, or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed; each R 2 is C1-C4 or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r > -A 2 -(CH2)s-> wherein A 2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R 3 is a substituted C3-C12 alkyl, hydroxyalkyl, alkenyl, aryl , or alkaryl group having substitution sites; R 4 is C1-C12 alkylene, hydroxyal kyl ene, alkenyl ene
• the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene- penta ine.
• Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference.
• Another group of preferred clay soil removal/ anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference.
• clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985, all of which are incorporated herein by reference.
• CMC carboxy methyl cellulose
• Brightener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions hereof. The choice of brightener for use in detergent compositions will depend upon a number of factors, such as the type of detergent, the nature of other components present in the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.
• the brightener selection is also dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners which will be effective for a variety of fabrics. It is of course necessary that the individual components- of such a brightener mixture be compatible.
• optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, cou arin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference.
• Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.
• Certain derivatives of bis(triazinyl)aminostilbene which may be useful in the present invention may be prepared from 4,4'-diamine- stilbene-2,2'-disulfonic acid.
• Coumarin derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.
• Carboxylic acid derivatives which may be useful in the present invention include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.
• Cinnamic acid derivatives which may be useful in the present invention can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.
• the styrylazoles can be further subclassified into styrylbenz- oxazoles, styrylimidazoles and styrylthiazoles, as disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaus ⁇ tive list of subgroups into which styrylazoles may be subclassified.
• optical brighteners which may be useful in the present invention are the derivatives of dibenzothiophene-5,5- dioxide disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology, Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962), the disclosure of which is incorporated herein by reference, and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.
• Another class of brighteners which may be useful in the present invention are the derivatives of 6-membered-ring heterocycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.
• miscellaneous agents may also be useful as brighteners.
• miscel ⁇ laneous agents are disclosed at pages 93-95 of the Zahradnik refer ⁇ ence, and include l-hydroxy-3,6,8-pyrenetri- sulphonic acid; 2,4- dimethoxy-l,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolone- disulphonic acid; and derivatives of pyrazoline- quinoline.
• optical brighteners which may be useful in the present invention are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988, the disclosure of which is incorporated herein by reference. These brighteners include the PhorwhiteTM series of brighteners from Verona.
• Tinopal UNPA Tinopal CBS and Tinopal 5BM
• Ciba-Geigy available from Ciba-Geigy
• Arctic White CC available from Hilton-Davis, located in Italy
• 2-(4-styryl-phenyl)-2H- naphthol[l,2-d]triazoles 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes
• 4,4'-bis(styryl)bis- phenyls 4,4'-bis(styryl)bis- phenyls
• the y-aminocoumarins include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l,2-d]triazoles; 4,4'-bis- (l,
• these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis- (-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis- (benzoxazol-2-yl)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole.
• Suds suppressors can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositions include a relatively high sudsing surfactant in combination with the polyhy ⁇ droxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front loading auto ⁇ matic washing machines.
• These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consequently, in reduced cleaning performance.
• the use of suds suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.
• suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
• One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John, said patent being incorporated herein by reference.
• the monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
• Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. These materials are a preferred category of suds suppressor for detergent compositions.
• the detergent compositions may also contain non-surfactant suds suppressors.
• non-surfactant suds suppressors include, for example, list: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
• suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., sodium, potassium, lithium) phosphates and phosphate esters.
• the hydrocarbons, such as paraffin and haloparaffin can be utilized in liquid form.
• the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40'C and about 5'C, and a minimum boiling point not less than about 110'C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about lOO'C.
• the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al., incorporated herein by reference.
• the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
• the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
• Non-surfactant suds comprises silicone suds suppressors.
• This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
• Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al . and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S., both incorporated herein by reference.
• silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
• Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al . , issued March 24, 1987.
• An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
• polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25*C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 SiO ⁇ /2 units of
• Suds suppressors when utilized, are preferably present in a "suds suppressing amount.”
• Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds, controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
• the amount of suds control will vary with the detergent surfactants selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desired suds control than with lesser foaming surfactants.
• a sufficient amount of suds suppressor should be incorporated in low sudsing detergent compositions so that the suds that form during the wash cycle of the automatic washing machine (i.e., upon agitation of the detergent in aqueous solution under the intended wash temperature and concentration conditions) do not exceed about 75% of the void volume of washing machine's containment drum, preferably the suds do not exceed about 50% of said void volume, wherein the void volume is determined as the difference between total volume of the containment drum and the volume of the water plus the laundry.
• compositions hereof will generally comprise from 0% to about 5% of suds suppressor.
• monocarboxylic fatty acids, and salts thereof When utilized as suds suppressors, monocarboxylic fatty acids, and salts thereof, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
• from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
• Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
• from about .01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
• these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
• Monostearyl phosphates are typically used in amounts of from about 0.1% to about 2%, by weight, of the composition.
• Hydrocarbon suds suppressors are typically utilized in amounts ranging from about .01% to about 5.0%, although higher levels can be used.
• Other Ingredients are typically utilized in amounts ranging from about .01% to about 5.0%, although higher levels can be used.
• compositions hereof A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
• Liquid detergent compositions can contain water and other water-miscible solvents as carriers.
• Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol , and isopropanol are suitable.
• Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
• the detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and about 10.5.
• Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0.
• Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known in the art.
• This invention further provides a method for improving the performance of detergents containing polymeric dispersing agent and detersive surfactant by additionally incorporating into such composition at least about 1%, by weight, of the polyhydroxy fatty acid amide surfactant described above.
• This invention further provides a method for cleaning substrates, such as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate, with a detergent composition comprising one or more anionic, nonionic, or cationic surfactants, at least about 0.5%, by weight, polymeric dispersing agent, and at least 1% of the polyhydroxy fatty acid amide.
• a detergent composition comprising one or more anionic, nonionic, or cationic surfactants, at least about 0.5%, by weight, polymeric dispersing agent, and at least 1% of the polyhydroxy fatty acid amide.
• compositions hereof are also preferred in the above methods.
• EXPERIMENTAL This exemplifies a process for making a N-methyl, 1-deoxyglucityl lauramide surfactant for use herein.
• one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium.
• the other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution: a wide-bore side-arm is important in case of very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet.
• the latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap.
• a 500 watt heating mantle with a variable transformer temperature controller (“Variac”) used to heat the reaction is so placed on a lab-jack that it may be readily raised or lowered to further control temperature of the reaction.
• Variac variable transformer temperature controller
• N-methylglucamine (195 g., 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g., 1.0 mole) are placed in a flask.
• the solid/liquid mixture is heated with stirring under a nitrogen sweep to form a melt (approximately 25 minutes).
• catalyst anhydrous powdered sodium carbonate, 10.5 g., 0.1. mole, J. T. Baker
• the nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 5 inches (5/31 atm.) Hg. vacuum. From this point on, the reaction temperature is held at 150 * C by adjusting the Variac and/or by raising or lowering the mantle.
• Examples 1-4 are formulations for preferred use of about 1400 ppm, wash water weight basis, for temperatures below about 50'C.
• TMS/TDS tartrate monosuccinate/tartrate disuc Ingredients 9
• Examples 5-10 are preferably used at about 2000 ppm, wash water weight basis, for wash temperatures below about 50'C. These are prepared by combining non-aqueous solvents, aqueous surfactant pastes or solutions, melted fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylenpenta ine, buffering agents, caustic, and the remaining water. The pH is adjusted using either an aqueous citric acid solution or sodium hydroxide solution to about pH 8.5. After pH adjustment, the final ingredients, such as soil release agents, enzymes, colorants, and perfume, are added and the mixture stirred until a single phase is achieved. EXAMPLE 11
• An alternate method for preparing the polyhydroxy fatty acid amides used herein is as follows.
• a reaction mixture consisting of 84.87g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75g. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04g. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51g. methyl alcohol is used.
• the reaction vessel comprises a standard, reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux).
• the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point.
• the reaction mixture is maintained at reflux for 4 hours. After removal of the methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 106.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction makes an overall percentage yield value meaningless.
• the reaction can be carried out at 80% and 90% reactant concentrations for periods up to 6 hours to yield products with extremely small by-product formation.
• the polyhydroxy fatty acid amides are, by virtue of their amide bond, subject to some instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about 11, preferably 10, nor below about 3 for unduly extended periods. Final product pH (liquids) is typically 7.0-9.0. During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. While any acid can be used for this purpose, the detergent formulator will recognize that it is a simple and convenient matter to use an acid which provides an anion that is otherwise useful and desirable in the finished detergent composition.
• citric acid can be used for purposes of neutralization and the resulting citrate ion ⁇ ca. 1%) be allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process.
• the acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
• the polyhydroxy fatty acid amides derived from coconut alkyl fatty acids are more soluble than their tallow alkyl (predominantly C 16 -C 18 ) counterparts. Accordingly, the C 12 -C 1 materials are somewhat easier to formulate in liquid compositions, and are more soluble in cool-water laundering baths. However, the C 16 -C 18 materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C 16 -C 18 materials may be better detersive surfactants than their C i2 -Ci 4 counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.
• solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation and/or chain branching in the fatty acid moiety.
• materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.
• polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. will ordinarily be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions.
• polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as detergents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants.
• LAS alkylbenzene sulfonate
• the polyhydroxy fatty acid amides can be manufactured not only from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose” corn syrup, “high maltose” corn syrup, etc. can conveniently and economically be used. De-ligni- fied, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.
• the formu ⁇ lator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a modicum of maltose (e.g., 1% or more).
• the resulting mixture of polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a broader range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fatty acid amide.
• the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation. In some instances, however, some loss of grease removal performance (dishwashing) may be noted at fatty acid maltamide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of malta ide-derived polyhydroxy fatty acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture).
• the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., maltose) from about 4:1 to about 99:1.
• monosaccharides e.g., glucose
• di- and higher saccharides e.g., maltose
• the manufacture of polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30'C-90'C, preferably about 50'C-80'C. It has now been determined that it may be convenient for the formulator of, for example, liquid detergents to conduct such processes in 1,2- propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation.
• the formulator of, for example, solid, typically granular, detergent compositions may find it convenient to run the process at 30'C-90'C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8) C ⁇ 2 -C ⁇ 4 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
• ethoxylated alcohols such as the ethoxylated (EO 3-8) C ⁇ 2 -C ⁇ 4 alcohols, such as those available as NEODOL 23 E06.5 (Shell).
• ethoxylates it is preferred that they not contain substantial amounts of unethoxylated alcohol and, most preferably, not contain substantial amounts of mono-ethoxylated alcohol.
• T designation.
• the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty acid amides will comprise: Step 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the N-alkyl amine and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Step 2 - reacting the aforesaid polyhydroxy amine with, preferably, a fatty ester to form an amide bond. While a variety of N-alkyl polyhydroxy amines useful in Step 2 of the reaction sequence can be prepared by various art-disclosed processes, the following process is convenient and makes use of economical sugar syrup as the raw material.
• the Gardner Color for the adduct is much worse as the temperature is raised above about 30 ⁇ C and at about 50°C, the time that the adduct has a Gardner Color below 7 is only about 30 minutes. For longer reaction, and/or holding times, the temperature should be less than about 20'C.
• the Gardner Color should be less than about 7, and preferably less than about 4 for good color glucamine.
• the time to reach substantial equilibrium concentration of the adduct is shortened by the use of higher ratios of amine to sugar.
• equilibrium is reached in about two hours at a reaction temperature of about 30'C.
• the time is at least about three hours.
• the combination of amine:sugar ratio; reaction temperature; and reaction time is selected to achieve substantially equilibrium conversion, e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1, for the adduct.
• the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.
• the starting sugar material must be very near colorless in order to consistently have adduct that is acceptable.
• the sugar has a Gardner Color of about 1, the adduct is sometimes acceptable and sometimes not acceptable.
• the Gardner Color is above 1 the resulting adduct is unacceptable. The better the initial color of the sugar, the better is the color of the adduct.
• Hvdrooen Reaction - Adduct from the above having a Gardner Color of 1 or less is hydrogenated according to the following procedure.
• the resulting product in each case is greater than about 95% N-methyl glucamine; has less than about 10 ppm Ni based upon the glucamine; and has a solution color of less than about Gardner 2.
• the crude N-methyl glucamine is color stable to about 140'C for a short exposure time.
• adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1).
• adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N 2 at about 10-20'C. About 330 g of about 70% corn syrup (near water-white) is degassed with N 2 at about 50'C and is added slowly to the methylamine solution at a temperature of less than about 20'C. The solution is mixed for about 30 minutes to give about 95% adduct that is a very light yellow solution.
• About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H 2 at about 20'C.
• the H 2 pressure is raised to about 200 psi and the temperature is raised to about 50'C.
• the pressure is raised to 250 psi and the temperature is held at about 50-55 * C for about three hours.
• the product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85 * C for about 30 minutes and the product, after removal of water and evaporation, is about 95% N-methyl glucamine, a white powder.
• Ni content in the glucamine is about 100 ppm as compared to the less than 10 ppm in the previous reaction.
• a 200 ml autoclave reactor is used following typical procedures similar to those set forth above to make adduct and to run the hydrogen reaction at various temperatures.
• Adduct for use in making glucamine is prepared by combining about 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 moles) (the solution is made using 99DE corn syrup from CarGill, the solution having a color less than Gardner 1) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).
• the reaction procedure is as follows:
• the adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
• the glucamine adduct hydrogen reactions are as follows: 1. Add about 134 g adduct (color less than about Gardner 1) and about 5.8 g G49B Ni to a 200 ml autoclave. 2. Purge the reaction mix with about 200 psi H 2 twice at about 20-30'C.
• the preparation of the tallow (hardened) fatty acid amide of N-methyl maltamine for use in detergent compositions according to this invention is as follows.
• Step 1 - Reactants Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM); Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
• the reactants are added to glass liner (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry - 50 g Raney Ni) and placed in 3 L rocking autoclave, which is purged with nitrogen (3X500 psig) and hydrogen (2X500 psig) and rocked under H 2 at room temperature over a weekend at temperatures ranging from 28'C to 50'C.
• the crude reaction mixture is vacuum filtered 2X through a glass microfiber filter with a silica gel plug.
• the filtrate is concentrated to a viscous material.
• the final traces of water are azetroped off by dissolving the material in methanol and then removing the methanol/water on a rotary evaporator.
• Step 2 Reactants: N-methyl maltamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level 50% (wt.).
• 20.36 g of the tallow methyl ester is heated to its melting point (water bath) and loaded into a 250 ml 3-neck round-bottom flask with mechanical- stirring. The flask is heated to ca. 70'C to prevent the ester from solidifying.
• the product is allowed to remain in the reaction flask at 110'C (external temperature) for 60 minutes.
• the product is scraped from the flask and triturated in ethyl ether over a weekend.
• Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder.
• Any remaining N-methyl maltamine is removed from the product using silica gel.
• a silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol.
• a concentrated sample of the product (20 g in 100 ml of 100% methanol) is loaded onto the silica gel and eluted several times using vacuum and several methanol washes.
• the collected eluant is evaporated to dryness (rotary evaporator). Any remaining tallow ester is removed by trituration in ethyl acetate overnight, followed by filtration.
• the filter cake is dried overnight.
• the product is the tallowalkyl
• Step 1 of the foregoing reaction sequence can be conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose.
• the resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.
• Step 2 of the foregoing reaction sequence can be carried out in 1,2-propylene glycol or NEODOL.
• the propylene glycol or NEODOL need not be removed from the reaction product prior to its use to formulate detergent compositions.
• the methoxide catalyst can be neutralized by citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide.
• the compositions herein can contain more or less of various suds control agents.
• various suds control agents For dishwashing high sudsing is desirable so no suds control agent will be used.
• a wide variety of suds control agents are known in the art and can be routinely selected for use herein. Indeed, the selection of suds control agent, or mixtures of suds control agents, for any specific detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide used therein, but also on the other surfactants present in the formulation.
• silicone-based suds control agents of various types are more efficient (i.e., lower levels can be used) than various other types of suds control agents.
• the silicone suds control agents available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful.
• the formulator of fabric laundering compositions which can advantageously contain soil release agent has a wide variety of known materials to choose from (see, for example, U.S. Patents
• Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of C x -C 4 alkoxy-terminated polyethoxy units (e.g., CH 3 [0CH 2 CH 2 ]i 6 0H), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of pol (oxyethylene)oxy units (e.g., polyethylene glycol 1500); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) especially wherein the mole ratio of oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about 0.5:1.
• Such nonionic soil release agents are of the general formula
• alkyl especially methyl
• x and y are each integers from about 6 to about 100
• m is an integer of from about 0.75 to about 30
• n- is an integer from about 0.25 to about 20
• R 2 is a mixture of both H and CH 3 to provide a mole ratio of oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
• soil release agent useful herein is of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substantially free of monomers of the H0R0H type wherein R is propylene or higher alkyl.
• the soil release agents of U.S. Patent 4,877,896 can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid
• these additional soil release agents can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid.
• Such agents are preferred for use in granular laundry detergents.
• the formulator may also determine that it is advantageous to include a non-perborate bleach, especially in heavy-duty granular laundry detergents.
• a non-perborate bleach especially in heavy-duty granular laundry detergents.
• peroxygen bleaches are available, commercially, and can be used herein, but, of these, percarbonate is convenient and economical.
• the compositions herein can contain a solid percarbonate bleach, normally in the form of the sodium salt, incorporated at a level of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8% to 15% by weight of the composition.
• Sodium percarbonate is an addition compound having a formula corresponding to 2Na 2 C0 3 . 3H 2 0 2 , and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxy- ethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
• a heavy metal sequestrant such as EDTA, 1-hydroxy- ethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate
• the percarbonate can be incorporated into detergent co posi- tions without additional protection, but preferred embodiments of the invention utilize a stable form of the material (FMC).
• sodium silicate Si0 2 :Na 2 0 ratio from 1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution and dried to give a level of from 2% to 10% (normally from 3% to 5%), of silicate solids by weight of the percarbonate.
• Magnesium silicate can also be used and a chelant such as one of those mentioned above can also be included in the coating.
• the particle size range of the crystalline percarbonate is from 350 micrometers to 450 micrometers with a mean of approximately 400 micrometers. When coated, the crystals have a size in the range from 400 to 600 micrometers.
• the percarbonate While heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other ingredients of the product. It has been found that the total level of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.
• a modern, condensed laundry detergent granule is as follows.
• Layered silicate builders are known in the art. Preferred are the layered sodium silicates. See, for example, the layered sodium silicate builders of U.S. Patent 4,664,859, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.
• a suitable layered silicate builder is available as SKS-6 from Hoechst. 2 AvaiTable from Novo Nordisk A/S, Copenhagen.
• Highly preferred granules of the foregoing types are those which comprise from about 0.0001% to about 2% by weight of active enzyme and at least about 1% by weight of said polyhydroxy fatty acid amide, and, most preferably, wherein the anionic surfactant is not an alkylbenzene sulfonate surfactant.
• EXAMPLE 14 The following illustrates a perborate bleach-plus-bleach activator detergent composition of the present invention which is prepared by admixing the listed ingredients in a mixing drum.
• Zeolite A refers to hydrated crystalline Zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 3 to 5 microns;
• LAS refers to sodium c i 2 . 3 linear alkylbenzene sulfonate; AS refers to sodium C 14 -C 15 alkyl sulfate;
• nonionic refers to coconut alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol and stripped of unethoxylated and monoethoxylated alcohol, also abbreviated as CnAE6.5T.; and DTPA refers to sodium diethylenetriamine pentaacetate. Parts by Weight of
• NAPAA wet cake which typically consists of about 60% water, about 2% peroxyacid available oxygen (AvO) (corresponding to about 36% NAPAA), and the rest (about 4%) unreacted starting material, is obtained.
• This wet cake is the crude reaction product of NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide which is subsequently quenched by addition to water followed by filtration, washing with distilled water, phosphate buffer washing and final suction filtration to recover the wet cake.
• a portion of the wet cake is air-dried at room temperature to obtain a dry sample which typically consists of about 5% AvO (corresponding to about 90% NAPAA) and about 10% unreacted starting material. When dry, the sample pH is about 4.5.
• NAPAA granules are prepared by mixing about 51.7 parts of the dried NAPAA wet cake (containing about 10% unreacted), about 11.1 parts of sodium C 12 . 3 linear alkyl benzene sulfonate (LAS) paste (45% active), about 43.3 parts of sodium sulfate, and about 30 parts of water in a CUISINART mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 14 Tyler mesh sieve and retaining all par-ticles not passing through a No. 65 Tyler mesh. The average amide peroxyacid particle (agglomerate) size is about 5-40 microns and the median particle size is about 10-20 microns, as determined by Malvern particle size analysis.
• LAS linear alkyl benzene sulfonate
• NOBS nonanoyloxybenzene sulfonate
• Zeolite granules having the following composition are made by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich R08 energy intensive mixer.
• Zeolite A (includes bound water) 70.00 76.99
• the PEG 8000 is in an aqueous form containing 50% water and is at a temperature of approximately 55'F (12.8'C).
• the CnAE6.5T is in a liquid state and is held at approximately 90'F (32.2'C).
• the two liquids are combined by pumping through a 12 element static mixer.
• the resulting binder material has an outlet temperature of approximately 75'F (23.9'C) and a viscosity of approximately 5000 cps.
• the ratio of PEG 8000 and CnAE6.5T through the static mixer is 72:28 respectively.
• the Eirich R08 energy intensive mixer is operated in a batch type mode. First, 34.1 kg of powdered Zeolite A is weighed into the pan of the mixer.
• the mixer is started by first rotating the pan in a counterclockwise direction at approximately 75 rotations per minute (rpm), and then rotating the rotor blade in a clockwise direction at 1800 rpm.
• the binder material is then pumped from the static mixer directly into the Eirich R08 energy intensive mixer which contains Zeolite A.
• the feed rate of the binder material is about 2 minutes.
• the mixer continues to mix for an additional 1 minute for a total batch time of approximately 3 minutes.
• the batch is then discharged and collected in a fiber drum.
• the batch step is repeated until approximately 225 kg of wet product has been collected. This discharged product is then dried in a fluid bed at 240-270'F (116-132'C). The drying step removes most of the free water and changes the composition as described above.
• the total energy input by the mixer to the product in a batch mode is approximately 1.31X10 12 erg/kg. at a rate of approximately 2.18X10 9 erg/kg-s.
• the resulting free flowing agglomerates have a mean particle size of about 450-500 microns.
• a granular laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows. Ingredient Wt. %
• ⁇ OKALAN sodium poly-aerylate/maleate available from Hoechst.
• X2-3419 is a silicone suds suppressor available from Dow Corning.
• the procedure for preparing the granules comprises various tower-drying, agglomerating, dry-additions, etc., as follows. The percentages are based on the finished composition.
• a surfactant mixture of 20% DOBANOL C 12 . 15 E0(3) and 80% C 16 -C 18 N-methyl glucose amide is obtained and coagglomerated with 10% sodium carbonate.
• the above particle is then coagglomerated with a high active paste (70%) of a sodium salt of C 14 -C 15 alkyl sulfate and
• the silicone suds suppressor X2-3419 (95%-97% high molecular weight linear silicone; 3%-5% hydrophobic silica) ex Dow Corning is coagglomerated with Zeolite A (2-5 ⁇ size), starch and stearyl alcohol binder. This particle has the following formulation: Zeolite A 0.22%
• the detergent preparation exhibits excellent solubility, superior performance and excellent suds control when used in European washing machine, e.g., using 85 g detergent in a AEG-brand washing machine in 30'C, 40'C, 60'C and 90'C cycles.
• the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/maltamide surfactants derived from plant sugar sources.
• the use of ethanol- amides appears to help cold temperature stability of the finished formulations.
• the use of sulfobetaine (aka “sultaine”) surfactants provides superior sudsing.
• the formulator of high sudsing compositions will desirably avoid the introduction of suds- suppressing amounts of such fatty acids into high sudsing composi ⁇ tions with the polyhydroxy fatty acid amides, and/or avoid the formation of C 14 and higher fatty acids on storage of the finished compositions.
• One simple means is to use C 12 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative sudsing effects caused by the fatty acids.
• anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and greater) of anionic or polyanionic substituents such as the polycarboxylate builders may find it useful to pre-mix the bright- ener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition.
• Polyglutamic acid or polyaspartic acid dispersants can be usefully employed with zeolite-built detergents.
• AE fluid or flake and DC-544 are other examples of useful suds control agents herein.

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• 1991
  • 1991-09-25 AU AU88791/91A patent/AU8879191A/en not_active Abandoned
  • 1991-09-25 WO PCT/US1991/007022 patent/WO1992006153A1/en not_active Application Discontinuation
  • 1991-09-25 EP EP91919572A patent/EP0550692B1/de not_active Expired - Lifetime
  • 1991-09-25 SK SK258-93A patent/SK25893A3/sk unknown
  • 1991-09-25 DE DE69114859T patent/DE69114859T2/de not_active Expired - Fee Related
  • 1991-09-25 HU HU89193A patent/HUT64783A/hu unknown
  • 1991-09-25 JP JP3518262A patent/JP3007154B2/ja not_active Expired - Fee Related
  • 1991-09-25 CZ CS93425A patent/CZ42593A3/cs unknown
  • 1991-09-25 BR BR919106908A patent/BR9106908A/pt unknown
  • 1991-09-25 CA CA 2092187 patent/CA2092187C/en not_active Expired - Fee Related
  • 1991-09-27 MA MA22582A patent/MA22299A1/fr unknown
  • 1991-09-27 IE IE341391A patent/IE913413A1/en unknown
  • 1991-09-27 CN CN 91110489 patent/CN1029320C/zh not_active Expired - Fee Related
  • 1991-09-30 NZ NZ24003091A patent/NZ240030A/en unknown
  • 1991-09-30 MX MX9101365A patent/MX9101365A/es not_active IP Right Cessation
  • 1991-10-15 TW TW80108118A patent/TW227013B/zh active

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