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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0094—High foaming 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
  • C11D1/66—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
  • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
  • C11D1/88—Ampholytes; Electroneutral compounds
  • C11D1/94—Mixtures with anionic, cationic or non-ionic 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
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2003—Alcohols; Phenols
  • C11D3/2006—Monohydric alcohols
  • C11D3/201—Monohydric alcohols linear
• • 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
  • C11D1/29—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
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • 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
• • 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
  • C11D1/75—Amino oxides

Definitions

• the present invention relates to detergent compositions com ⁇ prising one or more anionic sulfate or sulfonate surfactants, one or more polyhydroxy fatty acid amides and a critically selected suds enhancing agent.
• it relates to detergent composi- tions which possess enhanced cleaning and sudsing properties, are mild to the hand, and are especially suitable for use in dishwashing applications.
• compositions when compared to anionic sulfated or sulfonated surfactants, milder to the hand, have improved rinsability, are not as slippery to the touch, and are easier to formulate due to a reduced need for process additives such as solvents and hydrotropes.
• compositions containing a sulfate or a sulfonate surfactant with a particular polyhydroxy fatty acid amide discloses detergent compositions containing a sulfate or a sulfonate surfactant with a particular polyhydroxy fatty acid amide.
• the polyhydroxy fatty acid amide component contained in the composition of the present invention is also known in the art, as are several of its uses.
• N-acyl, N-methyl glucamides for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Thermo- tropic Liquid-Crystalline Properties of Some Straight Chain Carbohy ⁇ drate 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 Deter ⁇ gent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574.
• 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 Com ⁇ pounds, a New Class of Non-Ionic Detergents For Membrane Bio- chemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K.
• U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz relates to aqueous detergent compositions containing the condensa ⁇ tion 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.
• the thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl 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 alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates
• nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether,
• 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 4,021,539 issued May 3, 1977, to H. M ⁇ ller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxyalkyl-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.
• 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.
• R is a sugar residue of glucamine
• Rl is a C10-C20 alkyl radical
• R2 is a C1-C5 acyl radical.
• 5 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.
• RC(0)NRl(R 2 ) wherein RC(0) contains from about 10 to about 14 carbon atoms, and R 1 and R 2 each are H or Ci-C ⁇ alkyl groups, said alkyl groups containing a total number of carbon atoms of from 2 to about
• compositions provide substantially uniform improved sudsing performance across 10 varying temperature and humidity conditions.
• R2 - C - N - Z wherein R* is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R 2 is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
• the present invention is also directed toward a method for cleaning soiled dishes, said method comprising treating said dishes with the detergent compositions claimed herein.
• the detergent compositions of the present invention comprise from about 5% to about 65%, preferably from about 10% to about 50%, most preferably from about 15% to about 40% by weight of a surfactant mixture comprising one or more anionic sulfated or sulfonated surfactants, one or more polyhydroxy fatty acid amides, and a critically selected suds enhancing agent. These and other ingredients typically found in liquid detergent compositions are set forth below.
• the detergent compositions of the present invention are preferably in the form of a liquid or a gel, more preferably light-duty liquid detergent compositions, most preferably light-duty liquid dishwashing detergent compositions.
• the surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more anionic sulfate or sulfonate surfactants.
• the anionic sulfate or sulfonate surfactant may be any organic sulfate or sulfonate surfactant, but is preferably selected from C 1X -C 15 alkyl benzene sulfonates, C 10 -C l6 alkyl sulfates and their ethoxy analogues containing up to twelve moles of ethylene oxide per mole of alkyl ethoxy sulfates, C 13 -C 18 paraffin sulfonates, C 10 -C 16 olefin sulfonates, C 10 -C 20 alkyl glyceryl ether sulfonates, C9-C17 acyl-N-(C ⁇ -
• the anionic surfactant is selected from linear alkyl benzene sulfonates, alkyl ethoxy sulfates, alkyl glyceryl ether sulfonates and paraffin sulfonates.
• Alkyl benzene sulfonates useful in compositions of the present invention are those in which the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 10-13 carbon atoms, a material with an average carbon chain length of 11.2 being most
• the phenyl isomer distribution i.e., the point of attachment of the alkyl chain to the benzene nucleus, is not critical, but alkyl benzenes having a high 2-phenyl isomer content are preferred.
• Suitable alkyl sulfates are primary alkyl sulfates in which the
• 10 alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms preferably in a linear chain.
• C 10 -C 16 alcohols derived from natural fats, or Ziegler olefin build-up, or 0X0 synthesis, form suitable sources for the alkyl group.
• Examples of synthetically derived materials include Dobanol 23 (RTM) sold by
• -•- are coconut oil and palm kernel oil and the corresponding fatty acids.
• Alkyl ethoxy sulfate surfactants comprise a primary alkyl ethoxy sulfate derived from the condensation product of a C 10 -C 16 alcohol with an average of up to 6 ethylene oxide groups.
• C 10 -C 16 alcohol itself can be obtained from any of the sources previously described for the alkyl sulfate component.
• C 12 -C 14 alkyl ethoxy sulfates are preferred.
• Blends can be made of material having different degrees of ethoxylation and/or different ethoxylate distributions arising from the specific ethoxylation techniques employed and subsequent
• Paraffin sulfonates useful in the present invention have from 13 to 18 carbon atoms per molecule, more desirably 13 to 16 carbon atoms per molecule. These sulfonates are preferably prepared by subjecting a cut of paraffin, corresponding to the chain lengths specified above, to the action of sulfur dioxide and oxygen in accordance with the well-known sulfoxidation process. The product of this reaction is a secondary sulfonic acid which is then neutralized with a suitable base to provide a water-soluble secondary alkyl sulfonate.
• Similar secondary alkyl sulfonates may be obtained by other methods, e.g., by the sulfochlorination method in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates.
• the proportions of disulfonate or higher sulfonated material will be minimized, although some may be present.
• the monosulfonate may be terminally sulfonated or the sulfonate group may be joined on the 2-carbon or other carbon of the linear chain.
• any accompanying disulfonate usually produced when an excess of sulfonating agent is present, may have the sulfonate groups distributed over different carbon atoms of the paraffin base, and mixtures of the onosulfonates and disulfonates may be present.
• Mixtures of monoalkane sulfonates wherein the alkanes are of 14 and 15 carbon atoms are particularly preferred wherein the sulfonates are present in the weight ratio of C 14 -C 15 paraffins in the range from 1:3 to 3:1.
• Olefin sulfonates useful in the present invention are mixtures of alkene-1-sulfonates, alkene hydroxysulfonates, alkene disulfon ⁇ ates and hydroxydisulfonates, and are described in the commonly assigned U.S. Patent 3,332,880, issued to P. F. Pflauner and A. Kessler on July 25, 1967.
• Suitable alkyl glyceryl ether sulfonates are those derived from ethers of coconut oil and tallow.
• Other sulfate surfactants include the C9-C17 acyl-N-(C ⁇ -C4 alkyl) or -N-(C ⁇ -C2 hydroxyalkyl) glucamine sulfates, preferably those in which the C9-C17 acyl group is derived from coconut or palm kernel oil. These materials can be prepared by the method disclosed in U.S. Patent 2,717,894, issued September 13, 1955 to Schwartz.
• the counterion for the anionic surfactant component is preferably selected from sodium, potassium, magnesium, ammonium or alkanol-ammonium, and mixtures thereof, with magnesium being most preferred.
• the molar amount of magnesium ion in the compositions is controlled to correspond to 0.35-0.65X where X is the number of moles of C 10 -C 16 alkyl sulfate present.
• the magnesium ion content is adjusted to provide the stoichiometric equivalent, i.e., half the molar amount of the alkyl sulfate present. In such positions the magnesium ion will be present at a level of from about 0.15% to about 3.0% by weight, preferably from 0.25% to 1.5% by weight of the composition.
• the surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% to about 60% by weight of one or more polyhydroxy fatty acid amides having the structural formula: 0 Rl (I) R2 - C - N - Z wherein: R 1 is H, C1-C4 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 C ⁇ -C ⁇ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least
• 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.
• Z preferably will be selected from the group consisting of -CH 2 -(CH0H) n -CH 2 0H, -CHtCHzOHMCHOHJn-x-
• R 1 can be, for example, N-methyl, N-ethyl,
• R 2 -C0-N ⁇ can be, for example, coca ide, stearamide, oleamide, lauramide, myristamide, caprica ide, palmitamide, tallowamide, etc.
• Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto- triotityl, etc.
• the most preferred polyhydroxy fatty acid amide has the general formula 0 CH3
• polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglyceride in a condensation/a idation step to form the N-alkyl, N-polyhydroxy fatty acid amide product.
• Processes for making 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.
• N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl , or N-hydroxypropyl
• the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodiu pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium
• 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 polyethoxyl- ates, alkylpolyglucosides, linear glucamide surfactant, and mixtures thereof.
• a phase transfer agent calculated on a weight percent basis of total reaction mixture, selected from saturated fatty alcohol polyethoxyl- ates, alkylpolyglucosides, linear glucamide 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 for ulator that they can be prepared wholly or primarily from natural, renewable, non- petrochemical 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. Suds Enhancing Agent
• the surfactant mixture of the present invention further comprises from about 1% to about 20%, preferably from about 2% (more preferably 5%) to about 20% by weight of a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, and certain nonionics.
• a suds enhancing agent selected from the group consisting of amine oxides, betaines, sultaines, and certain nonionics.
• Amine oxides useful in the present invention include those compounds having the formula
• R 3 is selected from an alkyl, hydroxyalkyl , acylamidopropyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8 to 16 carbon atoms;
• R 4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, prefer ⁇ ably 2 carbon atoms, or mixtures thereof;
• x is from 0 to 3, prefer ⁇ ably 0; and each R 5 is an alkyl or hydroxyalkyl group containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferably 1, ethylene oxide groups.
• the R 5 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 C 10 -C 18 alkyl dimethyl amine oxides and C 8 -C 12 alkoxy ethyl dihydroxyethyl amine oxides.
• examples of such materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl di ethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide.
• Preferred are C ⁇ o-18 alkyl dimethylamine oxide, and C ⁇ o-18 acylamido alkyl dimethylamine oxide.
• the betaines useful in the present invention are those com ⁇ pounds having the formula wherein R is a C ⁇ -Ci8 hydrocarbyl group, preferably a C10-C16 alkyl group, each R 1 is typically Ci-C 3 alkyl, preferably methyl, and R 2 is a C1-C5 hydrocarbyl group, preferably a C1-C3 alkylene group, more preferably a C1-C2 alkylene group.
• betaines examples include coconut acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C12-14 acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4[Ci4-i6 acyl ethylamidodiethylammonio]-l-carboxybutane; c 16-18 acylamidodi ethylbetaine; C12-I6 acylamidopentanediethyl- betaine; [C1 -I6 acylmethylamidodimethylbetaine.
• Preferred betaines are C1 -I8 dimethyl-am onio hexanoate and the C ⁇ o-18 acylamidopro- pane (or ethane) dimethyl (or diethyl) betaines.
• the sultaines useful in the present invention are those com ⁇ pounds having the formula R(R 1 ) 2 N+R 2 S0 3 - wherein R is a C ⁇ -Cis hydrocarbyl group, preferably a C10-C16 alkyl group, more preferably a 12-C13 alkyl group, each R 1 is typically Ci-C 3 alkyl, preferably methyl, and R 2 is a C1-C6 hydrocarbyl group, preferably a C1-C3 alkylene or, preferably, hydroxyalkylene group.
• Suitable sultaines include Cj2-14 dimethylammonio-2-hydroxypropyl sulfonate, C1 -14 amido propyl ammonio-2-hydroxypropyl sultaine, c 12-14 dihydroxyethylammonio propane sulfonate, and Ci6-i8 dimethylammonio hexane sulfonate, with C12-14 a ido propyl ammonio- 2-hydroxypropyl sultaine being preferred.
• Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laugh!in 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. In a pre ⁇ ferred embodiment, 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, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. 2.
• the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms.
• Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of alcohol.
• condensation products of alcohols having an alkyl group containing from 10 to 14 carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of alcohol examples include TergitolTM 15-S-9 (the condensation product of Cn-Cj5 linear alcohol with 9 moles ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of C12-C1 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), Neodol ⁇ M 23-6.5 (the condensation product of c l2 _ Cl3 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 5 C14-C15 linear alcohol with 4 moles of ethylene
• the condensation products of ethylene oxide with a hydro- 10 phobic base formed by the condensation of propylene oxide with propylene glycol.
• 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
• reaction product of ethylenediamine and excess propylene oxide 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
• nonionic surfactant examples include certain of the commercially available TetronicTM compounds, marketed by BASF.
• Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galac- tosyl moieties can be substituted for the glucosyl moieties.
• the hydrophobic group is attached at the 2-, 3-, 4-, etc.
• 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.
• the preferred alkyleneoxide is ethylene oxide.
• Typical hydrophobic groups include alkyl groups, either saturated or unsatu- rated, branched or unbranched containing from 8 to 18, preferably from 10 to 16, carbon atoms.
• the alkyl group is a straight-chain saturated alkyl group.
• the alkyl group can contain up to about 3 hydroxyl 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 hexaglu- cosides, 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 H 2 nO)t(glycosyl) x
• R 2 is selected from the group consisting of alkyl, alkyl- phenyl, hydroxyalkyl , hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 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 ⁇ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl , and -(C2H4 ⁇ ) x H, where x is in the range of from 1 to 3.
• Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.
• Preferred suds enhancing agents are C ⁇ o-18 alkyl dimethyl amine oxides, C ⁇ o-18 acyl amide alkyl dimethyl amine oxides, betaines, sultaines, condensation products of aliphatic alcohols with ethylene
• Liquid Carrier 15 oxides, and alkylpolysaccharides, and mixtures thereof.
• the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions comprise from about 95% to
• a liquid carrier e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g, ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred
• a liquid carrier e.g., water, preferably a mixture of water and a C1-C4 monohydric alcohol (e.g, ethanol, propanol, isopropanol, butanol, and mixtures thereof), with ethanol being the preferred
• liquid 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 and about 9, more
• Liquid product formulations preferably have a pH in the range of from about 5.0 to about 10.5, more preferably from about 6.0 to about 9.0, most preferably from about 6.5 to about 7.5.
• Techniques for controlling pH at recom ⁇ mended usage levels include the use of buffers, alkali, acids, etc.,
• the detergent compositions of the present invention may also be in the form of a gel.
• Such compositions are typically formulated in the same manner as liquid detergent compositions, except they contain an additional thickening agent.
• any material or materials which can be admixed with the aqueous liquid to provide shear-thinning compositions having sufficient yield values can be used in the compositions of this invention.
• Materials such as colloidal silica, particulate polymers, such as polystyrene and oxidized polystyrene, combinations of certain surfactants, and water-soluble polymers such as polyacrylate are known to provide yield values.
• a preferred thickening agent useful in the compositions of the present invention is a high molecular weight polycarboxylate polymer thickener. By "high molecular weight” it is meant from about 500,000 to about 5,000,000, preferably from about 750,000 to about 4,000,000.
• the polycarboxylate polymer may be a carboxyvinyl polymer.
• a carboxyvinyl polymer is an interpoly er of a monomeric mixture comprising a monomeric olefinically unsaturated carboxylic acid, and from about 0.1% to about 10% by weight of the total monomers of a polyether of a polyhydric alcohol, which polyhydric alcohol contains at least four carbon atoms to which are attached at least three hydroxyl groups, the polyether containing more than one alkenyl group per molecule.
• Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable on exposure to air.
• Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol ; more preferred are oligosaccharides, most preferred is sucrose. It is preferred that the hydroxyl groups of the polyol which are modified be etherified with allyl groups, the polyol having at least two ally! ether groups per polyol molecule. When the polyol is sucrose, it is preferred that the sucrose have at least about five allyl ether groups per sucrose molecule.
• the polyether of the polyol comprise from about 0.1% to about 4% of the total monomers, more preferably from about 0.2% to about 2.5%.
• Preferred monomeric olefinically unsaturated carboxylic acids for use in producing carboxyvinyl polymers used herein include monomeric, poly erizable, alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids; more preferred are monomeric monoolefinic acrylic acids of the structure R
• CH2 C - COOH
• R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.
• Carboxyvinyl polymers useful in formulations of the present invention have a molecular weight of at least about 750,000. Pre ⁇ ferred are highly cross-linked carboxyvinyl polymers having a molecular weight of at least about 1,250,000. Also preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000, which may be less highly cross-linked.
• Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910 having a molecular weight of about 750,000; preferred is Carbopol 941 having a molecular weight of about 1,250,000, and more preferred are Carbopols 934 and 940 having molecular weights of about 3,000,000 and 4,000,000, respec ⁇ tively.
• Carbopol 934 is a very slightly cross-linked carboxyvinyl polymer having a molecular weight of about 3,000,000. It has been described as a high molecular weight polyacrylic acid cross-linked with about 1% of polyallyl sucrose having an average of about 5.8 allyl groups for each molecule of sucrose.
• polycarboxylate polymers useful in the present invention are Sokolan PHC-25R, a polyacrylic acid available from BASF Corp., and Gantrez R a poly(methyl vinyl ether/maleic acid) interpoly er available from GAF Corp.
• Preferred polycarboxylate polymers of the present invention are non-linear, water-dispersible, polyacrylic acid cross-linked with a polyalkenyl polyether and having a molecular weight of from about 750,000 to about 4,000,000.
• Highly preferred examples of these polycarboxylate polymer thickeners are the Carbopol 600 series resins available from B. F. Goodrich. Especially preferred are Carbopol 616 and 617.
• these resins are more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000.
• Mixtures of polycarboxylate polymers as herein described may also be used in the present invention. Particularly preferred is a mixture of Carbopol 616 and 617 series resins.
• the polycarboxylate polymer thickener is utilized preferably with essentially no clay thickening agents. In fact, it has been found that if the polycarboxylate polymers of the present invention are utilized with clay in the composition of the present invention, a less desirable product, in terms of phase instability, results. In other words, the polycarboxylate polymer is preferably used instead of clay as a thickening/stabilizing agent in the present compositions.
• the polycarboxylate polymer also provides a reduction in what is commonly called “bottle hang-up". This term refers to the inability to dispense all of the dishwashing detergent product from its container. Without intending to be bound by theory, it is believed that the thickened compositions of the present invention provide this benefit because the force of cohesion of the composi ⁇ tion is greater than the force of adhesion to the container wall. With clay thickener systems, which most commercially available products contain, bottle hang-up can be a significant problem under certain conditions.
• the long chain molecules of the polycarboxylate polymer thick ⁇ ener help suspend solids in the thickened detergent compositions of the present invention and help keep the matrix expanded.
• the polymeric material is also less sensitive than clay thickeners to destruction due to repeated shearing, such as occurs when the composition is vigorously mixed. If the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of from about 0.1% to about 10%, preferably from about 0.2% to about 2% by weight.
• the thickening agents are used to provide a yield value of from about 50 to about 350 and most preferably from about 75 to about 250. Yield Value Analysis
• a liquid detergent composition in a typical European market application, from about 3 ml . to about 15 ml., preferably from about 3 ml. to about 10 ml. of a liquid detergent composition is combined with from about 1,000 ml. to about 10,000 ml., more typically from about 3,000 ml. to about 5,000 ml., of water in a sink having a volumetric capacity in the range of from about 5,000 ml. to about 20,000 ml., more typically from about 10,000 ml. to about 15,000 ml.
• the detergent composition has a surfactant mixture concentration from about 21% to about 44% by weight, preferably from about 25% to about 35% by weight.
• a detergent composition in a typical Latin American and Japanese market application, from about 1 ml . to about 50 ml., preferably from about 2 ml . to about 10 ml. of a detergent composition is combined with from about 50 ml. to about 2,000 ml., more typically from about 100 ml. to about 1,000 ml. of water in a bowl having a volumetric capacity in the range of from about 500 ml. to about 5,000 ml., more typically from about 500 ml. to about 1,000 ml.
• the detergent composition has a surfactant mixture concentration of from about 5% to about 40% by weight, preferably from about 10% to about 30% by weight.
• a device for absorbing liquid dishwashing detergent such as a sponge, is placed directly into a separate quantity of undiluted liquid dishwashing composition for a period of time typically ranging from about 1 to about 5 seconds.
• the absorbing device, and consequently the undiluted liquid dishwashing composition is then contacted individually to the surface of each of the soiled dishes to remove said soiling.
• the absorbing device is typically contacted with each dish surface for a period of time range from about 1 to about 10 seconds, although the actual time of application will be dependent upon factors such as the degree of soiling of the dish.
• the contacting of the absorbing device to the dish surface is preferably accompanied by a concurrent scrubbing.
• the mixture is mixed until a homogenous, clear solution product is obtained. Additional water, alcohol, and any desired additional hydrotropes (added as a solution) may then be added to trim the solution product viscosity to the desired level, ideally between 50 and 1000 cps, as measured by a Brookfield viscometer at 70°F.
• the pH of the solution product is then adjusted with either HCl or NaOH to a level of 7.0 + 0.7 for formulas containing ammonium ions, and 8.5 + 1.5 for formulas which do not contain ammonium ions.
• Perfume, dye and other ingredients are added as the last step.
• Lytron can be added directly as a dispersion with mixing.
• Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals.
• N-methyl glucamide 5.0 5.0 10.0 10.0 15.0
• Sodium C ⁇ .2 linear alkyl benzene sulfonate 10.0
• EXAMPLE VI The following detergent compositions are formulated on a weight percent basis. These compositions are prepared in the same manner as the compositions of Example I.
• Carbopol ® 617 2.0 Water & misc. (perfume, dye, etc.) --- balance to 100% —-
• EXAMPLE VIII 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% reaction concentrations for periods up to 6 months to yield products with extremely small by-product formation.
• 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.
• 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
• the acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly.
• 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 12 -C 14 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.
• 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-lignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.
• 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 Ste p 2 - reacting the aforesaid polyhydroxy amine with, preferably, a fatty ester to form an amide bond.
• the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.
• the above procedure is repeated with about 23.1 g of Raney Ni catalyst with the following changes.
• the catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 200 psig H 2 and the reactor is pressurized with H 2 at 1600 psig for two hours, the pressure is released at one hour and the reactor is repressurized to 1600 psig.
• the adduct is then pumped into the reactor which is at 200 psig and 20 * C, and the reactor is purged with 200 psig H 2 , etc., as above.
• 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).
• the reaction procedure is as follows: 1. Add about 119 g of the 50% methylamine solution to a N 2 purged reactor, shield with N 2 and cool down to less than about lO'C. 2. Degas and/or purge the 55% corn syrup solution at 10-20'C with
• the adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.
• 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
• 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 vacuum dried overnight.
• the product is the tallowalkyl N-methyl maltamide.
• 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.
• Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of Ci-C alkoxy-terminated polyethoxy units (e.g., CH 3 [0CH 2 CH 2 ] 16 0H), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(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 ormula
• 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 HOROH 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, ethyl ⁇ ene 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 a ino-phosphonate, that is incorporated during the manufacturing process.
• EDTA 1-hydroxy- ethylidene 1,1-diphosphonic acid
• HEDP 1-hydroxy- ethylidene 1,1-diphosphonic acid
• the percarbonate can be incorporated into detergent composi- tions without additional protection, but preferred embodiments of the invention utilize a stable form of the material (FMC).
• 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.
• Brightener 0.10 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
• a suitable layered silicate builder is available as SKS-6 from Hoechst.
• 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.
• compositions provided by the present invention can function in a variety of cleaning modes, they are most preferred for use in dishwashing operations, and the like.
• the following illustrates some preferred dishwashing liquids according to the invention.
• the surfact ⁇ ants comprise various alkyl ethoxy sulfate surfactants which, using standard terminology, are abbreviated to indicate their average degree of ethoxylation; thus C 12 . 13 E0(0.8) sulfate indicates a sulfated mixed C 12 -C 13 alcohol fraction having an average degree of ethoxylation of 0.8.
• These anionic ethoxy sulfates are preferably used in their Na+ or NH 4 + salt form.
• the C 12 . 13 amine oxide is a mixed C 12 _ 13 (average) dimethyl amine oxide.
• the C 1Z . 1 AP betaine is C 12 / 14 H 25 / 29 C0 H(CH 2 ) 3 N + (CH 3 ) 2 CH 2 C0 2 H.
• the C 12 - 14 AP sultaine is C 12 / 14 H 25 / 29 C0NH(CH 2 ) 3 N+(CH 3 ) 2 CH 2 CH(0H)CH 2 S0 3 H.
• the C 12 . 14 DM betaine is C 12 / 14 H 25 / 29 N + (CH 3 ) 2 CH 2 C0 2 H.
• the ethoxylated nonionic surfactant designated C 9 - ! E0(8) refers to C 9 -C alcohols ethoxyl ⁇ ated with an average of 8 moles of ethylene oxide.
• the Ca ++ and Mg ++ cations are conveniently introduced into the compositions as CaCl 2 and MgCl 2 .
• the balance of the compositions comprises water and citrate/propylene glycol present in the glucamide surfactant (1-5%) and 1-3% cumene sulfonate or xylene sulfonate hydrotrope.
• the pH is typically 6.8-7.4 (NH 4 + salts) or 7-8.2 (Na+ salts).
• 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 ethanola- mides appears to help cold temperature stability of the finished formulations.
• the use of sulfobetaine (aka “sultaine”) surfactants provides superior sudsing.
• compositions wherein especially high sudsing is desired e.g., dishwashing
• no suds suppressing agent be used.
• dishwashing composi ⁇ tions contain less than about 5%, preferably less than about 2%, most preferably substantially no C 14 or higher fatty acids.
• the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty acids into such compositions with the polyhydroxy fatty acid amide, and/or will avoid the formation of C 14 and higher fatty acids on storage of the finished compositions.
• 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.
• Polygluta ic acid or polyaspartic acid dispersants can be usefully employed with zeolite-built detergents. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.

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• 1991
  • 1991-09-25 ES ES91918348T patent/ES2059154T3/es not_active Expired - Lifetime
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  • 1991-09-25 DE DE69103759T patent/DE69103759T2/de not_active Expired - Fee Related
  • 1991-09-25 EP EP91918348A patent/EP0550653B1/en not_active Expired - Lifetime
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  • 1991-09-25 JP JP3517001A patent/JP3046070B2/ja not_active Expired - Lifetime
  • 1991-09-25 AU AU87396/91A patent/AU663854B2/en not_active Ceased
  • 1991-09-25 WO PCT/US1991/006981 patent/WO1992006161A1/en active IP Right Grant
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  • 1991-09-28 MY MYPI91001783A patent/MY110806A/en unknown
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• 1993
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  • 1993-03-26 FI FI931367A patent/FI931367A/fi unknown
• 1998
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